Copyrighted by John Wallace Pearce 1955 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. T H E P H Y S IC A L P R O P E R T IE S O F E L E C T R O L Y T IC D E P O S IT S F R O M S O L U T IO N S C O N T A IN IN G N IC K E L A D D IT IO N S O F V A R IO U S O R G A N IC S U B S T A N C E S By John W a lla c e P e a rc e A T H E S IS S u b m itte d to the School of G ra d u a te Studies of M ic h ig a n S ta te C o lle g e of A g r ic u lt u r e and A p p lie d S cience in p a r t ia l f u lf illm e n t of the re q u ire m e n ts fo r the d e g re e of D O C T O R O F P H IL O S O P H Y D e p a r tm e n t of C h e m is try 1953 Reproduced with permission o f the copyright owner. Further reproduction prohibited without permission. THE P H Y S I C A L P R O P E R T IE S O F E L E C T R O L Y T I C N IC K E L D E P O S I T E D F R O M S O L U T IO N S C O N T A IN IN G A D D IT IO N S O F V A R IO U S O R G A N IC S U B S T A N C E S By John W a lla c e AN P e a rc e ABSTRACT S u b m it t e d to t K e School of G ra d u a te S tu d ie s of M ic h ig a n S t a t e C o l l e g e of A g r ic u lt u r e and A p p lie d S c ie n c e i n p a r t i a l f u lf illm e n t of th e r e q u ir e m e n ts f o r the d e g re e of DOCTOR O F P H IL O S O P H Y D e p a r tm e n t of C h e m is t r y Y e a r 1953 Approved Reproduced with permission o f the copyright owner. Further reproduction prohibited without permission. 1 JO H N W A L L A C E P E A R C E ABSTRACT T h e p h y s ic a l p r o p e r t ie s , a p p e a ra n c e and s u rfa c e rou g h n ess of W a tts n ic k e l s o lu tio n d e p o s its have b ee n s tu d ie d and c o m p a re d w ith th e p r o p e r tie s o b ta in e d w hen s m a ll a d d itio n s of o rg a n ic sub­ stances w e r e p r e s e n t in the d e p o s itin g s o lu tio n . w e re o b ta in e d f r o m a H u ll- t y p e N ic k e l d ep o sits c e ll w h ic h y ie ld s a w id e c u r r e n t d e n ­ s ity ra n g e of m e t a l d e p o s itio n on a s in g le c a th o d e . o rg a n ic T h e group s of com pounds added to the W atts n ic k e l s o lu tio n in c lu d e d r e ­ ducing c a r b o h y d r a te s , p o ly m e r s , and un s a tu ra te d a lip h a tic c a rb o n y l com pounds, dyes and p h en o ls. com pounds, T h e e ffe c ts on a W a tts n ic k e l s o lu tio n d e p o s it of s in g le a d d itio n s of these com po unds, a d d itio n s in the p re s e n c e of 2 , 7 -n a p h th a le n e d is u lfo n ic a c id and, f o r the c a rb o n y ls com pounds, a d d itio n s in the p re s e n c e o f c o b a lt s u lfa te and a n ic k e l o rg a n ic a c id s a lt w e r e r e p o r te d . Som e e x p lo r a to r y d ata T o r p r e ­ dipping the cathode in a s o lu tio n of a p ro v e n b r ig h t e n e r o r c o v e rin g w ith f i l t e r p a p e r p re v io u s to d e p o s itio n in a W a tts n ic k e l s o lu tio n was als o r e p o r te d . A p p e a ra n c e ta b le s h a v e been c o n s tru c te d using the t e r m in o l­ ogy su g g ested by " M e t a lf in is h in g G uide B o o k - D ir e c to r y , 1950" fo r each g e n e r a l a d d itio n o u tlin e d and ph o to g rap h s o f the a p p e a ra n c e e f ­ fe c ts h av e b ee n in c lu d e d . S u rfa c e rou g h n ess e ffe c ts h av e been Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 2 JO HN W A L L A C E P E A R C E ABSTRACT e v a lu a te d a t 9 .0 a n d 6 .5 a m p ./s q . d m . R oughness data ta b le s h a v e been c o n s tru c te d to r e p o r t th e s u rfa c e data and c u rv e s h av e been in c lu d e d as p o s s ib le in te r p r e ta tio n s o f the tre n d s o b s e rv e d in th e rou g h n ess d ata. A ta b le o f d e c re a s in g b r ig h te n e r s tre n g th b a s e d on o p tim u m a p p e a ra n c e e ffe c ts h a s a ls o b een in c lu d e d . F u n c tio n a lity of the o rg a n ic m o le c u le has been su g gested as a v i t a l r e q u is ite f o r d e s ir a b le m o d ific a tio n of th e n ic k e l d e p o s it. S t r u c t u r a l is o m e r s of n itro p h e n o l v a r ie d in e ffe c t on the d e p o s it. T h is w a s o b s e rv e d le s s m a r k e d ly in the base o f the a m in o -p h e n o ls . D e g re e o f u n s a tu ra tio n ten d ed to be im p o r ta n t and d ir e c t ly r e la t e d to m o d ify in g of the d e p o s it. o rg a n ic T h e p o s s ib ility of a p i-c o m p le x m é t a ll o - com pound in the cathode l a y e r was sug gested. T re n d s to w a rd som e c o r r e la t io n b e tw e e n o x id a tio n p o te n tia l o f the c a rb o n y l c o m ­ pounds studied and th e ir b rig h te n in g p r o p e rtie s w e re d is c u s s e d and in te r p r e te d in v ie w of a p o s tu la te d m e t a l h e m i- a c e t a l in te r m e d ia t e s p e c ie s . T h e v ie w s of M a th e r s , who pro p o sed the th e o ry of the i m ­ p o rta n c e of c o m p le x com pounds in m e t a l d e p o s it m o d ific a tio n , w e r e c o n s id e re d q u a lita tiv e ly and extend ed to the u s e of o rg a n ic a d d itio n s fo r m o d ify in g a n ic k e l d e p o s it. B a s e d on the ite m s d is c u s s e d , som e fa v o r a b le a g r e e m e n t w as in d ic a te d . T h e r e s u lts w e re not d e fin ite ly Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 3 JO H N W A L L A C E P E A R C E ABSTRACT concluded to w a rd th e v ie w of M a th e r s , h o w e v e r, s in c e a d s o rp tio n ph en o m en a w e r e n o t e lim in a te d as a p o s s ib le e x p la n a tio n . T w o new b r ig h t e n e r s , M o n a s t r a l B lu e and P V M / M A , w e r e r e p o r te d . Reproduced with permission o f the copyright owner. Further reproduction prohibited without permission. ACKNOW LEDGM ENTS T h e w r i t e r w is h e s to e x p re s s h is s in c e r e a p p re c ia tio n to D r . D w ig h t T . E w in g w hose p r iv ile g e d a s s o c ia tio n , kin d in s p ir a tio n , and in te r e s t a r e h ig h ly v a lu e d . T h e w r i t e r is a ls o g r e a tly in d e b te d to D r . E . J. M i l l e r and M r . P . C o le m a n f o r t h e ir in d is p e n s a b le h elp in o b tain in g the in c lu d e d m e t a l s u rfa c e p h o to g ra p h s . The m any h e lp fu l sug gestio ns of the G u id a n ce C o m m itte e and fe llo w students a r e g r a t e f u lly a c k n o w le g e d . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. TABLE OF CONTENTS P ag e I N T R O D U C T I O N .................................................................................................... 1 C H E M IC A L S U S E D ............................................................................................. 8 E X P E R IM E N T A L ................................................................................................. 11 .................................................................................................... 11 The C e l l .............................................................................................................. 12 A p p e a ra n c e of the D e p o s i t ...................................................................... l8 Roughness of the D e p o s it 18 The S o lu tio n ...................................................................... D A T A A N D IN T E R P R E T A T IO N O u tlin e of D a ta A p p e a ra n c e ............................................................... 20 ............................................................................................. 21 .............................................. 26 ............................................................ 180 D IS C U S S IO N ............................................................................................................. 2 46 SUMMARY 253 Roughness T a b le s and Illu s t r a tio n s T a b le s and C u rv e s ■• • B I B L I O G R A P H Y ............................................................................. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 255 .IN T R O D U C T IO N I t is kno w n th a t the p re s e n c e of o rg a n ic su b stan ces p la tin g so lu tio n s m a r k e d ly a ffe c ts the p h y s ic a l p r o p e r t ie s ly tic n ic k e l. of v a rio u s of e le c tr o ­ N o g e n e r a l c o r r e la t io n w ith the type of such o rg a n ic compounds and the n a tu r e fo r m u la te d . in n ic k e l T h is of the e le c tr o d e p o s ite d n ic k e l has been in v e s tig a tio n is a study of the e ffe c t of the a d d itio n o rg a n ic com pounds to n ic k e l s u lfa te s o lu tio n s on a p p e a ra n c e and o th e r s u rfa c e p r o p e r t i e s . S c h lb tte r (1) has fo und th a t a r o m a tic p o ly s u lfo n a te s solutions of n ic k e l s u lfa te red u ce the c r y s ta l s iz e gloss c o m p a c t, a d h e re n t d e p o s it. added to and y ie ld a h ig h - H o w e v e r , the ran g e of c u r r e n t d e n s ity , t e m p e r a tu r e , and c o n c e n tra tio n of the s o lu tio n is n a r r o w . T his range f o r a c c e p ta b le o p tim u m c o n c e n tra tio n s dep osits is g r e a t ly im p ro v e d b y adding of a n o th e r o rg a n ic sub sta n ce. P in n e r , S o d e rb e rg , and B a k e r (2) have d iv id e d a d d itio n agents into two f a i r l y d is tin c t c la s s e s . c o b a lt s a lts , a r y l s u lfo n a m id e s , In the f i r s t c la s s , th e y have a s s ig n e d a r y l s u lfo n im id e s , a r y l s u lfo n ic a cid s as w e ll as a r y l p o ly s u lfo n ic a c id s . These substances a r e c h a ra c te r­ iz e d by not n e c e s s a r ily y ie ld in g b r ig h t d ep o sits b u t g iv in g g r a in r e ­ fin e m e n t to the d e p o s it. zin c The second c la s s in c lu d e d c a d m iu m and s a lts , s o d iu m f o r m a te , ald e h y d e s , k e to n e s , and a m in o p o ly a r y l Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. m eth an es . B y c o m b in in g su b stan ces of the two c la s s e s , m a x im u m b rig h tn e s s and s m o o th en in g a r e o b ta in e d . In a d d itio n to the org^.nic com pounds p o in te d out b y P in n e r et , gum tra g a c a n th (3 ), le a d c it r a t e n a tu r a l re s in s c e llu lo s e (8 ), s ta rc h a te s (5 ), s o d iu m fo r m a te s a fra n in e com pounds (1 1 ), th io u r e a (1 2 ), m e th y l c e llu lo s e (4 ), s u lfo n a te d o le o r e s in s and (6 ), azo com pounds (7 ), s u lfite (9 ), m e r c a p to p y r im id in e s (1 0 ), s u lf u r iz e d g e la tin (1 3 ), and c a r b o x y - (14) have b ee n c la im e d to g ive a c c e p ta b le d ep o sits of n ic k e l. H o w e v e r , alth o u g h m a n y o rg a n ic su b stan ces used as a d d itio n agents f a v o r a b ly m o d ify the d e p o s it, v e r y l i t t l e m a n n e r in w h ic h th ese a d d itio n agents a c t. A t le a s t f o u r th e o rie s have b een p ro p o s e d to e x p la in the m e c h a n is m s itio n . is know n about the of b r ig h t e le c tr o d e p o ­ We s h a ll b r i e f l y c o n s id e r th e m h e re in o r d e r of t h e ir a p ­ p e a ra n c e in the l it e r a t u r e . 1. A d s o rp tio n W. D . B a n c r o ft (1 5 , T h e o ry . In h is " A x io m s of E le c t r o p la t in g ," 16) o ffe r e d as h is fo u r th a x io m ; "The c r y s ta l size is d e c re a s e d w hen th e r e a r e p r e s e n t a t the cathode s u rfa c e , substances w h ic h a r e a d s o rb e d by the d e p o s ite d m e t a l . " and H . E . M e s s m o r e R . T a ft (17) e x p la in t h e ir d ata on the e le c tro d e p o s itio n of co p p er in the p re s e n c e o f g e la tin , m o s t d ir e c t ly , b y as s u m in g th at Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. the co p p er d e p o s ite d b y the c u r r e n t adsorbs g e la tin on its P . K . F r d l ic h (18) s u rfa c e . d e m o n s tra te d the c o n ta m in a tio n of d e p o s ite d n ic k e l w ith o rg a n ic m a t t e r w hen d e p o s ite d in the p re s e n c e o f g e la tin . found B a n c r o f t ’ s id e a o f an a d s o rb e d f il m the cathode h ig h ly h y p o th e tic a l. re s u lts w e r e u n a v a ila b le He o f the a d d itio n ag e n t a t F r o l ic h su g g ested th a t e x p e r im e n ta l to c o r r o b o r a te the th e o r y . p o in te d o u t th a t w o r k r e p o r te d b y H o lm e s F u r t h e r , he and C h ild (19) w ith g e la tin and an e m u ls ify in g agent, w h ic h r e p r e s e n te d o p tim u m c o n d itio n s fo r film f o r m a tio n , w as unable to e s ta b lis h any c o n c e n tra tio n of g e la tin a t so lu tio n in te r fa c e s . 2. R e d u cin g A g e n t T h e o r y . E . F . K e rn (20) o b s e rv e d th a t r e d u c ­ ing agents such as p o ly h y d ro x y p h e n o ls , ta n n in s , and a r o m a tic re fin e d the g r a in d ep o sits of c o p p e r, le a d , and s ilv e r . anions such as n it r a t e fa v o ra b le r e s u lt s . in an e le c t r o ly te is u n ten a b le . O x id a tiv e and p e r c h lo r a te did n o t, h o w e v e r, y ie ld such He suggested: ’ ’ The fu n c tio n o f an a d d itio n ag e n t is to m a in ta in a re d u c in g m e n s tru u m cathode w h ic h , in tu rn , cau ses the dep osit to f o r m H e n r ic k s a m in e s (21) has m a in ta in e d th a t th is a ro u n d the d e n s e r and s m o o th e r, re d u c in g ag e n t th e o ry H e b a s e d h is d e c is io n on the o b s e rv a tio n th a t f in e ­ g ra in e d m e ta l d ep o sits can be o b ta in e d f r o m tin p e r c h lo r a te so lu tio n s , a c id c o p p e r b ath s c o n ta in in g n it r a t e s , and c h ro m ic a c id b ath s. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 11 3. C o m p le x Io n T h e o r y . th a t e ffe c tiv e a d d itio n agents f o r m m e ta l. F . C . M a th e r s sug gested c o m p le x ions w ith the d e p o s itin g In v e s tig a tio n s b a s e d on r e fin in g s i lv e r d ep o s its to y ie ld sm ooth, h a r d , e n t ir e ly a d h e re n t cathodes f r o m n itr ic (22) has a c id b ath s c o n ta in in g t a r t a r i c Fuseya et s ilv e r n it r a t e , a c id le d to th is c o n cep t. G. (23) fo u n d th a t s ilv e r and c o p p e r f o r m e d c o m p le x ions w ith m e ta p h o s p h o ric a c id , t a r t a r i c p o s itiv e ly c h a rg e d . a c id , and g ly c o c o ll w h ic h w e re T h e s e w e r e the su b stances w h ic h e n te r e d into the cathode d e p o s its , in c r e a s e d t h e ir w e ig h t, and cau sed the c r y s ta l size to be s m a lle r . did not f o r m S u g ars and h ig h e r a lc o h o ls , on the o th e r hand, s ig n ific a n t c o m p le x e s w ith c o p p e r and s ilv e r and d id not in any w ay, o r o n ly v e r y s lig h tly , a ffe c t the cathode d e p o s it. F ro m the stu d ies of P a u li (24) and J. M a tu la and M . M a ts u - m u r a (2 5 ), i t w as in te r p r e te d th a t p r o te in has the p r o p e r t y of f o r m ­ ing c o m p le x c a tio n s w ith m e ta l io n s. N . Is g a r is chew ( 26) a s c e r ­ tain ed the e x is te n c e of c o m p le x c a tio n s , com po sed of g e la tin and zin c o r co p p er ions. He a ttr ib u te d the fa v o r a b le e ffe c t of g e la tin as an ad d itio n ag en t to th is c o m p le x -fo r m in g p r o p e r ty . v ie w , the g ro w th of c r y s ta ls is A c c o rd in g to h is r e ta r d e d upon adding g e la tin since the v e lo c ity of s e p a ra tio n of f r e e m e t a llic ions f r o m c o m p le x ions is not g r e a t. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. T h is v ie w is to be s h a r p ly d iff e r e n t ia te d f r o m F u s e y a e_t th a t of G. (23) in t h e i r e f f o r t to d ev elo p the c o m p le x io n th e o r y . H e re , w h ile the p r o p e r t y of f o r m in g c o m p le x ca tio n s is an e s s e n tia l to m a k e g e la tin a good a d d itio n agent, the c o d e p o s itio n of the c o m ­ p le x catio n s w ith m e t a llic ions w il l be the p r in c ip a l cause of h in d ra n c e to c r y s ta l g ro w th . 4. C atho de In te r f e r e n c e cluded th a t th e c r y s ta llin g s tr u c tu r e T h e o ry . L . B . H u n t (27) has co n ­ of an e le c tr o d e p o s ite d m e ta l w ill be g o v e rn e d b y the r e la t io n of the m e ta l io n c o n c e n tra tio n in the cathode f i l m that f i l m . to the c o n c e n tra tio n o f the o th e r c o n s titu e n ts of If the p r o p o r tio n of m e ta l ions to in e r t p a r t ic le s is p a r a t iv e ly h ig h , th e re w i l l be l i t t l e and c o a r s e ly c r y s ta llin e com ­ in te r f e r e n c e w ith c r y s ta l g ro w th d e p o s its w i l l r e s u lt . I f the p r o p o r tio n is low due to a lo w d e g re e of d is s o c ia tio n , c o m p le x ion fo r m a tio n , h ig h h y d ra tio n of the m e ta l io n s , o r p re s e n c e of c o llo id m a t t e r th a t has m ig r a te d c a ta p h o r e tic a lly in to the f i l m o r has b een jo in e d th e r e in , th e re w il l be c o n s id e ra b le in te r f e r e n c e w ith c r y s ta l g ro w th , w ith c o n ­ sequent fo r m a tio n of m a n y n u c le i. w e re la y e r , The con tents of the cathode la y e r c o n s id e re d as co m p o s e d of sp e cie s a p p ro a c h in g , le a v in g the and those ra n d o m ly fo u n d in the la y e r . S p ecies c o n s id e re d ap p ro ach in g the cathode l a y e r b e s id e s the m e ta l ions a re o th e r cations Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. such as h y d ro g e n , c o m p le x c a tio n s , w a te r d ip o le s , and c o llo id a l b o d ies w hich a re cathode m ig r a n t. anions, and w a te r d ip o le s . s o c iated m o le c u le s L e a v in g the l a y e r a r e a n io n s , c o m p le x R a n d o m ly fo u n d in the l a y e r a r e u n d is ­ and s o lv e n t m o le c u le s . The f i r s t e v e n t on the a p p ro a c h of a c a tio n to the cathode w ill be the lo s s of its a n io n ic a tm o s p h e re , w h ic h w i l l be fo llo w e d by the lo s s o f the s o lv e n t sh eath o r the c o m p le x p o r tio n of the ion. The l a t t e r m a y r e m a in a d s o rb e d to a s lig h t e x te n t and thus be i n ­ cluded in the d e p o s it. M o le c u le s r e tu r n in to s o lu tio n , w h e re a s a d s o rb e d f r o m the cathode w il l c o llo id a l m a t t e r w il l n o t, b u t m a y a c ­ cu m u late t e m p o r a r ily as a d ia p h ra g m , a s h o rt d is ta n c e f r o m cathode, p r i o r to its the r e d is t r ib u t io n b y d iffu s io n o r e le c tr o p h o r e s is .. F u r t h e r , c e r t a in c o llo id a l p a r t ic le s , m o re p a r t ic u la r l y those c o n s is tin g of b a s ic m a t t e r , w i l l be a d s o rb e d m o r e f i r m l y and in g r e a t e r am o u n t owing to t h e ir a tta c h m e n t to the m e ta l io n , and w i l l behave in a m a n n e r s i m il a r to c o m p le x io n s. H u n t's th e o r y of in te r f e r e n c e has b een g iv e n c o n s id e ra b le su p p o rt b y c o n s id e ra tio n s of the m e c h a n is m e le c tro n th e o r y of m e ta ls , m e t a llic of la tt ic e fo r m a tio n , the co h esio n , in t e r f a c ia l phen o m en a, in c lu s io n of b a s ic m a t t e r in the d e p o s it, and the d e p o s itio n of fo r e ig n c a tio n s . I t w as sug gested th a t changes in p o la r iz a tio n co u ld n o t be Reproduced with permission o f the copyright owner. Further reproduction prohibited without permission. exp ected to a c c o u n t f o r the v a r ia t io n s in s t r u c t u r e o f e le c tr o d e p o s ite d m e ta ls . R a th e r, e a c h s p e c ie s p r e s e n t in the e le c t r o ly te m u s t be c o n s id e re d on its ow n m e r it s w ith r e s p e c t to the fo r c e s a c tin g upon it and its b e h a v io r u n d e r th e s e fo r c e s . J. A . H e n d ric k s (21) has e x te n d e d the v ie w s of H u n t. H e has c o n s id e re d th a t a b r ig h te n in g p r o c e s s m a y be c o m p a re d w ith the L ie se gang p h e n o m e n a w h ic h is o fte n e x p la in e d as a p e r io d ic s a tu ra tio n and p r e c ip ita tio n . s u p e r­ F o r b r ig h t d e p o s itio n , a p u ls a tin g a d ­ s o rp tio n of a c o llo id and the d e p o s itio n c o u ld e x p la in the p ro d u c tio n of a s t r ia t e d d e p o s it. P e rh a p s m o r e le lis m s ig n ific a n tly , H e n d r ic k s p o in te d out the p a r a l ­ b e tw e e n b r ig h te n e r s o r in h ib ito r p r o p e r tie s and t h e i r p r o p e r t ie s as of t h e ir re d u c tio n p ro d u c ts . fo llo w in g steps in h is m e c h a n is m : (a) an a c tiv e a h ig h e r p o te n tia l th a n the s u rro u n d in g c r y s ta ls ; d uction of a d ja c e n t b r ig h te n e r s " in h ib i t o r s ' ' He a s s u m e d the c e n te r of m e ta l a t (b) e le c t r o ly t ic re ­ a t the h ig h e r p o te n tia l, (c) te m p o r a r y h a lt o f g ro w th of in h ib ite d p o in t, (d) u n in h ib ite d l a y e r co n tin u es to g ro w u n til e a c h in tu r n in c r e a s e s p o te n tia l and b ec o m es f ilm e d w ith in h ib ito r , (e) f ilm e d cathode s h ifts to cathode d e p o s itio n , and (f) r e p e titio n of the a d s o rp tio n c y c le . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. C H E M IC A L S U S E D F e rro u s s u lfa te , B a k e r and A d a m s o n . C o b a lt s u lfa te , M e r c k . N ic k e l s u lfa te , H a rs h a w , p la te r's g rade. N ic k e l carb o n ate. B a k e r s C . P. N ic k e l c h lo rid e . B a k e r s C. P. N ic k e l fo r m a te . B o r ic a c id , M e r c k A , C, S. S p e c ific a tio n . E le c t r o ly t ic N ic k e l anodes. S te e l cath o d es. A c tiv a te d carbon, N o r i t À. S o d iu m h yd ro xid e. B a k e r. S o d iu m m e t a - s ilic a t e , E im e r and. Am end C . P . T r is o d iu m phosphate. S o dium carbo nate. S o d iu m a c e ta te , M a llin c k r o d t, A . C . S. S p e c ific a tio n . C a rb o n t e tr a c h lo r id e . 2 ,7 -N a p h th a le n e di s u lfo n ic acid, G ly c e ra ld e h y d e , p r e p a r e d by D r . E a s tm a n W h ite L a b e l. Speck. D - X y lo s e , P h a n s tie h l C. P . D -G lu c o s e , P h a n s tie h l C. P . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. L a c to s e h y d ra te , P h a n s tie h l C , P . R a ffin o s e h y d r a te , E a s tm a n W h ite L a b e l. D e x tr in , P h a n s tie h l C . P . C a m p h o r, D u P o n t. p -B ro m o a c e to p h e n o n e , E a s tm a n W h ite L a b e l. C innam aldéhyde-, R e d is tille d , E a s tm a n W h ite L a b e l. A c e ta ld e h y d e , E a s tm a n W h ite L a b e l. C h lo r a l, E a s tm a n W h ite L a b e l. P y ru -vic a c id , E a s tm a n W h ite L a b e l. B u ty l c h lo r a l, p r e p a r e d by D r . G o e r n e r . b e ta -M e th y l u m b e llif e r o n e , K o p p e rs . M e th y l c e llu lo s e , D o w , v is c o s ity 400 c e n tip o is e s . P o ly m e th y l v in y l e t h e r - m a le ic a n h y d rid e , G en. A n ilin e also r e f e r r e d to as P V M / M A . & F i lm ; h e r e a f t e r P o ly v in y l a lc o h o l, D u P o n t E lv a n o l 5 1 -0 5 . A c r y lic a c id , G o o d ric h G la c ia l. " M o n a s t r a l" B lu e B G , D u P o n t. C la y to n Y e llo w , N a tio n a l A n ilin e . 4 ,4 '-D ih y d r o x y b ip h e n y l, D o w . 3 , 5 , 3 ', 5 '- T e t r a n i t r o - 4 , 4 ' -d ih y d r o x y b ip h e n y l, p r e p a r e d by D r . H a r t . P h e n o l, R e d is tille d , D o w . o -N itr o p h e n o l, E a s tm a n W h ite L a b e l, Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 10 p - N itro p h e n o l, E a s tm a n W h ite L a b e l. Chlo ra c e tic a c id , E a s tm a n W h ite L a b e l. F o r m ic ac id . B a k e r s C. P . o -A m in o p h e n o l h y d ro c h lo r id e , E a s tm a n W h ite L a b e l. p -A m in o p h e n o l h y d ro c h lo r id e , E a s tm a n W h ite L a b e l. C a tec h o l, E a s tm a n W h ite L a b e l. R e s o rc in o l, E a s tm a n W h ite L a b e l. b e ta -N a p h th o l, E a s tm a n W h ite L a b e l. 1 ,4 -B u ty n e d io l.. E th y l p y r u v a te , p r e p a r e d b y a F is c h e r e s t é r ific a t io n of p y r u v ic a c id and e th y l a lc o h o l and d is t illa t io n w ith re d u c e d p r e s s u r e . G ly o x a l, M a th e s o n 30% s o lu tio n . P r im u lin e Y e llo w , N a tio n a l A n ilin e . M e th y le n e B lu e N . F . IX , N a tio n a l A n ilin e . T o lu id in e B lu e O , N a tio n a l A n ilin e . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. E X P E R IM E N T A L The S o lu tio n In o r d e r to o b s e rv e the e ffe c ts of o r g a n ic s u b sta n ces upon a n ic k e l d e p o s it, a s ta n d a rd W a tts n ic k e l- p la t in g s o lu tio n w as used . This s o lu tio n is of p r a c t ic a l im p o r ta n c e f o r d u ll- n ic k e l d e p o s itio n and is the b a s ic f o r m u la f o r m o s t of the p r e s e n t b r ig h t - n ic k e l p la tin g solutions (2 8 ). T h e c o m p o s itio n o f th is N ic k e l s u lfa te N ic k e l c h lo r id e B o r ic a c id s o lu tio n w as: 2 40 g . / l . 45 g . / l . 30 g . / l . B e c a u s e of the e ffe c ts of im p u r it ie s on e le c tr o d e p o s its , in e le c tr o p la tin g r e p o r te d b y E w in g and G o rd o n (29) catio n of a ll e le c tr o p la tin g use in th is in v e s tig a tio n . so lu tio n s c a r e fu l p u r i f i ­ s o lu tio n s w as c a r r i e d o u t p r i o r to t h e ir C h e m ic a lly p u re o r e le c t r o p la t e r 's g ra d e salts w e r e u se d and f u r t h e r p u r if ie d a c c o rd in g to the p r o c e d u re sug­ gested b y P r o j e c t 5 o f the A m e r ic a n E l e c t r o p l a t e r s ' S o c ie ty (3 0 ). This p r o c e d u r e has b e e n f u lly d e s c r ib e d in the r e fe r e n c e b u t, b r i e f l y , c o n sis ts o f the fo llo w in g tr e a tm e n t: (1) a h ig h p H (a p p r o x im a te ly 5.5) p r e c ip a tio n o f im p u r it ie s fo llo w e d b y f i l t r a t i o n , d e n s ity e le c t r o ly s is , (2) a lo w c u r r e n t u sing an e le c t r o ly t ic n ic k e l anode and a c o rr u g a te d Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 12 cathode a t cathode c u r r e n t d e n s ity of 5 a m p e re s p e r p ro je c te d cathode a r e a , f o r s q u a re fo o t of 100 a m p e r e -h o u r s p e r g a llo n of s o lu ­ tion, and (3) a c a rb o n t r e a tm e n t o f the n ic k e l s o lu tio n . pure n ic k e l c a rb o n a te and s u lfu r ic of the s o lu tio n . E le c t r o ly s is C h e m ic a lly a c id w e r e u se d to a d ju s t the p H w as c a r r i e d o u t a t p H 2 .2 , w h ic h is the usu al a c id ity of lo w p H W a tts n ic k e l- p la t in g s o lu tio n . A c tiv a te d carbo n t r e a t m e n t c o n s is te d of an a d d itio n of 15 g r a m s p e r l i t e r of N o r it A to the h o t s o lu tio n , c o o lin g and f il t e r i n g . T h e C e ll F o r th is in v e s tig a tio n , m e ta l d e p o s itio n w as c a r r i e d out in a H u ll-t y p e c e ll (3 1 ). In th is m a n n e r, a la r g e ties c o u ld be o b s e rv e d on a s in g le ca th o d e . c o n ta in e r 2 j in ch es b y 5 - 1 / 4 span of c u r r e n t d e n s i­ A r e c t a n g u la r g la s s in c h e s , and deep enough to h o ld 1 l i t e r of p la tin g s o lu tio n , h e ld the co n ten ts of the c e ll. - A nodes of e le c t r o ly tic o th e r end , n ic k e l w e re cathod es 2 in ch es b y 4 - 1 / 1 6 of p la c e d 0 .0 1 6 in ch es at in c h one m ild end of s te e l, the c e ll. h a v in g At the d im e n s io n s (3 2 ), w e r e p la c e d so th a t the lo n g e r d i­ m e n s io n of the cathode spanned the n a r r o w e r d im e n s io n of the m u seu m j a r and the le a d in g edge of the cathod e w as anode, w h ile the t r a ilin g 1 illu s t r a t e s 1 -7 /8 edge w as 5 in ch es f r o m a top v ie w of the c e ll. in ch es f r o m the anode. the F ig u r e T h r e e a m p e re s of c u r r e n t w e re Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 13 2 1/2'i ANODE 1 7 /8 4 1 /6 " FIGURE 1. A T O P VIEW O F T H E CELL USED F O R D E P O S IT IO N A T VARIANT C U R R E N T D E N S I T Y . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 14 passed f o r 20 m in u te s (3 3 ). F ig u r e 2 shows a p lo t o f c u r r e n t d e n s ity v e rs u s o b s e rv e d p la tin g ran g e f o r th is p r o c e d u r e . The e le c t r o ly t ic n ic k e l anodes w e r e d ip p ed in 20 p e r c e n t H C l, w ashed w ith r e d i s t il le d w a te r and p la c e d in an 8 ounce c o tto n d r i l l cloth anode bag p r i o r to im m e r s io n in the c e ll. In o r d e r to red u c e c o n ta m in a tio n b y the anode bag d u rin g e le c tr o d e p o s itio n , a l l anode bags w e r e d e s iz e d b e fo re use. the c lo th in 0 . 0 0 I N . h y d ro c h lo r ic T h is p ro c e d u re c o n s is te d o f b o ilin g a c id f o r d is t ille d w a t e r , w a s h in g w ith 0 .0 0 I N . 15 m in u te s , w a s h in g w ith s o d iu m c a rb o n a te s o lu tio n , f in a lly w a s h in g w it h copious am oun ts of d is t ille d w a t e r . using the d e s iz e d anode b ag s, th e y w e r e and B e fo r e r in s e d c a r e f u lly w ith d o u bly d is t ille d w a t e r . B e fo r e m a n n e r. d e p o s itio n , cathodes w e re T h is c o n s is te d of; c le a n e d in a c o n v e n tio n a l (1) p r e l im i n a r y d e g re a s in g in c a rb o n t e t r a c h lo r id e , (2) ano dic e le c tr o c le a n in g f o r 2 m in u te s p e r s q u a re d e c im e t e r , and (4) a t 10 a m p e re s (3) dipping in 20 p e r c e n t h y d r o c h lo r ic r in s in g w ith double d is t ille d w a te r . n e c e s s a ry b e tw e e n steps (2) and (3 ). a c id , Im m e r s io n rin s e s w e re The a lk a lin e e le c t r o c le a n e r had. the fo llo w in g c o m p o s itio n : S o d iu m h y d ro x id e S o d iu m m e t a - s ilic a t e T r i s o d iu m phosphate S o d iu m c a rb o n a te S o d iu m a c e ta te 21 g ./l. 15 g ./l. 18 g ./l. 6 g ./l. 7.5 g . / l . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 15 1 4 .0 S o 9 10.0 & >§ D H g oS ci D U 0.5 3 1 0.7 5 2 O B S E R V E D D E P O S I T I O N R A N G E , IN C H E S F R O M HIGH C U R R E N T D E N S IT Y E D G E 4 F I G U R E 2 . C U R R E N T D E N S IT Y D IS T R I B U T I O N O V E R T H E C A T H O D E IN A H U L L C E L L . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 16 T h is c le a n e r w as re n e w e d e v e r y fe w d ay s. A p p e a ra n c e o f the D e p o s it B a sed on the c u r r e n t d e n s ity d is tr ib u tio n o f F ig u r e a p p earan ce ta b le s w e r e M e ta l F in is h in g (32) 2, a s e t of a s s e m b le d usin g te r m in o lo g y s e t down in to d e s c rib e the d e p o s it o v e r the ra n g e o b s e rv e d . G ra d a tio n s b e tw e e n a s e m ib r ig h t and d u ll d e p o s it s e e m e d in a d e q u a te , h o w e v e r, so the r e la t iv e The t e r m t e r m s , h a z e and h a z e -b r ig h t w e r e in s e r te d . h a ze w a s u s e d to in te r p o la te b e tw e e n d u ll d e p o s its and s e m ib r ig h t d e p o s its ‘w h e r e g r a in r e fin e m e n t is v is ib le . A h a z e - b r ig h t p an el a r e a w as in te r p o la te d b e tw e e n b r ig h t and s e m ib r ig h t. N o r m a lly , in th is c a s e , the d e p o s it is m a r k e d ly b r ig h t w ith an im p e r f e c t c a s t to be c la s s ifie d h a z e - b r ig h t . In the g e n e r a l s c h e m e , the f i r s t b ro a d g ro u p of p a n e ls i l l u s ­ tr a te the e ffe c t o f s in g le a d d itio n agents on the d e p o s it o b ta in e d f r o m a W a tts n ic k e l- p la tin g o b ta in e d f r o m the p u re s o lu tio n . 3 5 ° , 5 5 ° , and 75° of v a r ia n c e f r o m ta b le s . - W a tts n ic k e l s o lu tio n u n d e r the sam e con­ d itio n s o f t e m p e r a tu r e and p H . 2 5 °, T h is g ro u p is c o m p a re d w ith p a n e ls E ffe c ts w e re o b s e rv e d a t t e m p e r a tu r e s C . f o r so lu tio n s a t p H 2 .2 and 3 .8 . The a m o u n t th e s e c o n d itio n s is in d ic a te d in the a p p e a ra n c e In no cas e w as a s o lu tio n used f o r m o r e than one a d d itio n Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 17 agent e ffe c t. A lw a y s , n e w p u r if ie d n ic k e l s o lu tio n w as used f o r the nex t a d d itio n a g e n t. The f i r s t g ro u p of p a n e ls c o m p r is e e ffe c ts of o rg a n ic ents w h ic h b r o a d ly m a y be c la s s e d as c a rb o h y d r a te s bonyl, p o ly m e r s , d ye s, and p h e n o ls . the m o re c o m m o n c la s s e s f r o m s u b s titu ­ (re d u c in g ), The c a rb o h y d r a te s c a r­ re p re s e n t t r io s e to p o ly m e r ic c a r b o h y d r a te . The c a rb o n y l g ro u p w e r e in the m a in ch o sen f o r t h e ir r e la t iv e o x id a tio n p o te n tia l. so lu b le ty p e s . The p o ly m e r s T h e p h e n o ls w e r e r e p r e s e n t the m o r e c o m m o n w a te r ch o sen to i llu s t r a t e is o m e r ic and s t r u c tu r a l e ffe c ts . T h e second b r o a d g ro u p o f p a n e ls w e r e d e p o s ite d w ith n ic k e l in o r d e r to c o m p a re the e ffe c ts o f s in g le a d d itio n a g e n ts , o r r e p r e ­ s e n ta tiv e s o f the c la s s e s o f s in g le a d d itio n a g e n ts , w ith e ffe c ts in the p re s e n c e of 2 , 7 -n a p h th a le n e di s u lfo n ic a c id . of the o rg a n ic H e r e , c o n c e n tra tio n c o n s titu e n t w as v a r ie d and d e p o s itio n n o r m a lly w as c a r r ie d out a t 65° C . and p H 3 .8 0 . N e x t, a g ro u p o f a llo y d e p o s its of n ic k e l w e r e m a d e . H e re c a rb o n y l s u b s titu e n ts w e r e added to the e q u iv a le n t o f a c la s s ic a l W e is b e rg n ic k e l- c o b a lt p la tin g s o lu tio n (34) in o r d e r to o b s e rv e the e ffe c t of r e p la c in g fo rm a ld e h y d e o r n ic k e l f o r m a te o r b o th. ch o ice of c a rb o n y ls w as b a s e d on r e s u lts o b ta in e d f r o m The the f i r s t group of p a n e ls . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 18 T h re e s o lu tio n s e x te n d in g a llo y d e p o s itio n to ir o n w e r e als o a tte m p te d . F in a lly , b a s e d on the r e s u lts o f th ia z in e dyes .o b ta in e d in group one, som e cath o d es w e r e p re d ip p e d b e fo r e d e p o s itio n in a v a r ia n t m a n n e r. R oughness o f the D e p o s it The ro u g h n ess of e le c tr o d e p o s its w as e v a lu a te d on a m o d e l S A -2 B ru s h S u rfa c e A n a ly z e r . d riv e n p ic k -u p The in s tr u m e n t c o n s is te d of a m o t o r - a r m , a c a lib r a tin g a m p l if i e r , a d ir e c t in k in g o s c illo ­ g rap h , and a R M S (r o o t m e a n s q u a re ) m e t e r . T h is in s t r u m e n t has been c a r e fu lly e x p la in e d and illu s t r a t e d e ls e w h e r e Since the m e t a l p a n e ls o b ta in e d in th is (3 5 ). stu d y r e p r e s e n te d a range of c u r r e n t d e n s ity , i t w as n e c e s s a r y to is o la te tie s on eac h p a n e l f o r sm o o th n ess e v a lu a tio n . a m p e re s p e r s q u a re d e c im e t e r w e r e c h o sen . a t 1 and 1^ in c h e s , r e s p e c tiv e ly , f r o m c u r r e n t d e n s i- V a lu e s of 9.0 and 6.5 T h e s e v a lu e s a r e fo und the h ig h c u r r e n t d e n s ity edge of the p a n e l w hen i t is p la te d in th e c e ll d e s c rib e d above. T h e re ­ f o r e , a s m a ll m e t a l te m p la te w as c o n s tru c te d to id e n tify the a re a s on e a c h p a n e l and the p ic k -u p a rm o f the s u rfa c e a n a ly z e r w as a l ­ lo w e d to t r a v e r s e the d e p o s ite d s u rfa c e in a d ir e c tio n n o r m a l to the Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 19 c u r r e n t d e n s ity v a r ia t io n . B o th p r o f ilo g r a p h s , w h ic h a r e o b ta in e d fr o m the d ir e c t in k in g o s c illo g ra p h , and R M S v a lu e s o f the s u rfa c e w e re o b ta in e d . B e c a u s e w e w e r e n o t p a r t i c u l a r l y in te r e s te d in the s m o o th e n ing a c tio n o f the d e p o s its b u t r a t h e r in the r e la t iv e each d e p o s it, s u re d . s m o o th n e s s of sm o o th n e ss o f the b a s is m e t a l w as n o t a lw a y s m e a ­ H o w e v e r, s e v e r a l s a m p le s of the b a s is m e ta l w e r e e v a lu a te d f o r sm o o th n ess and the span of s u rfa c e sm o o th n ess o f the b a s is m e ta l w as e n c lo s e d b y s tr a ig h t lin e s on a ll g ra p h s . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. D A T A A N D IN T E R P R E T A T IO N A g ro u p o f a p p e a ra n c e ta b le s h av e b e e n c o n s tr u c te d d e s c r ib ­ ing the in d iv id u a l p a n e ls w ith c u r r e n t d e n s ity lim ita t io n s .. A n o u tlin e of data has b e e n in c lu d e d in o r d e r to p o in t o u t the o r g a n iz a tio n of these ta b le s . In o r d e r to d e s c r ib e the p a n e l a p p e a ra n c e , n o r m a lly , a p p ro p ria te t e r m s w e r e u sed s t a r tin g w ith the h ig h c u r r e n t d e n s ity end of th e p a n e l and id e n tify in g e a c h c u r r e n t zone w ith the p r o p e r re m a rk s . F o llo w in g the a p p e a ra n c e ta b le s f o r e a c h g ro u p o f o rg a n ic com pounds in v e s tig a te d , b la c k and w h ite p h o to g ra p h s of the m e ta l p an els a r e in c lu d e d . E a c h p h o to g ra p h e d p a n e l c o n ta in s the n u m b e rs of the s o lu tio n as w e ll as the in d iv id u a l p a n e l n u m b e r, id e n tic a l w ith the n u m b e rs c o n ta in e d in the a p p e a ra n c e ta b le s . The in d iv id ­ ual p a n e ls w e r e n u m b e re d a t the lo w c u r r e n t d e n s ity end o f the p a n e l. Th u s, in a l l c a s e s , the h ig h c u r r e n t d e n s ity end o f the p a n e l is lo c a te d a t the b o tto m of the p a n e l w h ile the lo w c u r r e n t d e n s ity end is lo c a te d a t the top o f the p a n e l. F o llo w in g the a p p e a ra n c e d a ta , ta b le s o f the o r g a n iz a tio n have b e e n c o n s tru c te d to r e p o r t s u rfa c e of the d e p o s it. sam e g e n e r a l rou g h n ess d a ta In a s i m i l a r m a n n e r , fo llo w in g eac h g ro u p o f o rg a n ic a: Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 21 com pounds in v e s tig a te d , p lo ts o f s u rfa c e roughness w e r e in c lu d e d . The lin e s c o n n e c tin g p o in ts of m e a s u r e d ro u g h n ess a r e in te n d e d o n ly as p o s s ib le in te r p r e ta t io n s of the tre n d s o f th e ro u g h n ess d a ta . O u tlin e o f D a ta A. S in g le A d d itio n A g e n t E f f e c t s . I. II. III. W a tts S o lu tio n P a n e ls . C a r b o h y d r a te s (re d u c in g ). a. S o lu tio n 7 - b. S o lu tio n 3 - X y lo s e . c. S o lu tio n 4 - G lu c o s e . d. S o lu tio n 5 - L a c to s e h y d r a te . e. S o lu tio n 6 - R a ffin o se h y d ra te f. S o lu tio n 8 - P o ly m e r s G ly c e r a ld e h y d e . (n o n re d u c in g ). D e x tr in . and U n s a tu r a te d A lip h a tic a. S o lu tio n 9 - M e th y l c e llu lo s e . b. S o lu tio n 1 6 - P o ly v e n y l a lc o h o l. c. S o lu tio n 4 3 - A c r y lic d. S o lu tio n 53 - e. S o lu tio n 10 - P V M / M A . f. S o lu tio n 101, C o m p ounds. a c id . 1 ,4 -B u ty n e d io l. 102, 103 - M o le c u la r w e ig h t v a r ia n c e of P V M /M A . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 22 IV . C a rb o n y l C o m p o u n d s. a. S o lu tio n 11 - C a m p h o r. b. S o lu tio n 12 - p -B ro m o a c e to p h e n o n e . c. S o lu tio n 13 - d. S o lu tio n 26 - A c e ta ld e h y d e . e. S o lu tio n 17 - f. S o lu tio n 14 - P y r u v ic g- S o lu tio n 40 - B u ty l c h lo r a l. h. S o lu tio n 15 - b e ta - M e t h y lu m b e llif e r o n e . C in n a m a ld é h y d e . C h lo r a l. a c id . D ye s. a. S o lu tio n 28 - M o n a s t r a l B lu e b. S o lu tio n 31 - C la y to n Y e llo w . c. S o lu tio n 32 - P r im u lin e Y e llo w . d. S o lu tio n 33 - M e th y le n e B lu e . e. S o lu tio n 34 - (Phthaloc^ T o lu id in e B lu e . P h e n o ls . a. S o lu tio n 30 - 4 ,4 'D ih y d ro x y b ip h e n y l. b. S o lu tio n 27 - 3 ,5 ,3 ',5 ' - T e t r a n i t r o - 4 , 4 ' - d ih y d ro x y b ip h e n y l. c. S o lu tio n 41 - P h e n o l. d. S o lu tio n 42 - o -N itr o p h e n o l. e. S o lu tio n 48 - p -A m in o p h e n o l h y d ro c h lo r id e . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 23 B. f. S o lu tio n 49 - o -A m in o p h e n o l h y d r o c h lo r id e . g. S o lu tio n 50 - C a te c h o l. h. S o lu tio n 51 - R e s o r c in o l. i. S o lu tio n 52 - b e ta -N a p h th o l. 2 ,7 -N a p h th a le n e d is u lfo n ic A c id and S in g le A d d itio n A g e n t E f f e c t s . V II. V III. 2 , 7 - n a p h th a le n e d is u lfo n ic a c id o n ly . C a r b o h y d r a te (re d u c in g ). a. IX . X I. S o lu tio n 381 - C h lo r a l. P o ly m e r and Un s a tu r a te d A lip h a t ic C o m p ounds. a. S o lu tio n 3 6 l - b. S o lu tio n 4 6 - A c r y lic c. S o lu tio n 531 - P V M /M A . a c id . 1 ,4 -B u ty n e d io l. Dyes. b. c. X II. G lu c o s e . C a rb o n y l C o m p o u n d s . a. X. S o lu tio n 371 - S o lu tio n 351 - M o n a s t r a l B lu e . S o lu tio p 311 - C la y to n Y e llo w . S o lu tio n 321 - P r im u lin e S o lu tio n 331 - M e th y le n e B lu e . S o lu tio n 341 - T o lu id in e B lu e . Y e llo w . P h e n o ls . à. S o lu tio n 301 - 4 , 4 * -D ih y d r o x y b ip h e n y l. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 24 C. b. S o lu tio n 271 - 3 ,5 ,3 ', 5' - T e t r a n it r o - 4 , 4 ' - d ih y d r o x y b ip h e n y l. c. S o lu tio n 411 - P h e n o l. d. S o lu tio n 421 e. S o lu tio n 47 - p -N itr o p h e n o l, f. S o lu tio n 481 - p -A m in o p h e n o l. g. S o lu tio n 491 - o -A m in o p h e n o l. h. S o lu tio n 501 - C a te c h o l. i. S o lu tio n 511 - R e s o r c in o l. j. S o lu tio n 521 r b e ta -N a p h th o l. - o - N itr o p h e n o l, A llo y - C a r b o n y l E f f e c t s . X in . N ic k e l C o b a lt. a. S o lu tio n 18 - C in n a m a ld é h y d e . b. S o lu tio n 19 - C h lo r a l w ith a m m o n iu m s u lfa te . c. S o lu tio n 20 - d. S o lu tio n 24 - A c e ta ld e h y d e . e. S o lu tio n 29 - E t h y l p y r u v a te . C h lo r a l. G ly o x a l. X IV . f. S o lu tio n 39 - B u ty l C h lo r a l. g. S o lu tio n 44 - C h lo r a c e tic a c id and c h lo r a l. h. S o lu tio n 45 - A c r y lic a c id and c h lo r a l. N ic k e l Ir o n . a. S o lu tio n 21 - C h lo r a l, n ic k e l f o r m a te , t a r t a r i c a c id . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 25 D. b. S o lu tio n 22 - F e rro u s s u lfa te , c h lo r a l. c. S o lu tio n 25 - N ic k e l p ro p io n a te , c h lo r a l. E x te r n a l T r e a t m e n t o f C a th o d e . XV. S o lu tio n 2 3 -, F i l t e r p a p e r and c in n a m a ld é h y d e . S o lu tio n 312 - D ip p in g in C la y to n Y e llo w . S o lu tio n 332 - D ip p in g in M e th y le n e B lu e . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 26 T ab le Panel N o. 1. S o lu tio n s d e p o s its . pH 1 and 2; th e a p p e a ra n c e o f W a tts n ic k e l s o lu tio n Tem p. (° C ath o d e A p p e a ra n c e C .) 12 2.20 25 E x f o lia t e . D u ll above 14.0 a m p . / s q . d m . ; * h a ze 14 .0 to 3.2 a m p ./s q .d m .; u n d e r, d u ll. 13 2.2 0 35 D u ll to h a z e abo ve 14.0 a m p ./s q .d m .; 14.0 to 1.0 a m p ./s q .d m .; u n d e r, d u ll. 14 2,2 0 • 54 D u ll. 15 2.30 74 D u ll. 22 3.50 ■ 25 E x f o lia t e . H a z e above 14.0 a m p ./s q .d m .; s e m ib r ig h t 14.0 to 9-0 a m p ./s q .d m .; u n d e r, haze. 23 3.50 35 B r ig h t a t h ig h c u r r e n t d e n s ity ed g e. haze. 24 3.70 54 D u ll above 2.1 a m p ./s q .d m .; 25 3.80 74 D u ll above 14.0 a m p ./s q .d m .; h a z e 3.2 a m p ./s q .d m .; u n d e r, d u ll. d u ll D u ll to u n d e r, h a z e . 14.0 to * A m p e r e s p e r s q u a re d e c im e t e r . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 27 Table 2. Panel No. S o lu tio n 7; the e f fe c t of g ly c e ra ld e h y d e in c o n c e n tra tio n s of 0 .5 g . / l . and 2 .0 g . / l . on the app earanjce of W a tts n ic k e l s o lu tio n d e p o s its . pH Tem p. r C atho de A p p e a ra n c e C .) 0 .5 g . / l . G ly c e r a ld e h y d e 740 2.21 23 E x f o lia t e . H a z e above 9 .0 a m p ./s q .d m .; s e m ib r ig h t 9 .0 to 1.6 a m p ./s q .d m .; u n d e r, haze. 730 2 .2 4 34 H a z e above 14.0 a m p ./s q .d m .; h a z e - b r ig h t 14.0 to 9. 7 a m p ./s q .d m .; u n d e r, h a z e . 720 2 .1 7 54 H a z e h ig h c u r r e n t d e n s ity ed g e. 710 2 .1 2 73 D u ll. 71 3 .7 6 23 E x fo lia te above 14.0 a m p ./s q .d m . B r ig h t above 2 .1 a m p ./s q .d m .; u n d e r, h a z e . 72 3.60 35 B r ig h t h ig h c u r r e n t d e n s ity edge, h a z e . 73 3.60 55 D u ll above 9.0 a m p . /s q .d m . : h a ze 9 .0 to 2 .6 a m p ./s q .d m .; u n d e r, d u ll. 74 3.85 76 D u ll. D u ll. 2.0 g . / l . G ly c e r a ld e h y d e 750 2.20 26 E x f o lia t e . H a z e above 9 .7 a m p ./s q .d m .; h a z e - b r ig h t 9 .7 to 6.4 a m p ./s q .d m .; u n d e r, haze. 760 2.2 0 35 H a z e - b r ig h t above haze. 770 2.2 7 55 H aze. 11.8 a m p ./s q .d m .; u n d e r, Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 28 T a b le 2 (C o n tin u ed ) Tem p. Panel No. pH 780 2.20 76 D u ll. 78 3.70 26 E x f o lia t e . H a z e above 9.0 a m p ./s q .d m .; s e m ib r ig h t 9.0 to 5.9 a m p ./s q .d m .; u n d e r , haze. 77 3.70 35 E x f o lia t e . 76 3,82 54 S e m ib r ig h t above 15.1 a m p ./s q .d m .; d u ll 15.1 to 1.6 a m p ./s q .d m .; u n d e r, d a rk , d u ll. 75 3.8 8 75 D u ll C athode A p pearaince ( “ C .) H aze. KM* Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 29 T a b le Panel N o. 3. S o lu tio n 3; the e ffe c t o f x y lo s e in c o n c e n tra tio n s of 0 .5 g . / l . and 2 .0 g . / l . on the a p p e a ra n c e o f W a tts n ic k e l s o lu ­ tio n d e p o s its . pH Tem p. (° C atho de A p p e a ra n c e C .) 0 .5 g . / l . X y lo s e 35 2 .1 5 26 E x fo lia te . H a z e above 14 .0 a m p ./s q .d m .; h a ze to s e m ib r ig h t 14.0 to 3.2 a m p ./s q . d m .; u n d e r, h a z e . 36 2 .20 35 H a z e h ig h c u r r e n t d e n s ity ed g e. H a z e to s e m ib r ig h t above 11.8 a m p ./s q .d m .; u n d e r, haze. 37 2 .1 8 54 D u ll. 38 2 .1 8 73 D u ll. 31 3.75 27 E x f o lia t e . H a z e a t h ig h c u r r e n t d e n s ity . B r ig h t above 8 .6 a m p ./s q .d m .; u n d e r, h a z e . 32 3.70 34 B r ig h t above to d u ll. 33 3 .8 5 55 D u ll. 34 3.85 ■ 72 D u ll. 14.0 a m p ./s q .d m . u n d e r, h a ze 2 .0 g . / l . X y lo s e 330 2 .1 7 24 E x fo lia te . H a z e above 9 .0 a m p ./s q .d m .; s e m ib r ig h t 9.0 to 4 .3 a m p ./s q .d m .; u n d e r, haze. 340 2 .20 35 H a z e a t h ig h c u r r e n t d e n s ity e d g e. S e m ib r ig h t above 13.0 a m p ./s q .d m .; u n d e r, d u ll. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 30 T a b le Tem p. 3 (C o n tin u ed ) Panel No. pH 320 2 .2 0 54 D u ll. 310 2 .1 3 73 D u ll. 350 3.60 24 E x fo lia te above 10.8 a m p ./s q .d m . B r ig h t above 25 a m p ./s q .d m .; u n d e r, h a z e . 360 3.75 36 H aze. 370 3.80 59 D u ll. 380 3.78 73 D u ll. (° C atho de A p p e a ra n c e C .) ' Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 31 T ab le 4. Panel No. S o lu tio n 4; the e f fe c t of g lu c o s e in c o n c e n tra tio n of 0 .5 g . / l . and 2 .0 g . / l . on the a p p e a ra n c e o f W atts n ic k e l s o lu tio n d e p o s its . pH Tem p. r C ath o d e A p p e a ra n c e c .) 0 .5 g . / l . G lu c o se 45 2 .0 0 26 E x f o lia t e . H a z e above 9 .7 a m p ./s q .d m .; h a z e to s e m ib r ig h t 9 .7 to 4 .3 a m p ./s q .d m .; u n d e r, h aze . 46 2 .2 5 35 H a z e a t h ig h c u r r e n t d e n s ity edg e. H aze to s e m ib r ig h t above 1 0 .8 a m p ./s q .d m .; u n d e r haze. 47 2 .2 0 54 D u ll. 48 2 .2 0 73 D u ll. 41 3.50 27 H a z e above 14.0 a m p ./s q .d m .; s e m ib r ig h t 14.0 to 7 .6 a m p ./s q .d m .; u n d e r, h a z e . 42 3.45 34 H a z e a t h ig h c u r r e n t d e n s ity ed g e. S e m i­ b r ig h t above 10.8 a m p ./s q .d m .; u n d e r, h a z e . 43 3.30 55 D u ll to h a z e . 44 3.30 72 D u ll. 2.0 g . / l . G lu c o se 430 2 .1 7 24 E x fo lia te above 15.1 a m p ./s q .d m . H aze above 9 .0 a m p ./s q .d m .; s e m ib r ig h t 9.0 to 3.2 a m p ./s q .d m .; u n d e r, h a z e . 440 2 .2 0 35 H a z e a t h ig h c u r r e n t d e n s ity edge. H a ze to s e m ib r ig h t above 6 .5 a m p ./s q .d n o .; u n d e r, d u ll. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 32 T a b le Tem p. 4 (C o n tin u ed ) Panel N o. pH 420 2.21 54 B r ig h t to h a ze a t h ig h c u r r e n t d e n s ity ed g e. D u ll. 410 2 .2 5 73 D u ll. 450 3 .8 5 24 . E x fo lia te above 1 1 .8 a m p ./s q .d m . H aze abo ve 9 .0 a m p ./s q .d m .; b r ig h t 9.0 to 2.1 a m p ./s q .d m .; u n d e r, h a z e . 460 3 .5 7 . 36 H ig h c u r r e n t d e n s ity b r ig h t r in g . H aze abo ve 7.0 a m p ./s q .d m .; u n d e r, d u ll. 470 3.75 59 D u ll. 480 3 .6 5 73 D u ll. (° C athode A p p e a ra n c e C .) Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 33 T ab le Panel No. 5. S o lu tio n 5; the e f fe c t of la c to s e h y d ra te in c o n c e n tra tio n s of 0 .5 g . / l . and 2 .0 g . / l . on the a p p e a ra n c e o f W atts n ic k e l s o lu tio n d e p o s its . pH Tem p. (° C atho de A p p e a ra n c e C .) 0 .5 g . / l . L a c to s e H y d r a te 55 2 .2 8 26 H a z e above 9 .7 a m p ./s q .d m .; s e m ib r ig h t 9 .7 to 1.0 a m p ./s q .d m .; u n d e r, h a z e . 56 2 .2 3 35 H a z e a t h ig h c u r r e n t d e n s ity ed g e. H azeb r ig h t above 9 .7 a m p ./s q .d m .; u n d e r, h a z e . 57 2 .2 6 54 H a z e - b r ig h t above h a z e , p itte d . 58 2 .2 6 73 D u ll. 51 3.70 27 E x fo lia te above 14.0 a m p ./s q .d m . H a ze above 11.8 a m p ./s q .d m .; u n d e r, s e m ib r ig h t. 52 3 .7 3 34 S e m ib r ig h t, p itte d above 9 .0 a m p ./s q .d m .; u n d e r, h a z e . 53 3.80 55 D u ll and p itte d 54 3.80 72 D u ll. 2 .0 g . / l . 14.0 a m p ./s q .d m .; u n d e r, L a c to s e H y d r a te 5 30 2 .20 24 E x fo lia te . H a z e above 7.0 a m p ./s q .d m .; h a z e - b r ig h t 7.0 to 1.0 a m p ./s q .d m .;, u n d e r, haze. , 540 2 .2 2 35 H a z e above 14.0 a m p ./s q .d m .; h a z e -b r ig h t 14.0 to 8 .6 a m p ./s q .d m .; u n d e r, d u ll. 520 2.21 54 H a z e a t h ig h c u r r e n t d e n s ity edge. p itte d . D u ll, Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 34 T a b le 5 (C o n tin u ed ) Tem p. P anel N o. pH 510 2 .20 73 D u ll, p itte d . 550 3 .62 24 E x f o lia t e . P it t e d , h a ze ab o ve 1 0 .8 a m p ./s q . drn.; u n d e r, b r ig h t.' 560 3.50 36 H a z e a t h ig h c u r r e n t d e n s ity e d g e . B r ig h t above 9 .7 a m p ./s q .d m .; u n d e r, h a z e . 570 3 .8 8 59 D u ll. 580 3 .8 7 73 D u ll. (° C atho de A p p e a ra n c e C .) Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 35 T ab le Panel No. 6, S o lu tio n 6; the e ffe c t o f r a ffin o se h y d ra te in c o n c e n tra tio n s of 0 .5 g . / l . and 2 .0 g . / l . on the a p p e a ra n c e of W a tts n ic k e l s o lu tio n d e p o s its . pH Tem p. r C atho de A p p e a ra n c e C .) 0 .5 g . / l . R a ffin o se H y d r a te 65 2 .2 2 26 66 2 .2 2 35 67 2.20 54 H a z e above p itte d . 68 2.20 73 D u ll. 61 3.82 27 E x fo lia te . H a z e above 11.8 a m p ./s q .d m ,; h a z e - b r ig h t 11.8 to 1.0 a m p ./s q .d m .; u n d e r, haze. 62 3.85 34 H a z e - b r ig h t above haze. 63 3.70 55 D u ll, p itte d . 64 3,70 72 D u ll, p itte d . E x f o lia t e . H a z e abo ve 9.0 a m p ./s q .d m .; h a z e - b r ig h t 9.0 to 3 .2 a m p ./s q .d m .; u n d e r, haze. ■ H a z e - b r ig h t above haze. 1 0.8 a m p ./s q .d m .; 1.0 a m p ./s q .d m .; u n d e r, u n d e r, d u ll, 1 1 .8 a m p ./s q .d m .; u n d e r, 2.0 g . / l . R a ffin o se H y d r a te 630 2 .1 3 24 H a z e , e x fo lia te above 11.8 a m p ./s q .d m . h a z e - b r ig h t 11.8 to 1.0 a m p ./s q .d m .; u n d e r, haze. 640 2 .2 2 35 H a z e a t h ig h c u r r e n t d e n s ity edge. H azeb r ig h t above 9 .7 a m p ./s q .d m .; u n d e r, h a z e . 0 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 36 T a b le 6 (C o n tin u ed ) Tem p. Panel No. pH 620 2 .1 8 54 H aze. 610 2 .1 8 73 D u ll. 650 3 .8 8 24 E x f o lia t e , haze above u n d e r, b r ig h t . 66o 3 .7 2 36 H a z e - b r ig h t above haze. 670 3 .8 8 59 D u ll. 680 3.70 73 D u ll, p itte d . (° C atho de A p p e a ra n c e C .) 10.8 a m p ./s q .d m .; 14.0 a m p ./s q .d m .; u n d e r, Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 37 Tab le 7. Panel No. S o lu tio n 8; th e e ffe c t of d e x tr in in c o n c e n tra tio n s of 0 .5 g . / l . and 2 .0 g . / l . on the a p p e a ra n c e of W a tts n ic k e l so­ lu tio n d e p o s its . pH Tem p. r C atho de A p p e a ra n c e c .) 0 .5 g . / l . D e x t r in 840 2 .2 5 23 E x fo lia te above 14.0 a m p ./s q .d m . H aze above 2 .6 a m p ./s q .d m .; u n d e r, s e m ib r ig h t. 830 2 .2 5 34 H a z e above 1 0.8 a m p ./s q .d m .; h a z e - b r ig h t 10.8, to 6.5 a m p ./s q .d m .; u n d e r , h a z e . 820 2 .1 7 54 B r ig h t above 8.1 a m p ./s q .d m .; u n d e r, h a z e . 810 2 .1 2 73 S e m ib r ig h t a t h ig h c u r r e n t d e n s ity ed g e. D u ll. 81 3.80 23 E x fo lia te above 14.0 a m p ./s q .d m . H aze above 5 .4 a m p ./s q .d m .; u n d e r, h a z e - b r ig h t . 82 3.83 35 H a z e above 4 .3 a m p ./s q .d m .; b r ig h t 4 .3 to 1.0 a m p ./s q .d m .; u n d e r, h a z e to d u ll. 83 3.80 55 H a z e - b r ig h t above 6 .5 a m p ./s q .d m ,; h a ze to d u ll. 84 3.75 76 D u ll. 2.0 g . / l . u n d e r, D e x tr in 850 2 .2 5 26 E x fo lia te above 860 2.20 35 H a z e above 870 2.18 55 S e m ib r ig h t above 5 .4 a m p ./s q .d m .; haze. 14.0 a m p ./s q .d m . 1.0 a m p ./s q .d m .; H aze. u n d e r, b r ig h t. u n d e r, Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 38 T a b le Tem p. 7 (C o n tin u ed ) Panel No. pH 880 2 .2 4 76 H a z e a t h ig h c u r r e n t d e n s ity ed g e. 88 3.70 26 E x fo lia te above 14.0 a m p ./s q .d m . H aze ab o ve 1 .6 a m p ./s q .d m .; u n d e r, h a z e - b r ig h t . 87 3 .8 8 35 H a z e above 3 .2 a m p ./s q .d m .; u n d e r, s e m i­ b r ig h t . 86 3 .8 8 54 B id g h t above 10.8 a m p ./s q .d m ,; h a z e to 2 .1 a m p ./s q .d m .; u n d e r, d u ll. 85 3 .7 3 75 H a z e a t h ig h c u r r e n t d e n s ity edg e. r c .) C atho de A p p e a ra n c e D u ll. 10.8 D u ll. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 39 # '^ 4 . ... W\ n • V i . - # i 1 * h i F ig u r e 3. T h e e ffe c t of c a rb o h y d ra te s on th e a p p e a ra n c e of W a tts n ic k e l d e p o s its a t p H 2 .2 . Reproduced with permission o f the copyright owner. Further reproduction prohibited without permission. 40 M F ig u r e 4 . W T h e e ffe c t of c a rb o h y d ra te s on the a p p e a ra n c e o f W a tts n ic k e l d e p o s its a t p H 2 .2 . ... Reproduced with permission o f the copyright owner. Further reproduction prohibited without permission. 41 e 84 J F ig u r e 5. • r 53 # 43 • e 44 54 # » l i ; T h e e ffe c t of c a rb o h y d ra te s on th e a p p e a ra n c e o f W a tts n ic k e l d e p o s its a t p H 3 ,8 . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 42 F ig u r e 6. T h e e ffe c t o f c a rb o h y d ra te s on th e a p p e a ra n c e of W a tts n ic k e l d e p o s its a t p H 3 .8 . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 43 T a b le 8. S o lu tio n 9; the e ffe c t of m e th y l c e llu lo s e in c o n c e n tra tio n o f 0 .5 g . / l . on the a p p e a ra n c e o f W tts n ic k e l s o lu tio n d e ­ p o s its . Tem p. Panel No. pH 910 2.20 28 H a z e above 14.0 a m p ./s q .d m .; h a z e - b r ig h t 14.0 to 2 .6 a m p ./s q .d m .; u n d e r, h a ze . 920 2.20 37 H a z e a t h ig h c u r r e n t d e n s ity e d g e. H azeb r ig h t above 8 .6 a m p ./s q .d m .; u n d er, h a z e . 930 2.20 57 D u ll. 940 2 ,2 5 75 D u ll, d a r k . 94 3.8 2 28 H a z e ab o ve 15.1 a m p ./s q .d m .; h a z e - b r ig h t 15.1 to 10.8 a m p ./s q .d m .; u n d e r, h a z e . 93 3.70 39 D u ll above 2 .6 a m p ./s q .d m .; 92 3.65 58 D u ll. 91 3.81 73 D u ll, d a r k . C athode A p p e a ra n c e C c .) u n d e r, h a z e . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 44 T a b le 9. Panel No. S o lu tio n l6 ; the e f fe c t o f p o ly v in y l a lc o h o l in c o n c e n tr a tio n o f 0 .5 g . / l . on the a p p e a ra n c e o f W a tts n ic k e l s o lu tio n d e ­ p o s its . pH Tem p. (° C atho de A p p e a ra n c e C .) 1640 2 .2 1 23 E x f o lia t e . 1630 2 .2 0 37 H a z e above 1620 2 .2 0 56 H a z e abo ve 8 .6 a m p ./s q .d m .; b r ig h t . 1610 2 .2 0 75 H a z e ab o ve 1 1 .8 a m p . / s q. d m . ; unde r , h a z e to m il k y . 164 3 .6 5 25 E x f o lia t e . H a z e abo ve 14.0 a m p ./s q .d m .; h a z e - b r ig h t 14.0 to 8 .6 a m p ./s q .d m .; u n d e r, haze. 163 3.80. 36 H a z e a t h ig h c u r r e n t d e n s ity e d g e . B r ig h t above 15.1 a m p ./s q .d m .; h a ze 15.1 to '2.1 a m p ./s q .d m .; u n d e r, b r ig h t . 162 3 .8 2 56 D u ll above 14.0 a m p ./s q .d m ,; b r ig h t r in g a t 14.0 a m p ./s q .d m .; u n d e r, h a z e . I6 l 3 .7 5 75 D u ll, d a r k . H a z e , p itte d . 1.0 a m p ./s q .d m .; u n d e r, b r ig h t . u n d e r, h a z e - Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 45 Tab le Panel No. 10. S o lu tio n 43; the e f fe c t o f a c r y lic a c id in c o n c e n tra tio n s o f 0 .5 g . / l . an d 2 .0 g . / l . on the a p p e a ra n c e o f W a tts n ic k e l s o lu tio n d e p o s its . pH - Tem p, C C ath o d e A p p e a ra n c e c .) 0 .5 g . / l . A c r y li c A c id 4310 2 .2 5 .2 5 4320 2 .2 5 38 H a z e - b r i g h t above d e r, haze. 4330 ,2 .5 0 55 H a z e abo ve 2 .6 a m p . /s q .d m . ; u n d e r, d u ll, p itt e d . 4340 2 .2 5 74 H a z e above d a rk . 431 3 .8 8 24 E x f o lia t e . B r ig h t above u n d e r, h a z e . 432 3 .5 5 35 S e m ib r ig h t a t h ig h c u r r e n t d e n s ity e d g e. H a z e above 2 .6 a m p ./s q .d m .; u n d e r, d u ll. 433 3 .5 5 55 H a z e a t h ig h c u r r e n t d e n s ity ed g e. d a rk . 434 3 .8 5 73 D u ll, d a r k . E x f o lia t e . H a z e - b r i g h t above s q .d m .; u n d e r, d u ll. 1 0 .8 a m p ./ 1 1 .8 a m p ./s q .d m .; 14.0 a m p ./s q .d m .; un­ u n d e r, d u ll, 1 1 ,8 a m p ./s q .d m .; D u ll, 2 .0 g . / l . A c r y li c A c id 4350 2 .2 0 24 E x fo lia te a t h ig h c u r r e n t d e n s ity edg e. S e m ib r ig h t above 10 .8 a m p ./s q .d m .; u n d e r, haze. 4360 2 .2 5 35 H a z e a t h ig h c u r r e n t d e n s ity e d g e . H azeb r ig h t above 1 0 .8 a m ÿ . / s q .d m .; h a z e 10.8 to 2 .6 a m p ./s q .d m .; h a z e - b r ig h t , p itte d 2 .6 to 2.1 a m p ./s q .d m .; u n d e r, h a z e . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 46 T a b le Panel ^o . pH 10 (C o n tin u e d ) Tem p. (° C ath o d e A p p e a ra n c e C .) 4370 2 .2 5 56 H a z e - b r i g h t above d u ll. 4380 - 70 D u ll , 435 3.8 5 24 E x f o lia t e . B r ig h t above u n d e r , d u ll. 436 3.75 35 H a z e - b r i g h t above 14 .0 a m p ./s q .d m .; h a z e to d u ll. 437 3 .7 8 55 D u ll . 438 3.85 75 D u ll, d a r k . 1 1 .8 a m p ./s q .d m .; u n d e r, d a rk . 1 1 .8 a m p ./s q .d m .; u n d e r, Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 47 Table P an el No. 11. S o lu tio n 53; th e e f f e c t of 1 ,4 -b u ty n e d io l in c o n c e n tra tio n s o f 0 .5 g . / l . an d 2 .0 g . / l . on the a p p e a ra n c e o f W a tts n ic k e l s o lu tio n d e p o s its . pH Tem p. (° C ath o d e A p p e a ra n c e C .) 0 .5 g . / l . 5310 2 .20 26 1 ,4 -B u ty n e d io l E x f o lia t e . H a z e abo ve 1 0 .8 a m p ./s q .d m .; h a z e - b r ig h t 1 0 .8 to 4 .8 a m p ./s q .d m .; u n d e r, h & ze . 5320 2 .2 0 3? H a z e a t h ig h c u r r e n t d e n s ity ed g e. H azeb r ig h t ab o ve 14.0 a m p ./s q .d m .; u n d e r, h a z e . H a z e - b r i g h t r in g a t 2 .6 a m p ./s q .d m . 5330 2.20 54 H a z e a b o v e 15.1 a m p ./s q .d m .; 5340 2 .2 2 74 D u ll, p it t e d above 9 .7 a m p ./s q .d m .; u n d e r, h a z e , p itt e d . 531 3.70 25 E x f o lia t e . B r ig h t , p itt e d above 5 .4 a m p ./ s q .d m .; u n d e r, h a z e - b r ig h t . 532 3.80 36 B r ig h t . 533 3.70 57 H a z e - b r i g h t , p itt e d above u n d e r, b r ig h t . 534 3.75 75 H a z e - b r ig h t , p itt e d . 2.0 g , / l . u n d e r, d u ll. 15.1 a m p ./s q .d m .; 1 ,4 -B u ty n e d io l 5350 2.20 27 E x f o lia t e . B r ig h t , p itte d . 5360 2.20 37 E x f o lia t e . B r ig h t , p itte d . 5370 2.20 55 B r ig h t , p itte d . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 48 T a b le Panel No. pH 11 (C o n tin u e d ) Tem p. C ath o d e A p p e a ra n c e ( “ C .) 5380 2 .2 0 75 S e m ib r ig h t, p itte d . 535 3.60 26 E x f o lia t e . B r ig h t , p itte d . 536 3.70 35 E x f o lia t e . B r ig h t , p itte d . 537 3.80 55 B r ig h t , p itte d . 538 3 .75 75 S e m ib r ig h t. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 49 T ab le 12. S o lu tio n 10; the e f fe c t o f P V M / M A ’*^ (p o ly m e th y l v in y l e t h e r - m a le ic a n h y d rid e ) in c o n c e n tra tio n of 0 .5 g . / l . on the a p p e a ra n c e o f W a tts n ic k e l s o lu tio n d e p o s its . Panel No. pH Tem p. 104 2 .2 0 28 E x fo lia te . 103 2 .2 2 39 B r ig h t , 102 2 .2 5 58 H a z e above 13,0 a m p ./s q .d m .; b r ig h t , s p o tte d w h ite . 101 2 .1 0 73 H a z e ab o ve 1 1 .8 a m p ./s q .d m ,; u n d e r, h a z e b r ig h t and s trb s s c r a c k e d , sp o tted w h ite . 1010 2.5 0 28 E x f o lia t e . 1020 2 .7 0 37 B r ig h t . 1030 2 .7 5 57 H a z e above 1 1 .8 a m p ./s q .d m .; h a z e - b r ig h t 1 1 .8 to 4 .3 a m p ./s q .d m .; u n d e r, h a z e . 1040 3.00 75 H a z e to d u ll. 1050 2 .2 0 73 H a z e above C a th o d e A p p e a ra n c e ( “ C .) ;. * S p e c ific v is c o s ity , B r ig h t. s p o tte d w h ite . u n d e r, h a z e - B r ig h t . 1 0 .8 a m p ./s q .d m .; u n d e r, b r ig h t . 2 .6 . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 50 4310 9 F ig u r e 7. T h e e ffe c t o f p o ly m e r s and u n s a tu ra te d a lip h a tic com pounds on the a p p e a ra n c e o f W a tts n ic k e l d e p o s its a t p H 2 .2 . R eproduced with permission of the copyright owner. Further reproduction prohibited without permission. 51 l ÿ • (9 - ’4 3 t / '-% # 4 .J tù fc - v i.' V ..... {,'.< ' 24 l' I F ig u r e 8 . - T h e e f f e c t o f p o ly m e r s and u n s a tu ra te d a lip h a tic com pounds on the a p p e a r a n c e of W a tts n ic k e l d e p o s its a t pH 3 *8. R eproduced with permission of ttie copyright owner. Further reproduction prohibited without permission. 52 T ab le 13. S o lu tio n s 101, 102, and 10 3; the e ffe c t of th e s p e c ific v is c o s it y of the P V M / M A (p o ly m e th y l v in y l e t h e r m a le ic a n h y d rid e ) on the a p p e a ra n c e o f W a tts n ic k e l s o lu tio n d e p o s its w it h in c r e a s in g c o n c e n tra tio n s of c o p o ly m e r. (S o lu tio n 101 s p e c ific v is c o s ity , 0 .4 ; S o lu tio n 102 s p e ­ c if ic v is c o s it y , 2 .6 ; S o lu tio n 10 3 s p e c ific v is c o s ity , 3 .2 .) Panel No. pH Tem p. r C .) A d d i­ tio n (g. PVM/ MA) T o ta l A d d i­ tio n (g. C athode A p p e a ra n c e PVM/ MA) 3 .8 2 57 0.1 0.1 D u ll to h a z e . 2 .2 0 75 0 .1 0 .1 D u ll to h a z e . 1031 2 .8 0 57 0.1 0 .1 D u ll to h a z e . 1012 2.60 55 - . ■ 0 .1 D u ll to h a z e . 2 .3 0 56 - 0.1 D u ll to h a z e . 1032 2 .6 5 55 - 0 .1 D u ll to h a z e . 1 0 1 3 ** 2 .5 4 55 0 .2 0 .3 D u ll above 6 .5 a m p ./s q . d m .; u n d e r, h a ze to 1011 105* 106* b r ig h t, p itte d . 1023 2.6 2 55 0 .2 0 .3 D u ll above 7 .6 a m p ./s q . d m .; u n d e r, haze to b r ig h t, p itte d . 1033 2.60 55 0 .2 0 .3 D u ll above 1.0 a m p ./s q . d m .; u n d e r, h a ze to b r ig h t, p itte d . 1014 2 .7 0 58 - 0 .3 D u ll, p itte d , tre e d . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 53 T a b le Panel No. A d d i­ tio n (g. PVM/ MA) Tem p. pH ( “ C .) 1024 2 .8 0 58 1034 2 .7 2 58 1015 2. 6 2 56 1025 2 .6 5 1035 - 13 (C o n tin u e d ) T o ta l A d d i­ tio n (g. C atho de A p p e a ra n c e PVM/ MA) 0 .3 D u ll abo ve 8 .6 a m p ./s q . d m .; u n d e r, 'h a z e 0 .3 D u ll above 1.0 a m p ./s q . d r m .; u n d e r, h a z e to b r ig h t . 0 .1 0 .4 D u ll above 6.5 a m p ./s q . d m .; u n d e r, b r ig h t, p itte d , s tr e s s e d . 56 0 .1 0 .4 D u ll above 10 .8 a m p ./ s q .d m .; u n d e r, b r ig h t to h a z e . 2 .5 5 56 0 .1 0 .4 D u ll to h a z e . 1016 2 .7 4 56 0 .1 0 .5 D u ll above 9 .7 a m p ./s q . d m .; u n d e r, b r ig h t , s tr e s s e d , p itte d . 1026 2 .6 5 56 0 .1 0 .5 D u ll above 10.8 a m p ./ s q .d m .; u n d e r, b r ig h t to h a z e , s tr e s s e d . 1036 2 .6 4 56 0 .1 0 .5 D u ll to h a z e above 2.1 a m p ./s q .d m .; u n d e r, b r ig h t, p itte d . 1017 2 .8 2 65 0 .1 0 .6 D u ll above 8 .6 a m p ./s q . d m .; u n d e r, b r ig h t, s tr e s s e d , p itte d . , . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 54 T a b le Panel No. pH Tem p. (° C .) A d d i­ tio n (g. ■ PVM/ MA) 13 (C o n tin u ed ) T o ta l A d d i­ tio n (g . PVM/ MA) C ath o d e A p p e a ra n c e 1027 2 .6 5 65 0 .1 0 .6 B r ig h t to h a z e , 1037 2 .6 5 65 0 .1 0 .6 D u ll to h a ze above 3 .2 a m p ./s q .d m .; u n d e r, b r ig h t , p itte d . . s tr e s s e d . 1 1018 2 .9 5 65 0 .6 B r ig h t , s tr e s s e d above 1.0 a m p ./s q .d m .; u n d e r, d u ll, b la c k . 1028 2 .8 3 65 0 .6 D u ll above 1 0 .8 a m p ./ s q .d m .; u n d e r, b r ig h t to h a z e , s tr e s s . 1038 2 .7 5 65 0 .6 D u ll to h a ze above 7 .6 a m p ./s q .d m .; u n d e r, b r ig h t , p itte d . * S o lu tio n 102. * * A l l p la te s n u m b e rin g 3 o r g r e a t e r f r o m the so lu tio n s d e m ­ o n s tra te d the p o ly m e r a c tu a lly d e p o s itin g on the cath o d e. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 55 F ig u r e 9. T h e e ffe c t o f s p e c ific v is c o s ity o f P V M / M A on th e a p p e a ra n c e of W a tts n ic k e l s o lu tio n d e p o s its . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 56 T ab le Panel N o. 14. S o lu tio n 11; the e f fe c t o f c a m p h o r in c o n c e n tra tio n o f 0 .5 g . / l . on the a p p e a ra n c e o f W a tts n ic k e l s o lu tio n d e ­ p o s its . . pH Tem p. r C ath o d e A p p e a ra n c e C .) 1110 2.21 28 H a z e above 1 1 .8 a m p ./s q .d m .; h a z e - b r ig h t 11 .8 to 2 .1 a m p ./s q .d m ,; u n d e r, h a z e . 1120 2 .2 5 37 H a z e above 15.1 a m p '-./s q .d m .; h a z e - b r ig h t 15.1 to 1 0 .8 a m p ./s q .d r n ,; u n d e r, h a z e . 1130 2 .2 5 57 H a z e a t h ig h c u r r e n t d e n s ity e d g e . 1140 2 .2 0 75 D u ll, p itte d . 114 3.70 28 E x f o lia t e , h a z e above 1 1 .8 a m p ./s q .d m .; h a z e - b r ig h t 1 1 .8 to 6 .5 a m p ./s q .d m .; u n d e r, D u ll. haze. 113 3 .82 39 H a z e - b r ig h t a t h ig h c u r r e n t d e n s ity edge. D u ll. 112 3.70 58 D u ll. 111 3,7 2 74 D u ll. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 57 Tab le Panel No. 15. S o lu tio n 12; th e e f f e c t o f p -b ro m o a c e to p h e n o n e in co n c e n ­ t r a t io n o f 0 .5 g . / l . on the a p p e a ra n c e o f W a tts n ic k e l s o lu tio n d e p o s its . pH Tem p. (° C athode A p p e a ra n c e C .) 1210 2 .1 3 28 H a z e abo ve 14.0 a m p ./s q .d m .; h a z e - b r ig h t 14 .0 to 3 .2 a m p ./s q .d m .; u n d e r, h a z e . 1220 2 .2 4 37 H a z e a t h ig h c u r r e n t d e n s ity e d g e . H azeb r ig h t above 6.5 a m p ./s q .d m .; u n d e r, h a z e . 1230 2 .2 0 57 H a z e ab o ve 15 .1 a m p ./s q .d m .; u n d e r, d u ll, p itt e d . 1240 2 25 75 D u ll , p itte d . 124 3 .7 5 28 E x f o lia t e . B r ig h t above 8.1 a r n p ./s q .d m ., h a z e 8.1 to 1.0 a m p ./s q .d m .; u n d e r, h a z e b r ig h t . 123 3.75 39 B r i g h t a t h ig h c u r r e n t d e n s ity ed g e. H a ze to d u ll above 3.2 a m p ./s q .d m .; h a z e - b r ig h t 3 .2 to 2 .6 a m p ./s q .d m .; u n d e r, d u ll. 122 3.80 58 H a z e - b r ig h t above d u ll. 121 3.6 5 74 D u ll , d a r k , p itte d . 1 1.8 a m p ./s q .d m .; u n d e r, Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 58 Tab le Panel No. l6 . S o lu tio n 13; the e f f e c t o f c in n a m a ld é h y d e in c o n c e n tr a tio n o f 0 .5 g . / l . on the a p p e a ra n c e o f W a tts n ic k e l s o lu tio n d e p o s its . pH Tem p. (° C a th o d e A p p e a ra n c e C .) 1340 2 .2 2 25 B u rn e d , e x fo lia te abo ve u n d e r, h a z e , p itte d . 1330 2 .2 0 38 H a z e , p itte d . 1320 2 .1 8 53 D u ll, p itt e d . 1310 2 .1 8 75 D u ll , p itte d . 134 3 .77 25 B u rn e d , e x fo lia te above 7.0 a m p ./s q .d m .; h a z e - b r ig h t 7 .0 to 3 .2 a m p ./s q .d m .; u n d e r, haze. 133 3.80 38 H a z e , p itte d . 132 3.50 58 H a z e , p itte d above u n d e r, d u ll. 131 3 .80 75 D u ll, d a r k . 1 1 .8 a m p ./s q .d m .; 1 0 .8 a m p ./s q .d m .; Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 59 T a b le Panel No. 17. S o lu tio n 26; the e f fe c t o f a c e ta ld e h y d e in c o n c e n tra tio n o f 0 .5 g . / l . on th e a p p e a ra n c e of W a tts n ic k e l s o lu tio n d e p o s its . pH Tem p. C atho de A p p e a ra n c e C c.) 2610 2 .2 0 26 E x f o lia t e . S e m ib r ig h t above d m .; u n d e r, h a z e . 2620 2 .2 5 38 H a z e a t h ig h c u r r e n t d e n s ity e d g e . S e m ib r ig h t above 8 .6 a m p ./s q .d m .; u n d e r, h a z e . 2630 2 .2 8 55 D u ll. 2640 2 .2 0 75 • D u ll. 264 3 .80 26 B u rn e d above 15.1 a m p ./s q .d m .; b r ig h t 15.1 to 8 .6 a m p ./s q .d m .; u n d e r, h a z e . 263 3.70 38 B r ig h t a t h ig h c u r r e n t d e n s ity ed g e. 262 3 .8 0 55 D u ll to h a z e . 261 3 .8 2 75 D u ll. 1 .6 a m p ./s q . D u ll. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 60 T a b le Panel No. 18. S o lu tio n 17; th e e f fe c t o f c h lo r a l in c o n c e n tr a tio n of 0 .5 g . / l . on th e a p p e a ra n c e o f W a tts n ic k e l s o lu tio n d e p o s its . pH Tem p. C a th o d e A p p e a ra n c e ( “ C .) 1740 2.2 0 23 E x f o lia t e above 1 1 .8 a m p ./s q .d m . H azeb r ig h t above 2 .1 a m p ./s q .d m .; u n d e r, h a z e . 1730 2 .2 5 37 H a z e - b r ig h t ab o ve haze. 1720 2 .2 2 56 D u ll. 1710 2 .2 5 75 D u ll, p itt e d abo ve 2.1 haze. 174 3.80 25 E x f o lia t e . H a z e - b r i g h t abo ve 6.5 a m p ./ s q .d m .; u n d e r, h a z e . 173 3.80 36 B r ig h t above 172 3.75 171 3 .7 8 56 75 1 1 .8 a m p ./s q .d m .; a m p ./s q .d m .; 1 1 .8 a m p ./s q .d m .; u n d e r, u n d e r, u n d e r, h a z e . H a z e above 8 .6 a m p ./s q .d m .; u n d e r, h a z e b r ig h t. D u ll, p itte d . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 61 T a b le Panel N o. 19. S o lu tio n 14; the e f fe c t o f p y r u v ic a c id in c o n c e n tr a tio n of 0 ,5 g . / l . on th e a p p e a ra n c e of W a tts n ic k e l s o lu tio n d e p o s its . pH Tem p. (° C atho de A p p e a ra n c e C .) 1440 2 .1 8 25 H a z e abo ve 14.0 a m p ./s q .d m .; h a z e - b r ig h t 14.0 to 2 .1 a m p ./s q .d m .; u n d e r , h a z e . 1430 2 .20 38 H a z e - b r i g h t above 14.0 a m p ./s q .d m .; u n d e r, haze. 1420 2 .1 0 53 D u ll. 1410 2 .1 0 75 D u ll, d a r k . 144 3.73 25 E x fo lia te abo ve 14.0 a m p ./s q .d m .; b r ig h t 1 4.0 to 7 .0 a m p ./s q .d m .; u n d e r, h a z e . 143 3.50 38 B r i g h t a t h ig h c u r r e n t d e n s ity ed g e. 142 3.50 58 D u ll above 1 0 .8 a m p ./s q .d m .; u n d e r, d u ll, p it t e d , d a r k . 141 3,60 75 D u ll, p itt e d , d a r k . D u ll. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 62 Tab le 2 0 . S o lu tio n 40; the e f fe c t o f b u ty l c h lo r a l in c o n c e n tra tio n s o f 0 .5 g . / l . an d 2 .0 g . / l . on the a p p e a ra n c e o f W a tts n ic k e l s o lu tio n d e p o s its . Panel p tl Tem p. (® C ) » C a th o d e A p p e a ra n c e ' 0 .5 g . / l . B u ty l C h lo r a l 410 2 .1 3 25 E x fo lia te abo ve 1 1 .8 a m p ./s q .d m .; h a z e b r ig h t 1 1 .8 to 5 .4 a m p ./s q .d m .; u n d e r, h a z e . 420 2 .2 5 38 H a z e a t h ig h c u r r e n t d e n s ity e d g e. H aze- b r ig h t ab o ve 14,0 a m p ./s q .d m .; u n d e r, h a z e . 430 2 .5 0 55 H a z e - b r ig h t a t h ig h c u r r e n t d e n s ity edge. D u ll. 440 2 .2 5 74 D u ll above 6 .5 a m p ./s q .d m .; d a rk . 401 3.7 0 24 E x fo lia te haze. 402 3.5 0 35 D u ll above 9 .0 a m p ./s q .d m .; 40 3 3.6 5 55 H a z e - b r i g h t a t h ig h c u r r e n t d e n s ity ed g e. H aze. 404 3.6 5 73 H aze. above u n d e r, d u ll, 11 .8 a m p ./s q .d m .; u n d e r, u n d e r, h a z e . 2 .0 g . / l . B u ty l C h lo r a l 450 2 .2 2 24 E x fo lia te above 11 .8 a m p ./s q .d m .; u n d e r, b r ig h t . 460 2 .2 0 35 H a z e above 2 .6 a m p ./s q .d m .; u n d e r, b r ig h t . 470 2 .2 5 56 D u ll above 9 .7 a m p ./s q .d m .; u n d e r, b r ig h t. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 63 T a b le 20 (C o n tin u ed ) Tem p. Panel N o. pH 480 - 70 D u ll a t h ig h c u r r e n t d e n s ity ed g e. H azeb r ig h t above 14.0 a m p ./s q .d m .; u n d e r, h a z e , d a rk . 40 5 3.70 24 E x f o lia t e above h a z e - b r ig h t . 40 6 3.60 35 H a z e above 6 .5 a m p ./s q .d m ,; u n d e r, s e m ib r ig h t . 407 3.60 55 H a z e - b r ig h t above haze. 408 3.80 75 H aze. C ath o d e A p p e a ra n c e ( “ C .) 11.8 a m p ./s q .d m .; u n d e r, 13.0 a m p ./s q .d m .; u n d e r, Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 64 T a b le 21. Panel No. S o lu tio n 15; the e f fe c t o f b e t a - m e t h y l u m b e llife r o n e in c o n c e n tra tio n o f 0 .5 g . / l . on the a p p e a ra n c e o f W a tts n ic k e l s o lu tio n d e p o s its . pH Tem p. r C a th o d e A p p e a ra n c e c .) 1540 2 .2 2 25 B u rn e d , e x fo lia te abo ve 11 .8 a m p ./s q .d m .; h a z e - b r ig h t 1 1 .8 to 1.0 a m p ./s q .d m .; u n d e r, haze, T530 2 .20 38 H a z e - b r ig h t above 8 ,6 a m p ./s q .d m .; haze. 1520 2 .1 8 53 H a i e to d u ll. 1510 2.2 0 75. D u ll. 154 3.80 , 25 B u rn e d and e x fo lia te unde r , h a z e . 153 3.7 5 38 H a z e a t h ig h c u r r e n t d e n s ity ed g e. H azeb r ig h t above 13.0 a m p ./s q .d m .; u n d e r, h a z e . 152 3 ,88 58 D u ll. 151 3.80 75 D u ll. u n d e r, above 6.5 a m p ./s q .d m .; Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 65 F ig u r e 10. T h e e ffe c t o f c a rb o n y l com pounds on th e a p p e a ra n c e o f W a tts n ic k e l d e p o s its a t p H 2 .2 . Reproduced wfth permission o f the copyright owner. Further reproduction prohlM ed whhou, permission. 6 6 F ig u r e 11. T h e e ffe c t o f c a rb o n y l com pounds on th e a p p e a ra n c e o f W a tts n ic k e l d e p o s its a t p H 2 .2 . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 67 m i’ é .r -mm F ig u r e 1 2 . T h e e ffe c t o f c a rb o n y l com pounds on th e a p p e a ra n c e o f W a tts n ic k e l d e p o s its a t p H 3 .8 . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 68 F ig u r e 13. T h e e ffe c t o f c a rb o n y l com pounds on the a p p e a ra n c e o f W a tts n ic k e l d e p o s its a t p H 3 .8 . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 69 T a b le 2 2 . Panel No. S o lu tio n 28; th e e f fe c t o f M o n a s t r a l B l u e * in c o n c e n tra tio n o f 0 .5 g . / l . on th e a p p e a ra n c e of W a tts n ic k e l s o lu tio n d e p o s its . pH Tem p. C atho de A p p e a ra n c e ( “ C .) 2810 2 .2 0 26 H a z e above 1 0 .8 a m p ./s q .d m .; s e m ib r ig h t 10.8 to 4 .3 a m p ./s q .d m .; u n d e r, h a z e . 2820 2 .1 7 38 H a z e a t h ig h c u r r e n t d e n s ity e d g e . S e m ib r ig h t abo ve 1 0 ,8 a m p ./s q .d m .; u n d e r, d u ll. 2830 2 .2 4 55 D u ll, b lu e sp o ts. 2840 2 .2 2 75 D u ll, b lu e s p o ts . 284 3.60 26 B u rn e d a t h ig h c u r r e n t d e n s ity ed g e. H aze, p it t e d above 1 1 .8 a m p ./s q .d m .; h a z e - b r ig h t 11.8 to 4 ,3 a m p ./s q .d m .; u n d e r ,- h a z e . 283 3.50 38 H a z e - b r ig h t a t h ig h c u r r e n t d e n s ity ed g e. D u ll, b lu e spo ts. 282 3.70 55 D u ll, b lu e 281 3.80 75 D u ll, b lu e spo ts. sp o ts. * I t w as n e c e s s a r y to use t r a c e a m o u n ts of so d iu m l a u r y l su lfo n a te and a fe w d ro p s of e th a n o l to suspend the d ye . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 70 T a b le 2 3 , S o lu tio n 31; the e f fe c t C la y to n Y e llo w in 0 ,5 g . / l . co n ­ c e n tr a tio n on the a p p e a ra n c e o f W a tts n ic k e l s o lu tio n d e p o s its . Panel No. pH Tem p. C atho de A p p e a ra n c e ( “ C .) 3110 2 .2 0 27 H aze, 3120 2 .1 7 35 H a z e , s t r e a k e d - b r ig h t above 3130 2 .2 0 55 H a z e - b r ig h t , p itte d above 1 1 .8 a m p ./s q .d m .; h a z e 1 1 .8 to 1.0 a m p ./s q .d m .; u n d e r, b r ig h t s tre a k , h aze. 3140 2 .2 1 75 D u ll a t h ig h c u r r e n t d e n s ity edge. H aze, p itt e d above 6.5 a m p ./s q .d m .; u n d e r, d u ll. 311 3.90 ■•'27 312 3 .6 8 37 H a z e abo ve 10.8 a m p ./s q .d m .; 4 .3 a m p l/s q .d m .; u n d e r, h a z e . 313 3 .6 5 56 D u ll ab o ve 10,8 a m p ./s q .d m .; u n d e r, h a z e . 314 3.70 72 D u ll, d a r k . s tre a k e d . 1.0 a m p ./s q .d m . H a z e to s e m ib r ig h t. d u ll 10,8 to Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 71 T a b le Panel No. 24, S o lu tio n 32; the e f fe c t o f P r i m u li n e Y e llo w in 0 .5 g . / l . c o n c e n tra tio n on the a p p e a ra n c e o f W a tts n ic k e l s o lu tio n d e p o s its . pH Tem p. C ath o d e A p p e a ra n c e ( “ C .) 3210 2 .1 2 27 H aze. 3220 2 .1 8 37 H a z e above 3230 2 .20 56 H a z e - b r ig h t r in g above D u ll. 3240 2.20 71 D u ll above 1 0 .8 a m p ./s q .d m .; h a z e - b r ig h t 1 0 ,8 to 5 .9 a m p ./s q .d m .; u n d e r , h a z e . ' 321 3.60 27 H a z e above 5 .4 a m p ./s q .d m .; u n d e r, h a z e b r ig h t . 322 3 .6 4 37 S e m ib r ig h t a t h ig h c u r r e n t d e n s ity ed g e. H a z e above 9 .7 a m p ./s q .d m .; d u ll 9 .7 to 4 .3 a m p ./s q .d m ., u n d e r, d a r k g r a y , d u ll. 323 3.85 56 H a z e a t h ig h c u r r e n t d e n s ity r in g . D u ll, d a rk above 9 .7 a m p ./s q .d m .; u n d e r, h a ze to d u ll. 324 3 .8 8 72 D u ll, d a r k . 1.0 a m p ./s q .d m .; u n d e r, b r ig h t . 13.0 a m p ./s q .d m . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 72 T a b le 2 5 . Panel No. S o lu tio n 33; the e f fe c t o f M e th y le n e B lu e in 0 .5 g . / l . co n ­ c e n tr a tio n on the a p p e a ra n c e of W a tts n ic k e l s o lu tio n d e ­ p o s it s ,' pH Tem p. r c.) C atho de A p p e a ra n c e 3310 2 .2 0 27 D y e d e p o s ite d p r e f e r e n t ia lly ^ c u r r e n t d e n s ity ed g e. 3320 2 .2 0 37 D y e d e p o s ite d p r e f e r e n t ia ll y , s tr a in e d n ic k e l a t h ig h c u r r e n t d e n s ity e d g e . 3330 2 .2 5 56 D y e d e p o s ite d p r e f e r e n t ia lly ; s q .d m .; s tr a in e d n ic k e l. 3340 2 .2 5 71 D y e d e p o s ite d p r e f e r e n t ia lly ; above 14.0 a m p ./s q .d m .; u n d e r, s t r a in e d n ic k e l. 331 3.60 27 332 3.60 37 D y e d e p o s ite d , t r e e d n ic k e l, 333 3.50 56 D y e d e p o s ite d , t r e e d n ic k e l ; above 4 .3 a m p . / s q .d m ., s tr a in e d . 334 3.00 72 D y e d e p o s ite d , t r e e d n ic k e l; above 6.5 a m p . / s q .d m ., s tr a in e d . , b u rn e d a t h ig h above 3.2 a m p . D y e d e p o s ite d , t r e e d n ic k e l, b u rn e d a t h ig h c u r r e n t d e n s ity edg e. s tr a in e d . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. ' T a b le 2 6 . Panel N o. ■ 73 S o lu tio n 34; the e f fe c t o f T o lu id in e B lu e in 0 .5 g . / l . c o n c e n tra tio n on the a p p e a ra n c e o f W a tts n ic k e l s o lu tio n d e p o s its . pH Tem p. (° c . ) C atho de A p p e a ra n c e 3410 2 .2 0 28 D y e d e p o s ite d p r e f e r e n t ia ll y , b u rn e d a t h ig h c u r r e n t d e n s ity ed g e. 3420 2 .2 0 37 D y e d e p o s ite d p r e f e r e n t ia ll y . 3430 2 .2 5 56 D y e d e p o s ite d p r e f e r e n t ia ll y , n ic k e l. 3440 2 .2 2 74 D y e d e p o s ite d , t r e e d n ic k e l. 341 3.80 27 D y e d e p o s ite d , t r e e d n ic k e l, b u rn e d a t h ig h c u r r e n t d e n s ity edg e. 342 3.70 37 D y e d e p o s ite d , t r e e d n ic k e l; above a m p . / s q .d m ., t r e e d . 343 3;80 56 D y e d e p o s ite d , t r e e d n ic k e l above 14.0 a m p ./ s q .d m . S tr a in e d a t h ig h c u r r e n t d e n s ity edge 344 3.10 72 D y e d e p o s ite d , t r e e d n ic k e l; 14.0 a m p ./s q .d m . s p a rs e tr e e d 1 0.8 s tr a in e d above Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 74 F ig u r e 14. T h e e ffe c t of d yes on th e a p p e a ra n c e o f W a tts n ic k e l d e p o s its a t p H 2 .2 . Reproduced with permission o f the copyright owner. Further reproduction prohibited without permission. 75 ï I F ig u r e 15. T h e e ffe c t o f dyes on the a p p e a ra n c e of W a tts n ic k e l d e p o s its a t p H 3 .8 . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 76 T a b le 27, Panel No. S o lu tio n 30; ■the e ffe c t of 4 j4 * -d ih y d r o x y b ip h e n y l in c o n ­ c e n tr a tio n of 0 .3 g . / l . on the a p p e a ra n c e of W a tts n ic k e l s o lu tio n d e p o s its . pH Tem p. (° C ath o d e A p p e a ra n c e C .) 3010 3.60 26 E x fo lia te a t h ig h c u r r e n t d e n s ity ed g e. above 4 .3 a m p ./s q .d m .; u n d e r, d u ll. 3020 3 .8 2 37 H a z e above 3030 3.80 56 , H a z e to d u ll above u n d e r, d u ll. 3040 3.80 75 D u ll, h a z e - b r ig h t rin g a t 11.8 a m p ./s q .d m . 301 2 .1 9 27 E x fo lia te a t h ig h c u r r e n t d e n s ity edg e. S e m ib r ig h t above 6 ,5 a m p ./s q .d m .; u n d e r, h a z e . 302 2 .2 0 37 S e m ib r ig h t a t h ig h c u r r e n t d e n s ity edge. H a z e abo ve 9 .0 a m p ./s q .d m .; u n d e r, d u ll. 30 3 2.2 0 54 H a z e a t h ig h c u r r e n t d e n s ity ed g e. 304 2 .2 7 77 D u ll above 1.0 a m p ./s q .d m .; h a ze 0 .5 a m p ./s q .d m .; u n d e r, d u ll. 10.8 a m p ./s q .d m .; H aze u n d e r, d u ll. 1 1 .8 a m p ./s q .d m .; D u ll. 1,0 to Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 77 T a b le 28. Panel N o. S o lu tio n 27; the e f f e c t o f 3 , 5 , 3 ', 5 '- t e t r a n i t r o 4 ,4 '- d ih y d r o x y b ip h e n y l in c o n c e n tr a tio n o f 0 .3 g . / l . on the a p p e a ra n c e of W a tts n ic k e l s o lu tio n d e p o s its . pH . Tem p, C athode A p p e a ra n c e ( “ C .) 2710 2 .2 2 26 B u rn e d , s tr e s s e d above 8 .6 a m p ./s q .d m .; u n d e r , b r ig h t . 2720 2 .1 8 38 H a z e above 2730 2 .2 6 55 B r i g h t above 3 .2 a m p ./s q .d m .; u n d e r, d u ll. 2740 2 .2 0 75 B r ig h t above 274 2.80 26 B u rn e d above 2 .1 b r ig h t . 273 2.8 0 38 B u rn e d above b r ig h t . 272 3.55 55 B u rn e d a t h ig h c u r r e n t d e n s ity edge. Ex­ f o lia t e to ro u g h above 6 .5 a m p ./s q .d m .; u n d e r, h a z e - b r ig h t . 271 3.70 75 H a z e - b r ig h t , ro u g h above 8 .6 a m p ./s q .d m .; u n d e r , s e m ib r ig h t. 275 2 .5 5 63 B r ig h t above 3 .8 a m p ./s q .d m .; u n d e r, h a z e . 1.0 a m p ./s q .d m .; u n d e r, b r ig h t. 1.0 a m p ./s q .d m .; u n d e r, d u ll. a m p ./s q .d m .; 10 .8 a m p ./s q .d m .; u n d e r, h a z e - u n d e r, h aze [F iv e g r a m s o f 2 ,7 -n a p h th a le n e d is u lfo n ic a c id w as added to the s o lu tio n and d e p o s its m a d e a t 65° C .] 276 3.40 B r ig h t , s tre s s a t h ig h c u r r e n t d e n s ity . 277 2 .8 8 B r ig h t , s tre s s a t high c u r r e n t d e n s ity . 278 3.3 3 B r ig h t , som e ro u g h n ess. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 78 T a b le 28 (C o n tin u ed ) Tem p. Panel No. pH 279 5 .5 5 B r ig h t above 5 .4 a m p ./s q .d m .; u n d e r. h a z e b r ig h t . 2711 5 .1 6 B r i g h t above 5 .4 a m p ./s q .d m .; u n d e r. h a z e b r ig h t . 2712 3 .0 5 B r ig h t above 4 .3 a m p ./s q .d m .; u n d e r, h a z e b r ig h t . (° C .) C ath o d e A p p e a ra n c e Reproduced with permission of the copyright ownec Further reproduction prohibited without permission. 79 T a b le 2 9 . Panel N o. S o lu tio n 41; the e f fe c t o f p henol in c o n c e n tra tio n of 0 .5 g . / l . on the a p p e a ra n c e o f W a tts n ic k e l s o lu tio n d e p o s its . pH Tem p. (° C athode A p p e a ra n c e C .) 4110 2 .5 0 25 H a z e , e x fo lia te abo ve 14.0 a m p ./s q .d m .; h a z e to s e m ib r ig h t 14.0 to 9.0 a m p ./s q .d m .; u n d e r, h a z e . 4120 2 .2 0 38 H a z e a t h ig h c u r r e n t d e n s ity edg e. S e m i­ b r ig h t abo ve 10.8 a m p ./s q .d m .; u n d e r, h a z e . 4130 2 .5 0 55 D u ll. 4140 2 .2 5 74 D u ll. 411 3.00 24 E x fo lia te above 14.0 a m p ./s q .d m .; s e m i­ b r ig h t 14.0 to 2 .6 a m p ./s q .d m .; u n d e r, h a z e . 412 3.30 35 S e m ib r ig h t abo ve 13.0 a m p ./s q .d m .; haze. 413 3 .7 5 55 D u ll. 414 3 .5 5 73 D u ll ab o ve 14.0 a m p ./s q .d m .; d u ll, d a r k to 2.1 a m p ./s q .d m .; u n d e r, h a z e . u n d e r, 14.0 [ F iv e g r a m s of 2 , 7 -n a p h th a le n e d is u lfo n ic a c id added to the s o lu tio n .] 415 3.50 24 E x fo lia te , b r ig h t abo ve u n d e r, b r ig h t . 416 3 .70 35 B r ig h t . 417 3.20 . 56 B r ig h t above 70 H aze. 418 - 11.8 a m p ./s q .d m .; 11.8 a m p ./s q .d m .; u n d e r, h a z e . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 80 T a b le Panel No. 30. S o lu tio n 4 2 ; the e ffe c t of o -n itr o p h e n o l in c o n c e n tra tio n of 0 .5 g . / l , on the a p p e a ra n c e o f W a tts n ic k e l s o lu tio n d e p o s its . pH Tem p. C atho de A p p e a ra n c e (° c j 4210 2 .50 25 E x f o lia t e , h a ze above 1 1 .8 a m p ./s q .d m .; unde r , h a z e . 4220 2 .2 2 38 H a z e abo ve 9 .0 a m p ./s q .d m .; s e m ib r ig h t 9.0 to 2 .6 a m p ./s q .d m .; u n d e r, h a z e . 4230 2 .50 55 D u ll, p itte d . 4240 2.00 74 D u ll above d a rk . 421 3.50 24 E x f o lia t e , h a ze abo ve 13.0 a m p ./s q .d m .; s e m ib r ig h t 13.0 to 7 .6 a m p ./s q .d m .; u n d e r, haze. 422 3.72 35 S e m ib r ig h t a t h ig h c u r r e n t d e n s ity edge. D u ll. 423 3.70 55 D u ll, p itte d . 424 3.80 73 D u ll above 6 .5 a m p ./s q .d m .; d a rk . [ F iv e 11.8 a m p ./s q .d m .; u n d e r, d u ll, g r a m s o f 2 ,7 -n a p h th a le n e d is u lfo n ic a c id added to the s o lu tio n . 425 3.75 24 E x fo lia te and b r ig h t above d m .; u n d e r, b r ig h t. 426 3.80 35 B r ig h t. 427 3 .62 56 ' B r ig h t. 428 - 70 u n d e r, d u ll, 1 1.8 a m p . /s q . B r ig h t above 6.5 a m p ./s q .d m .; u n d e r, h a z e b r ig h t. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 81 T a b le Panel No. 31. S o lu tio n 48; th e e f f e c t o f p -a m in b p h e n o l h y d r o c h lo r id e in c o n c e n tra tio n s o f 0 .5 g . / l . and 2,0 g . / l . on the a p p e a ra n c e o f W a tts n ic k e l s o lu tio n d e p o s its . pH Tem p. r C atho de A p p e a ra n c e c .) 0 .5 g . / l . p - A^m inophenol H y d r o c h lo r id e 4810 2 .20 25 E x f o lia t e . H a z e a t h ig h c u r r e n t d e n s ity edge S e m ib r ig h t above 5 .4 a m p ./s q .d m .; u n d e r, haze. 4820 2 .2 0 37 S e m ib r ig h t a t h ig h c u r r e n t d e n s ity ed g e. H a z e abo ve 9 .7 a m p ./s q .d m .; s e m ib r ig h t 9 .7 to 3 .2 a m p ./s q .d m .; u n d e r, h a z e . 4830 2 .2 2 55 D a r k h a z e , c r a c k e d above 4 .3 a m p ./s q .d m .; u n d e r, d u ll, d a r k . 4840 2.2 0 73 D a r k h a z e , c r a c k e d above u n d e r, d u ll, c r a c k e d . 481 3 .7 8 26 B r ig h t , e x fo lia te above 10.8 a m p ./s q .d m .; u n d e r, b r ig h t , c r a c k e d . 482 3.60 38 E x fo lia te . H a z e , c r a c k e d above s q .d m .; u n d e r, h a z e , e x fo lia te . 483 3 .8 6 56 H a z e , e x fo lia te . 484 3.80 76 D a r k , e x fo lia te and c ra c k e d , 14.0 a m p ./s q .d m .; 3.8 a m p . / 2 .0 g . / l . p - A m ino p h en o l H y d ro c h lo r id e 4850 2 .2 2 27 H a z e , e x fo lia te above u n d e r, b r ig h t. 4860 2 .2 2 38 E x fo lia te . B r ig h t. 14.0 a m p ./s q .d m .; H a z e a t h ig h c u r r e n t d e n s ity edge. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 82 T a b le Panel N o. pH Tem p. 31 (C o n tin u ed ) C atho de A p p e a ra n c e ( ■ C .) 4870 2 .2 2 58 B r ig h t , e x fo lia te above 14.0 a m p ./s q .d m .; s e m ib r ig h t 14.0 to 7 .6 a m p ./s q .d m .; u n d e r, haze. 4880 2 .2 2 75 B r ig h t above 14.0 a m p ./s q .d m .; h aze 9 .7 a m p ./s q .d m .; u n d e r, d u ll, d a r k . 485 3.60 26 B r ig h t , e x fo lia te above 14.0 a m p ./s q .d m .; b r ig h t 14.0 to 3.2 a m p ./s q .d m .; u n d e r, b r ig h t e x f o lia te . 486 3.50 38 B r ig h t , e x fo lia te . 487 3 .7 5 54 B r ig h t , 488 3.85 74 B r ig h t , e x fo lia te . 14.0 to e x f o lia te . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 83 T a b le Panel N o. 32. S o lu tio n 49; the e ffe c t of o -a m in o p h e n o l h y d ro c h lo rid e in c o n c e n tra tio n s of 0 .5 g . / l . and 2.0 g . / l . on the a p ­ p e a ra n c e of W a tts n ic k e l s o lu tio n d e p o s its . pH Tem p. (° C athode A p p e a ra n c e C .) 0 .5 g . / l . o -A m in o p h e n o l H y d r o c h lo r id e 4910 2.20 25 E x fo lia te a t h ig h c u r r e n t d e n s ity edg e. H a z e above 2 .1 a m p ./s q .d m .; u n d e r, s e m i­ b r ig h t . 4920 2. 2 2 37 H a z e above 9 .7 a m p ./s q .d m .; h a z e -b r ig h t 9 .7 to 4 .3 a m p ./s q .d m .; u n d e r, s e m ib r ig h t. 4930 2 .1 8 55 D u ll, c r a c k e d above 8. 6 a m p ./s q .d m .; u n d e r , h a ze . 4940 2.20 73 D u ll, d a r k . dm . 491 3.60 26 E x f o lia t e . D a r k , h a ze , c ra c k e d . 492 3.80 38 E x f o lia t e . D a r k , h a z e , c ra c k e d . 493 3 .8 6 56 D a rk , d u ll, c r a c k e d . 494 3 .6 5 76 D a rk , d u ll, c ra c k e d . H aze r in g a t 14.0 a m p ./s q . 2.0 g . / l . 0 - A m inophe no 1 H y d r o c h lo r id e 4950 2 .2 3 27 H a z e , c r a c k e d above 10.8 a m p ./s q .d m .; h a z e - b r ig h t , c ra c k e d 10.8 to 3.2 a m p ./ sq. d m .; u n d e r, s e m ib r ig h t. 4960 2.20 38 C r a c k e d , e x fo lia te , haze above 6.5 a m p ./ s q .d m .; u n d e r, s e m ib r ig h t. 4970 2 .2 4 58 H aze. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 84 T a b le Panel No. pH Tem p. r c .) 32 (C o n tin u ed ) C athode A p p e a ra n c e 4980 2 .2 3 75 H a z e , c r a c k e d above 4 .3 a m p ./s q .d m ,; b la c k . 495 3.75 26 E x fo lia te , d u ll above 1 0 .8 a m p ./s q .d m .; u n d e r, d a r k , h a z e , c r a c k e d . 496 3.80 38 H a z e , e x fo lia te above 10.8 a m p ./s q .d m .; u n d e r, d a r k , c ra c k e d , h a z e -b r ig h t . 497 3.70 ' 54 D u ll, e x fo lia te above 1 3.0 a m p ./s q .d m .; u n d e r, d a r k , h a z e , c r a c k e d . 498 3.80 74 D u ll, e x fo lia te , b la c k above 15.1 a m p ./s q . d m .; u n d e r, d a r k , d u ll, c ra c k e d . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. d u ll, 85 T a b le 33, Panel No. S o lu tio n 50; the e ffe c t o f c a te c h o l in c o n c e n tra tio n s of 0 .5 g . / l . and 2.p' g . / l . on the a p p e a ra n c e of W a tts n ic k e l s o lu tio n d e p o s its : pH Tem p. (° C athode A p p e a ra n c e C .) ' 0 .5 g . / l . C a te c h o l 5010 2 .2 0 25 E x fo lia te . D u ll above unde r , h a z e . 5020 2 .2 0 37 S e m ib r ig h t a t h ig h c u r r e n t d e n s ity edge. H a z e , p itte d above 9 .7 a m p ./s q .d m .; d u ll 9 .7 to 2 .6 a m p ./s q .d m .; u n d e r, h a z e . 50 30 2 .2 5 55 H a z e above p itt e d . 5040 2.20 73 D u ll. 501 3,80 26 E x fo lia te . H a z e above 14.0 a m p ./s q .d m .; s e m ib r ig h t 14.0 to 7 .6 a m p ./s q .d m .; u n d e r, haze. 502 3.80 38 H a z e a t h ig h c u r r e n t d e n s ity edge. H azeb r ig h t above 14.0 a m p ./s q .d m .; u n d e r, d u ll. 50 3 3.90 56 D u ll. 504 3 .6 5 76 D u ll. 2.0 g . / l . 10.8 a m p ./s q .d m .; 14.0 a m p ./s q .d m .; u n d e r, d u ll, C a te c h o l 5050 2 .2 0 27 E x f o lia t e . H a z e - b r ig h t above 3.8 a m p ./s q . d m .; u n d e r, h a z e . 50 60 2 .2 0 38 H a z e a t h ig h c u r r e n t d e n s ity edg e. H azeb r ig h t above 11.8 a m p ./s q .d m .; d u ll 11.8 to 2 .6 a m p ./s q .d m .; u n d e r, h a ze . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 86 T a b le Panel No. pH 33 (C o n tin u ed ) Tem p. C athode A p p e a ra n c e (° C .) 5070 2 .2 5 58 H a z e - b r ig h t a t hig h c u r r e n t d e n s ity edg e. D u ll. 5080 2 .2 5 75 D u ll. 505 3 .8 3 26 E x fo lia te . H a z e above 14.0 a m p ./s q .d m .; h a z e - b r ig h t 14.0 to 8 .6 a m p ./s q .d m .; u n d e r, haze. 50 6 3.85 38 H a z e - b r ig h t a t h ig h c u r r e n t d e n s ity edge. H a z e above 4 .3 a m p ./s q .d m .; u n d e r, h a z e b r ig h t to h a z e . 50 7 3.80 54 D u ll, p itte d above 2.1 haze. 508 3.80 74 D u ll, p itte d . a m p ./s q .d m .; u n d e r, Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 87 T a b le Panel N o. 34. S o lu tio n 51; the e ffe c t of r e s o r c in o l in c o n c e n tra tio n s of 0 .5 g . / l . and 2 .0 g . / l . on the a p p e a ra n c e of W a tts n ic k e l s o lu tio n d e p o s its . pH Tem p. (° C athode A p p e a ra n c e C .) 0 .5 g . / l . R e s o r c in o l 5110 2.20 25 E x f o lia t e . H a z e above 10.8 a m p ./s q .d m .; s e m ib r ig h t 10.8 to 5.4 a m p ./s q .d m .; u n d e r, haze. 5120 2,20 37 H a z e a t h ig h c u r r e n t d e n s ity ed g e. S e m i­ b r ig h t above 10.8 a m p ./s q .d m .; u n d e r, h a z e . H a z e - b r ig h t rin g a t 2 .6 a m p ./s q .d m .; p itte d . 5130 2.20 55 P it t e d a t h ig h c u r r e n t d e n s ity . D u ll. 5140 2.20 73 P it t e d a t h ig h c u r r e n t d e n s ity . D u ll. 511 3 .8 3 26 E x fo lia te . H a z e , p itte d above 14.0 a m p ./s q . d m .; h a z e - b r ig h t 14.0 to 9.7 a m p ./s q .d m .; u n d e r, h a z e . 512 3.80 38 H a z e a t h ig h c u r r e n t d e n s ity edg e. B r ig h t above 13.0 a m p ./s q .d m .; u n d er, d u ll. 513 3.60 56 D u ll. 514 3 .75 76 D u ll, p itte d a t lo w c u r r e n t d e n s itie s . ■ 2 .0 g . / l . R e s o r c in o l 5150 2 .2 3 27 E x fo lia te a t h ig h c u r r e n t d e n s ity edge. H a z e , p itte d above 13.5 a m p ./s q .d m .; h a z e b r ig h t 13.5 to 6.5 a m p ./s q .d m .; u n d er, h a ze . 5160 2.20 38 H a z e a t h ig h c u r r e n t d e n s ity ed g e. S e m i­ b r ig h t above 10.8 a m p ./s q .d m .; u n d e r, h aze . H a z e b r ig h t rin g a t 2 .6 a m p ./s q .d m .; p itte d . 1 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 88 T a b le Panel N o. pH 34 (C o n tin u ed ) Tem p. C athode A p p e a ra n c e ( “ C .) 5170 2.20 5180 2.20 75 D u ll. 515 3.78 26 B u rn e d a t h ig h c u r r e n t d e n s ity ed g e. H a ze above 14.0 a m p ./s q .d m .; h a z e -b r ig h t 14.0 to 8 .6 a m p ./s q .d m .; u n d e r, h a ze . 516 3.85 38 H a z e a t h ig h c u r r e n t d e n s ity edg e. H azeb r ig h t above 14.0 a m p ./s q .d m .; u n d e r, h aze to d u ll. ^ 517 3.80 54 D u ll, 518 3.70 74 H a z e above ' 58 . P it t e d a t h ig h c u r r e n t d e n s ity . 11.8 a m p ./s q .d m .; D u ll. u n d e r, d u ll. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 89 T a b le Panel No. 35. S o lu tio n 52; the e ffe c t of b e ta -n a p th o l in c o n c e n tra tio n of 0 .5 g . / l . on the a p p e a ra n c e o f W a tts n ic k e l s o lu tio n d e p o s its . pH Tem p. i° C ath o d e A p p e a ra n c e C.) 5210 2 .2 0 26 B u rn e d , e x fo lia te above 8 .6 • a m p ./s q .d m .; h a z e - b r ig h t 8 .6 to 6.5 a m p ./s q .d m .; u n d e r, haze. ■ 5220 2 .2 0 38 B u rn e d , e x fo lia te above 10.8 a m p ./s q .d m .; h a ze 1 0 .8 to 0 .5 a m p ./s q .d m .; u n d e r, d u ll, d a rk . 5230 2 .2 2 54 B u rn e d a t h ig h c u r r e n t d e n s ity edg e. d a rk . 5240 2 .2 1 74 H a z e a t h ig h c u r r e n t d e n s ity ed g e. d a rk . 521 3.70 25 B u rn e d , e x fo lia te above 9 .7 a m p ./s q .d m .; h a z e - b r ig h t 9 .7 to 1.0 a m p ./s q .d m .; u n d e r, haze. 522 3.70 36 B u rn e d , e x fo lia te above 1 0 .8 a m p ./s q .d m .; h a z e - b r ig h t 10.8 to 9 .0 a m p ./s q .d m .: u n d e r, haze. 523 3 .70 57 B r ig h t a t h ig h c u r r e n t d e n s ity edg e. 524 3 .7 8 75 H aze. D u ll, D u ll, H aze. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 90 .-•pasiiï. ,;m«T: Î2 a R i ' 1 . 1 1 !.. -, # ' S N O .-•-swr^ , 1 I 1 itw.. 1 k & « .'• .. À.-** « w i •v < # M ,/ ... Ç I 1 1 1 » -- » » 1 1 1 i F ig u r e 16. T h e e ffe c t o f p h e n o ls on the a p p e a ra n c e of W a tts n ic k e l d e p o s its a t p H 2 .2 . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 91 h • F ig u r e 17. T h e e ffe c t o f p h en o ls on th e a p p e a ra n c e of W a tts n ic k e l d e p o s its a t p H 2 2 .. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 92 F ig u r e 18. T h e e ffe c t o f p h e n o ls on th e a p p e a ra n c e o f W a tts n ic k e l d e p o s its a t p H 3 .8 . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 93 ^ 421 F ig u r e 19. T h e e ffe c t o f p h e n o ls on th e a p p e a ra n c e o f W a tts n ic k e l d e p o s its a t p H 3 .8 . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 94 T ab le 36. The e ffe c t of 5 g . / I . of 2 , 7 , -n a p h th a le n e d is u lfo n ic a c id on the a p p e a ra n c e of W a tts n ic k e l s o lu tio n d e p o s its . 1 Tem p. Panel No. pH 4 1 1 -1 3.50 25 D u ll, e x fo lia te u n d e r, b r ig h t. 4 1 1 -2 3.60 35 D u ll, e x fo lia te a t h ig h c u r r e n t d e n s ity ed g e. B r ig h t . 4 1 1 -3 3.60 48 B r ig h t above 4 .3 a m p ./s q .d m .; u n d e r. d u ll. 4 2 1 -3 3.70 58 B r ig h t , p itte d above 9 .7 a m p ./s q .d m .; u n d e r , d u ll, p itte d . 4 2 1 -2 3.70 62 B r ig h t , p itte d above d u ll. 4 2 1 -1 3.60 67 H aze. C atho de A p p e a ra n c e ( “ C .) above 1 1 .8 a m p ./s q .d m , ; 14.0 a m p ./s q .d m .; under. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 95 T a b le 37. S o lu tio n 371; the e ffe c t o f 5.0 g . / I . of 2 , 7 -n a p h th a le n e d is u lfo n ic a c id and in c r e a s in g c o n c e n tra tio n s o f g lucose on the a p p e a ra n c e o f W a tts n ic k e l s o lu tio n d e p o s its . G1 ucose Panel No. pH Tem p. ( “ C .) A d d i. tio n (g.) T o ta l A d d i­ tio n C a th o d e A p p e a ra n c e (g.) ' 3 7 1 -1 3.80 64 - 3 7 1 -2 3.50 67 0 .0 0 1 ' 0 .0 0 1 B r ig h t ab o ve 14.0 a m p . / s q. d m .; u n d e r, h a ze . p itte d . 3 7 1 -3 3 .5 3 65 0 .0 0 2 0 .0 0 3 B r ig h t ab o ve 14.0 a m p . / s q. d m .; u n d e r, h a ze . p itte d . 3 7 1 -4 3.70 66 0 .0 0 4 0 .0 0 7 B r ig h t ab o ve 14.0 a m p . / s q. d m .; u n d e r, h a z e . p itte d . 3 7 1 -5 3 .6 5 65 0 .0 0 8 0 .0 1 5 B r ig h t ab o ve 14.0 a m p . / s q. d m .; u n d e r, h a ze . p itte d . 3 7 1 -6 3 .8 8 65 0 .0 1 6 0 .0 31 B r ig h t abo ve 14.0 a m p . / s q. d m .; u n d e r, h a ze . p itte d . 3 7 1 -7 3 .7 2 65 0 .0 3 2 0 .0 6 3 B r ig h t abo ve 14.0 a m p . / s q. d m .; u n d e r, h a z e , p itte d . 3 7 1 -8 3 .8 5 65 0 .0 6 4 0 .1 2 7 B r ig h t abo ve 14.0 a m p ./s q . d m .; u n d e r, h a ze . p itte d . 3 7 1 -9 3 .7 6 65 0 .1 2 8 0 .2 5 5 B r ig h t abo ve 14.0 a m p ./ sq. d m .; u n d e r, h a ze . p itte d . 3 7 1 -1 0 3 .8 2 65 0 .2 5 6 0 .5 1 1 B r ig h t above 14.0 am p ./s q . d m .; u n d e r, h a ze . p itte d . - H a z e , p itt e d . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 96 T a b le 37 (C o n tin u e d ) G lu c o s e Panel No. pH Tem p. r C .) A d d i­ tio n (g.) T o ta l A d d i­ tio n 1 C ath o d e A p p e a ra n c e (g.) T h e E f f e c t of T e m p e r a tu r e a t C o n c e n tr a tio n of P a n e l 3 7 1 -1 0 3 7 1 -1 1 • 25 B r ig h t above 11.8 a m p ./s q . d m .; u n d e r, h aze to d u ll. 3 7 1 -1 2 38 B r ig h t . 3 7 1 -1 3 52 B r ig h t. 3 7 1 -1 4 60 H a z e - b r ig h t , p itte d . T r e a t e d S o lu tio n w ith 0 .5 g . / l . 3 7 1 -1 5 60 o f A c tiv a te d C a rb o n H a z e above 11.8 a m p . /s q . d m .; b r ig h t 11.8 to 2.1 a m p ./s q .d m .; u n d er, h a z e . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 97 Table 38. S o lu tio n 381; th e e ffe c t of 5.0 g . / l . o f 2 ,7 -n a p h th a le n e d is u lfo n ic a c id and in c r e a s in g c o n c e n tra tio n s o f c h lo r a l o n ' the a p p e a ra n c e o f W a tts n ic k e l s o lu tio n d e p o s its . C h lo r a l Panel No. pH Tem p. ( “ C .) A d d itio n ( m l.) T o ta l A d d i­ tio n (m l./ C ath o d e A p p e a ra n c e g .)* 381 -1 3.77 64 3 8 1 -2 3 .6 3 67 0 .0 2 0 .0 2 / 0 .0 3 B r ig h t , p itte d above 14.0 a m p ./s q .d m .; u n d e r, h a z e . 3 8 1 -3 3.80 65 0 .0 4 0 .0 6 / 0 .0 9 B r ig h t , p itte d above 14.0 a m p ./s q .d m .; u n d e r, h a z e . - - H a z e , p itte d . 3 8 1 -4 3.62 66 0 .0 8 0 .1 4 / 0 .2 1 B r ig h t , p itte d above 10.8 a m p ./s q .d m .; u n d e r, h a z e . 3 8 1 -5 3.6 2 65 0.16 0 .3 0 / B r ig h t , p itte d above 10.8 a m p ./s q .d m .; u n d e r, h a z e . 0 .4 5 3 8 1 -6 3 .7 8 65 0 .3 2 0 .6 2 / 0 .9 3 M o ttle d h a ze and b r ig h t. 3 8 1 -7 3.65 65 0 .6 4 1.26 H a z e a t h ig h c u r r e n t den­ s it y ed g e. B r ig h t . 1.89 3 8 1 -8 3.85 65 0 .7 4 2 .0 0 / 3.01 B r ig h t above 1 0.8 a m p ./s q . d m .; h a ze 10.8 to 4 .3 a m p ./ s q .d m .; b r ig h t. 3 8 1 -9 3.8 5 65 2.0 4 .0 0 / 6 .0 3 H aze. i 3 8 1 -1 0 3.50 65 4 .0 8 .0 0 / 12.06 H a z e - b r ig h t above 5 .4 a m p . / s q .d m .; u n d e r, h a z e . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 98 T a b le 38 (C o n tin u e d ) C h lo r a l Panel No. PH A d d itio n (m l.) T o ta l A d d i­ tio n (m l./ C ath o d e A p p e a ra n c e g .)- T h e E f f e c t of T e m p e r a tu r e a t C o n c e n tra tio n of ■ P a n e l 3 8 1 -1 0 3 8 1 -1 1 28 B u rn e d above 11 .8 a m p ./ s q .d m .; b r ig h t 11.8 to 5 .4 a m p ./s q .d m .; u n d e r, d u ll. 3 8 1 -1 2 38 B r ig h t , p itte d above 8 .6 a m p ./s q .d m .; u n d e r, d u ll. 3 8 1 -1 3 52 B r ig h t , p itte d . 3 8 1 -1 4 60 B r ig h t . T r e a t e d S o lu tio n w ith 15 g . / l . 3 8 1 -1 5 60 of A c tiv a te d C a rb o n B r ig h t a t h ig h c u r r e n t den­ s ity ed g e. H a z e - b r ig h t above 5 .4 a m p ./s q .d m .; u n d e r, h a z e . * W e ig h ts c a lc u la te d using handbook v a lu e f o r s p e c ific g r a v ­ ity of c h lo r a l 1 .5 0 5 2 5 ° / 4 ° . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 99 Table 39. S o lu tio n S 6 l; the e f fe c t o f 5.0 g . / l . o f 2 ,7 -n a p h th a le n e d is u lfo n ic a c id and in c r e a s in g c o n c e n tra tio n s o f P V M / MAH« (p o ly m e th y l v in y l e t h e r and m a le ic a n h y d rid e ) on the a p p e a ra n c e o f W a tts n ic k e l s o lu tio n d e p o s its . P T M /M A Panel N o. pH Tem p, ( “ C .) tio n , . ir C ath o d e A p p e a ra n c e tio n '*•> (g.) 3 61 -1 3 .7 9 64 - - 3 6 1 -2 3 .7 5 67 0 .0 0 1 0 .0 0 1 B r ig h t above 14.0 a m p ./s q . d m .; u n d e r, h a z e . 3 6 1 -3 3 .3 5 65 0 .0 0 2 0 .0 0 3 B r ig h t above 14.0 a m p ./ s q .d m .; u n d e r, h a z e . 3 6 1 -4 3.30 66 0 .0 0 4 0 .0 0 7 B r ig h t above 14.0 a m p ./s q . d m .; u n d e r, h a z e . 3 6 1 -5 2 .9 0 65 0 .0 0 8 0 .0 1 5 B r ig h t above 14.0 a m p ./s q . d m .; u n d e r, h a z e . 3 6 1 -6 3.20 65 0.016 0 .0 3 1 B r ig h t above 1 0 .8 a m p ./s q . d m .; u n d e r, h a z e -b r ig h t . 3 6 1 -7 3 .0 2 65 0 .0 3 2 0 .0 6 3 B r ig h t , fe w w h ite 3 6 1 -8 3 .0 5 65 0 .0 6 4 0 .1 2 7 B r ig h t above 4 .3 a m p ./s q , d m .; u n d e r, h a z e -b r ig h t . 3 6 1 -9 3 .0 5 65 0 .1 2 8 0 .2 5 5 B r ig h t above 3 .2 a m p ./s q . d m .; u n d e r, h a z e -b r ig h t . 3 6 1 -1 0 3 .0 0 65 0 .2 5 6 0 .5 1 1 D u ll, ro u g h w ith b r ig h t unde r to n e . H aze. spots. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 100 T a b le 39 (C o n tin u ed ) P V M /M A Panel No. pH A d d itio n (g.) T o ta l A d d i­ tio n C ath o d e A p p e a ra n c e (g.) The E f f e c t o f T e m p e r a tu r e a t C o n c e n tra tio n s of P a n e l 3 6 1 -1 0 361-11 28 D u ll a t h ig h c u r r e n t d e n s ity B r ig h t . 36 1 -1 2 38 B r ig h t . 36 1 -1 3 52 B r ig h t . 3 6 1 -1 4 60 B r ig h t . T r e a t e d S o lu tio n w ith 3 6 1 -1 5 B r ig h t above 5 ,4 a m p ./s q . d m .; u n d e r, h a z e . 60 * S p e c ific v is c o s ity , 15 g . / l . A c tiv a t e d C a rb o n 2 .6 . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 101 Tab le 40. S o lu tio n 46; the e f fe c t o f 5.0 g . / l . o f 2 ,7 -n a p h th a le n e d i­ s u lfo n ic a c id and in c r e a s in g c o n c e n tra tio n s o f a c r y lic a c id on the a p p e a ra n c e of W a tts n ic k e l s o lu tio n d e p o s its . A c r y l i c A c id Panel No. pH Tem p. (° C .) A d d i­ tio n (g.) T o ta l A d d i­ tio n C atho de A p p e a ra n c e (g.) 4 6 -1 3.75 65 - - B r ig h t above 14.0 a m p ./s q . d m .; u n d e r, h a z e . 4 6 -2 3 .72 65 0 .0 0 1 0 .0 0 1 B r ig h t above 14.0 a m p ./s q . d m .; u n d e r, h a z e , p itte d . 4 6 -3 3.72 65 0 .0 0 2 0 .0 0 3 B r ig h t above 14.0 a m p ./s q . d m .; u n d e r, h a z e , p itte d 4 6 -4 3.80 65 0 .0 0 4 0 .0 0 7 B r ig h t above 14.0 a m p ./s q . d m .; u n d e r, h a z e , p itte d . 4 6 -5 3.70 64 0 .0 0 8 0 .0 1 5 B r ig h t above 1 1 .8 a m p ./s q . d m .; u n d e r, h a z e , p itte d . 4 6 -6 3.61 64 0 .0 1 6 0 .0 3 1 B r ig h t, p itte d above 11.8 a m p ./s q .d m .; u n d e r, h a z e , p itte d . 4 6 -7 3.60 65 0 .0 3 2 0 .0 6 3 B r ig h t , p itte d above 11.8 a m p ./s q .d m .; u n d e r, h a z e , p itte d . 4 6 -8 3.4 5 64 0 .0 6 4 0 .1 2 7 B r ig h t above 7 .6 a m p ./s q . d m .; u n d e r, h a z e , p itte d . 4 6 -9 3 .4 9 66 0 .1 2 8 0 .2 5 5 B r ig h t above 4 .3 a m p ./s q . dm .; u n d e r, h a z e . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 102 T a b le 40 (C o n tin u ed ) A c r y li c A c id Panel No. pH Tem p, ( “ c .) T o ta l A d d i­ tio n (g.) A d d i­ tio n -- C ath o d e A p p e a ra n c e ( g .r 4 6 -1 0 3 .3 5 66 0 .2 5 6 0 .5 1 1 B r ig h t above 1 .6 a m p ./s q . d m .; u n d e r, h a z e . 4 6 -1 1 3 .2 3 65 0 .5 1 2 1 .0 2 3 B r ig h t above 1 0 .8 a m p ./ s q .d m ,; u n d e r, d u ll. 4 6 -1 2 3.10 67 1 .0 2 4 2 .0 4 7 D u ll, c r a c k e d abo ve 9 .7 a m p ./s q .d m .; u n d e r, b r ig h t. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. PJIlfïîfSf.w,! I I 1 «Jîv: F ig u r e 2 0 . T h e e f fe c t o f in c r e a s in g c o n c e n tra tio n s o f g lu c o s e , c h lo r a P V M / M A , a c r y lic a c id , and 2 ,7 -n a p h th a le n e d is u lfo n ic aci< on th e a p p e a ra n c e o f W a tts n ic k e l d e p o s its . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 104 Tab le 41. S o lu tio n 531; the e ffe c t o f 5.0 g . / l . of 2 ,7 -n a p h th a le n e d is u lfo n ic a c id and in c r e a s in g c o n c e n tra tio n s o f 1 ,4 b u ty n e d io l on th e a p p e a ra n c e of W a tts n ic k e l s o lu tio n d e p o s its . T ,4 -B u ty n e d io l Panel No. pH Tem p. { “ C .) A d d i­ tio n (g.) T o ta l A d d i­ tio n C athode A p p e a ra n c e (g.) 5 3 1 -1 3.80 68 - 5 3 1 -2 3.80 65 0 .0 0 1 0 .0 0 1 B r ig h t a t h ig h c u r r e n t d e n s ity edge. H aze. 5 3 1 -3 3 .7 5 65 0 .0 0 2 0 .0 0 3 B r ig h t above 14.0 a m p ./s q . d m .; u n d e r, h a z e . 5 3 1 -4 3 .8 0 65 0 .0 0 4 0 .0 0 7 B r ig h t above 14.0 a m p ./s q . d m .; u n d e r, h a z e . 5 3 1 -5 3.8 0 65 0 .0 0 8 0 .0 1 5 B r ig h t above 14.0 a m p ./s q . d m .; u n d e r, h a z e . 5 3 1 -6 3,8 0 65 0.0016 0 .0 3 1 B r ig h t above 14.0 a m p ./s q . d m .; u n d er, h a z e . 5 3 1 -7 3 .7 8 65 0 .0 3 2 0 .0 6 3 B r ig h t above 5 .4 a m p ./s q . d m .; u n d er, h a z e -b r ig h t . 5 3 1 -8 3.80 65 0 .0 6 4 0 .1 2 7 H a z e - b r ig h t a t h ig h c u r r e n t d e n s ity r in g . B r ig h t. 5 3 1 -9 3.70 . 65 0 .1 2 8 0 .2 5 5 H a z e - b r ig h t r in g 15.1 am p. / s q .d m . B r ig h t. 5 3 1 -1 0 3.80 65 0 .2 5 6 0 .5 1 1 B r ig h t above 6 .5 a m p ./s q . d m . ; unde r , h a z e . - B r ig h t a t h ig h c u r r e n t d e n s ity edge. H aze. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 105 Tab le 42. S o lu tio n 351; the e f fe c t o f 5.0 g . / l . o f 2 ,7 -n a p h th a le n e d is u lfo n ic a c id and in c r e a s in g c o n c e n tra tio n s of M o n as t r a l B lu e on the a p p e a ra n c e of W a tts n ic k e l s o lu tio n d e p o s its . M onas t r a l 'B lu e Panel No. pH Tem p. r c .) A d d i­ tio n (g.) T o ta l A d d i­ tio n C ath o d e A p p e a ra n c e (g-) 3 51 -1 3.72 64 - - H aze. 3 5 1 -2 3.80 67 0 .0 0 1 0 .0 0 1 H aze. 3 5 1 -3 3.60 65 0 .0 0 2 0 ,0 0 3 H aze. 3 5 1 -4 3.80 66 0 .0 0 4 0 .0 0 7 H aze. 3 5 1 -5 3.50 65 0 .0 0 8 0 .0 1 5 H aze. ' 3 5 1 -6 3.90 65 0 .0 1 6 0 .0 3 1 H aze. 3 5 1 -7 3.80 65 0 ,0 3 2 0 .0 6 3 H aze. 3 5 1 -8 3.60 65 0 .0 64 0 .1 2 7 H aze. 3 5 1 -9 3.78 65 0 .1 2 8 0 .2 5 5 B r ig h t above 1.6 a m p . /s q . d m .; u n d e r, h a ze . 3 5 1 -1 0 3 .85 65 0 .2 5 6 0 .5 1 1 B r ig h t. The E f f e c t o f T e m p e r a tu r e a t C o n c e n tra tio n o f P a n e l 3 5 1 -1 0 3 5 1 -1 1 28 B r ig h t above 11.8 a m p ./s q . d m .; u n d e r, h a z e . 3 5 1 -1 2 38 B r ig h t. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 106 T a b le 42 (C o n tin u e d ) M o n as t r a l B lu e Panel No. pH Tem p. ( “ C .) A d d i­ tio n (gO T o ta l C atho de A p p e a ra n c e A d d i­ tio n (g.) . 1 3 5 1 -1 3 52 B r ig h t. 3 5 1 -1 4 60 B r ig h t. T r e a t e d S o lu tio n w ith 3 5 1 -1 5 60 15 g . / l . o f A c tiv a te d C a rb o n H a z e a t h ig h c u r r e n t den­ s it y edge. B r ig h t above 4 .3 a m p ./s q .d m .; u n d e r, haze. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 107 T a b le 43. S o lu tio n 311; th e e f fe c t of 5.0 g . / l . of 2 ,7 -n a p h th a le n e d is u lfo n ic a c id and in c r e a s in g c o n c e n tra tio n s of C la y to n Y e llo w on the a p p e a ra n c e of W a tts n ic k e l s o lu tio n d e ­ p o s its . C la y to n Y e llo w Panel N o. pH 3 1 1 -1 3 .4 5 3 1 1 -2 - Tem p. (° C .) C atho de A p p e a ra n c e tio n 62 - - B r ig h t above 6 .5 a m p ./s q . d m .; u n d e r, h a z e . 62 0 .0 0 1 0 .0 0 1 B r ig h t above 6.5 a m p ./s q . d m . ; unde r , h a z e . 3 1 1 -3 3.45 62 0 .0 0 2 0 .0 0 3 B r ig h t above 5 .4 a m p ./s q . d m .; u n d e r, h a z e . 311 4 3 .2 8 62 0 .0 0 4 0 .0 0 7 B r ig h t above 6.5 a m p ./s q . d m .; u n d e r, h a ze . 3 1 1 -5 3.40 63 0 .0 0 8 0 .0 1 5 B r ig h t above 4 .3 a m p . / sq. d m .; u n d e r, h a z e . 3 1 1 -6 3 .3 5 63 0 .0 1 6 0 ,0 3 1 B r ig h t above 3.2 a m p ./s q . d m .; u n d e r, h a z e -b r ig h t . 3 1 1 -7 3.30 64 0 .0 3 2 0 .0 6 3 B r ig h t. 3 1 1 -8 3.00 62 0 .0 6 4 0 .1 2 7 B r ig h t. 3 1 1 -9 3.00 62 0 .1 2 8 0 .2 5 5 B r ig h t. H a z e - b r ig h t rin g a t h ig h c u r r e n t d e n s ity . 3 1 1 -1 0 3.20 62 0 .2 5 6 0 .5 1 1 , B r ig h t . H a z e - b r ig h t rin g a t h ig h c u r r e n t d e n s ity . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 108 T a b le 4 3 (C o n tin u ed ) C la y to n Y e llo w Panel No. pH Tem p. r c .) A d d i­ tio n (g .) T o ta l A d d i­ tio n C athode A p p e a ra n c e (g.) [S o lu tio n 311 w as t r e a te d w ith 15 g. of a c tiv a te d c a rb o n a t 65° f ilt e r e d . and cath o d e w as p la te d in the c u s to m a r y m a n n e r.] 3 1 1 -1 1 3.10 62 C ., B r ig h t above 1.6 a m p ./s q . d m .; u n d er, h a z e . [C athode w as p la te d at 3 am p s . f o r 22. 5 a m p . h o u rs .] 62 3 1 1 -1 2 B r ig h t. T r e e d a t h ig h c u r r e n t d e n s ity . [C athode w as p la te d in th e c u s to m a r y m a n n e r .] 3 1 1 -1 3 3.00 62 B r ig h t above 10.8 a m p ./s q , d m .; u n d e r, h a z e . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 109 T a b le 44, S o lu tio n 321; the e f f e c t of 5,0 g . / l , of 2 ,7 -n a p h th a le n e d is u lfo n ic a c id and in c r e a s in g c o n c e n tra tio n s o f P r i m u lin e Y e llo w on the a p p e a ra n c e of W a tts n ic k e l s o lu tio n d e p o s its . P r im u lin e Y e llo w Panel N o, pH Tem p, (° C .) A d d i­ tio n (g.) 3 2 1 -1 3 2 1 -2 3.45 - . T o ta l A d d i­ tio n C ath o d e A p p e a ra n c e (g.) 62 - - B r ig h t above 6,5 a m p ./s q , d m .; u n d e r, h a z e . 62 0 ,0 0 1 0 ,0 0 1 B r ig h t above 6,5 a m p ,/ sq. d m ,; u n d e r, h a z e . 3 2 1 -3 2,70 62 0 ,0 0 2 0 .0 0 3 B r ig h t above 6,5 a m p ./s q . d m ,; u n d e r, h a z e . 3 2 1 -4 2,7 5 62 0 ,0 0 4 0 .0 0 7 B r ig h t above 6.5 a m p , / sq. d m ,; u n d e r, h a z e . 3 2 1 -5 2.90 62 0 ,0 0 8 0 .0 1 5 B r ig h t above 4 .3 am p . /s q . d m ,; u n d e r, h a z e -b r ig h t . 3 2 1 -6 3.20 63 0 ,0 1 6 0 .0 3 1 B r ig h t above 3,2 a m p ./s q , d m ,; u n d er, h a z e -b r ig h t . 3 2 1 -7 3,15 62 0 .0 3 2 0 .0 6 3 B r ig h t. 3 2 1 -8 3,30 62 0 ,0 6 4 0 .1 2 7 B r ig h t, 3 2 1 -9 3,30 62 0 .1 2 8 0 ,2 5 5 B r ig h t, H a z e r in g a t h ig h c u r r e n t d e n s ity . 3 2 1 -1 0 3.28 62 0 ,2 5 6 0 ,5 1 1 B r ig h t . H a z e rin g a t h ig h and lo w c u r r e n t d e n s ity . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 110 T a b le 44 (C o n tin u ed ) P r im u lin e Y e llo w Panel No. pH Tem p. (° C ath o d e A p p e a ra n c e C .) tio n [S olution 321 w as t r e a te d w ith 15 g, of a c tiv a te d c a rb o n a t 65° f ilt e r e d . and cath o d e w as p la te d in the c u s to m a r y m a n n e r .] 3 2 1 -1 1 3.20 62 C ., B r ig h t above 1 .6 a m p ./s q . d m .; u n d e r, h a z e . [C athode was p la te d a t 3 a m p s , f o r 22. 5 a m p . h o u rs .] 3 2 1 -1 2 - 62 B r ig h t. T r e e d a t h ig h c u r ­ r e n t d e n s ity . [C athode w as p la te d in th e c u s to m a r y m a n n e r .] 3 2 1 -1 3 3.1 2 62 B r ig h t above 6 .5 a m p ./s q . d m .; u n d e r, h a z e . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Ill F ig u r e 2 1 . T h e e ffe c t o f in c r e a s in g c o n c e n tra tio n s o f 1 ,4 -b u ty n e d io l and d yes; and 2 ,7 -n a p h th a le n e d is u lfo n ic a c id on the a p p e a ra n c e o f W a tts n ic k e l d e p o s its . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission 112 Tab le 45. S o lu tio n 331; the e ffe c t of 5.0 g . / l . o f 2 , 7 -n a p h th a le n e d is u lfo n ic a c id and in c r e a s in g c o n c e n tra tio n s o f M e th y ­ le n e B lu e on the a p p e a ra n c e o f W atts n ic k e l s o lu tio n d e p o s its . M e th y le n e B lu e Panel No. pH Tem p. C c .) A d d i­ tio n (g.) 3 31 -1 3 3 1 -2 3.52 - T o ta l A d d i­ tio n C atho de A p p e a ra n c e (g.) 62 - - 62 0 .0 0 1 0 .0 0 1 H a z e - b r ig h t above 1.0 a m p ./s q .d m .; u n d e r, d u ll. B r ig h t above 14.0 a m p ./s q . d m .; h a ze 14.0 to 1.0 am p. < s q .d m .; u n d e r, b r ig h t. 3 3 1 -3 3.40 62 0 .0 0 2 0 .0 0 3 B r ig h t above 1.0 a m p ./s q . d m .; u n d e r, d u ll. 3 3 1 -4 2 .8 5 62 0 .0 0 4 0 .0 0 7 B r ig h t. 3 3 1 -5 3.10 62 0 .0 0 8 0 .0 1 5 B r ig h t above 1.6 a m p . /s q . d m . ; unde r , h a z e . 3 3 1 -6 3.25 63 0 .0 1 6 0 .0 3 1 B r ig h t above 4 .3 a m p ./s q . d m .; u n d e r, h a z e . 3 3 1 -7 3.10 62 0 .0 3 2 0 .0 6 3 B r ig h t above 10.8 a m p ./s q . d m .; u n d er, h a z e , e x fo lia te , c o lo re d . 3 3 1 -8 3.30 63 0 .0 6 4 0 .1 2 7 H a z e -b r ig h t , e x fo lia te . c ra c k e d , c o lo re d . [S o lu tio n 331 w as t r e a te d w ith 1 15 g. of a c tiv a te d c a rb o n a t 65° f ilt e r e d . and the cathode w as p la te d in the u su al m a n n e r.] C ., Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 113 T a b le 45 (C ontinued) M e th y le n e B lu e Panel No. pH Tem p. r c.) A d d i­ tio n (g.) 3 3 1 -1 1 3 .3 5 62 T o ta l A d d i­ tio n C atho de A p p e a ra n c e (g-) S e m ib r ig h t hbove 3 .2 a m p ./ s q .d m .; u n d e r, h a z e . [C athode w as p la te d a t 3 am p s . f o r 2 2 .5 a m p . h o u rs .] 3 3 1 -1 2 - 62 S e m ib r ig h t. T r e e d a t h ig h c u r r e n t d e n s ity . [C athode w as p la te d in th e c u s to m a r y m a n n e r .] 3 3 1 -1 3 3 .3 2 62 D u ll above 10.8 a m p ./s q . d m .; u n d e r, s e m ib r ig h t. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 114 T ab le 46. S o lu tio n 341; the e f fe c t of 5.0 g . / l . of 2 , 7 -n a p h th a le n e d is u lfo n ic a c id and in c r e a s in g c o n c e n tra tio n s o f To lu i dine B lu e on th e a p p e a ra n c e o f W a tts n ic k e l s o lu tio n d e p o s its . T o lu id in e B lu e Panel No. pH Tem p. C C .) A d d i­ tio n (g.) 341 -1 3 4 1 -2 3.20 - 62 - 62 T o ta l A d d i­ tio n C atho de A p p e a ra n c e (g-) - S e m ib r ig h t. 0 .0 0 1 0 .0 0 1 S e m ib r ig h t. 3 4 1 -3 3.30 62 0 .0 0 2 0 .0 0 3 B r ig h t above 5 .4 a m p ./s q . d m .; u n d e r, s e m ib r ig h t. 3 4 1 -4 3.00 63 0 .0 0 4 0 .0 0 7 B r ig h t (v iv id ly ) above 8 .6 a m p ./s q .d m ,; u n d e r, d u ll. 3 4 1 -5 3.00 63 0 .0 0 8 0 .0 1 5 B r ig h t above 1.6 a m p ./s q . d m .; u n d e r, h a z e . 3 4 1 -6 3.20 64 0.016 0 .0 3 1 B r ig h t above 3 .2 a m p ./s q . d m .; u n d e r, h a z e . 3 4 1 -7 3.20 62 0 .0 3 2 0 .0 6 3 B r ig h t , e x fo lia te , c o lo re d above 7 .6 a m p ./s q .d m .; u n d e r, h a ze . 3 4 1 -8 3.32 62 0 .0 64 0 .1 2 7 H a z e - b r ig h t , e x fo lia te , c ra c k e d , c o lo re d . [S o lu tio n 341 w as t r e a t e d w ith 15 g . of a c tiv a te d c a rb o n a t 65 “ C . and- p e r m it t e d to stand o v e rn ig h t, f il t e r e d , and the cathode w as p la te d in the u s u a l m a n n e r .] 3 4 1 -1 1 3.40 62 D u ll above 11.8 a m p . / sq. d m .; u n d er, s em ib r ig h t. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 115 T a b le 46 (Continued.) T o lu id in e B lu e Panel No. pH Tem p. r c.) A d d i- T A d d i- C atho de A p p e a ra n c e (g.) [C athode w as p la te d a t 3 a m p s , f o r 2 2 .5 a m p . h o u rs .] 3 4 1 -1 2 - 62 D u ll, t r e e d above 2.1 a m p ./ s q .d m .; u n d e r, s e m ib r ig h t. [C athode w as p la te d in th e c u s to m a r y m a n n e r .] 3 4 1 -1 4 3.40 62 D u ll above 1 0.8 a m p ./s q . d m .; u n d e r, s e m ib r ig h t. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Il6 T a b le 47. S o lu tio n 3 0 1 ;the e f fe c t o f 5 .0 g . / l . of 2 ,7 -n a p h th a le n e d is u lfo n ic a c id and in c r e a s in g c o n c e n tra tio n s o f 4 , 4 ' d ih y d ro x y b ip h e n y l on the a p p e a ra n c e of W a tts n ic k e l so­ lu tio n d e p o s its . 4 , 4 '- D ih y d r o x y b ip h e n y l Panel N o. Tem p. pH ( “ C .) tio n IZ C atho de A p p e a ra n c e (g.) 3 0 1 -1 3.60 67 - - H a z e - b r ig h t above 14.0 a m p ./s q .d m .; u n d e r, h a z e , p itte d . 3 0 1 -2 3 .7 5 64 0 .0 0 1 0 .0 0 1 H a z e - b r ig h t above 14.0 a m p ./s q .d m .; u n d e r, h a z e , p itte d . 3 0 1 -3 3 .6 5 66 0 .0 0 2 0 .0 0 3 H a z e - b r ig h t above 14,0 a m p ./s q .d m .; u n d e r, h a z e , p itte d . 3 0 1 -4 3.80 64 0 .0 0 4 0 .0 0 7 H a z e - b r ig h t above 14,0 a m p ./s q .d m .; u n d e r, h a z e , • p itte d . 3 0 1 -5 3.85 64 0 .0 0 8 0 .0 1 5 H a z e -b r ig h t above 1 1.8 a m p ./s q .d m .; u n d e r, h a z e , p itt e d . 3 0 1 -6 3 .9 5 65 0 .0 1 6 0 .0 3 1 H a z e - b r ig h t above 11,8 a m p ./s q .d m .; u n d e r, h a z e , p itte d . 3 0 1 -7 4 .0 5 64 0 .0 3 2 0 .0 6 3 H a z e - b r ig h t above 8 .6 am p ., s q .d m .; u n d e r, h a z e , p itte d . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 117 T a b le 47 (C o n tin u ed ) 4 ,4 ’- D ih y d r o x y b ip h e n y l Panel No. pH Tem p. C C .) A d d i­ tio n (g>) T o ta l A d d i­ tio n C atho de A p p e a ra n c e (g.) 3 0 1 -8 3.15 63 0 .0 6 4 0 .1 2 7 H a z e - b r ig h t above 6.5 am p ., s q .d m .; u n d e r h a z e , p itte d . 3 0 1 -9 3 .25 63 0 .1 2 8 . 0 .2 5 5 H a z e - b r ig h t above 4 .3 a m p ., s q .d m .; u n d e r, h a z e . 3 0 1 -1 0 3.45 65 0 .2 5 6 0 .5 1 1 H a z e - b r ig h t above 11.8 a m p ./s q .d m .; u n d e r, h a ze , p itte d . E f f e c t of T e m p e r a tu r e at C o n c e n tra tio n of P a n e l 3 0 1 - 10 3 0 1 -1 2 3.85 47 B r ig h t p itte d above 11.8 a m p ./s q .d m .; u n d e r, h a ze . 3 0 1 -1 4 3.70 24 E x fo lia te h a ze above 11.8 a m p ./s q .d m .; b r ig h t 11.8 to 3 .8 a m p ./s q .d m .; u n d e r, haze. 3 0 1 -1 5 3.80 35 E x fo lia te above 11.8 a m p ./ s q .d m .; u n d e r, b r ig h t. 3 0 1 -1 6 3.60 55 B r ig h t above 11.8 a m p . / s q .d m .; u n d e r, h a z e . 3 0 1 -1 7 3.72 75 B r ig h t p itte d above 11.8 a m p ./s q .d m .; u n d e r, h a ze , p itte d . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 118 T ab le Panel No. 48. S o lu tio n 271; the e f fe c t of 5 .0 g . / I . o f 2 ,7 -n a p h th a le n e d is u lfo n ic a c id and in c r e a s in g c o n c e n tra tio n s o f 3 ,5 ,3 ', 5 ' - t e t r a n i t r o - 4 , 4 ' - d ih y d ro x y b ip h e n y l on the a p p e a ra n c e o f W atts n ic k e l s o lu tio n d e p o s its . pH Tem p. r 3 ,5 ,3 ', 5 'T e tr a n itr o 4 , 4 '- d i h y d ro x y b ip h e n y l C atho de A p p e a ra n c e c .) A d d i­ tio n (g.) T o ta l A d d i­ tio n (g.) 2 7 1 -1 3.83 67 - - 2 7 1 -2 3.70 64 0 .0 0 1 0 .0 0 1 B r ig h t above 1 1 .8 a m p . / s q .d m .; h a z e - b r ig h t 11.8 to 1 .6 a m p ./s q .d m .; u n d e r, b r ig h t. 2 7 1 -3 3.75 66 0 .0 0 2 0 .0 0 3 B r ig h t above 3 .2 a m p ./s q . d m .; u n d e r, h a z e . 2 7 1 -4 3.60 64 0 .0 0 4 0 .0 0 7 B r ig h t above 13.0 a m p ./s q . d m .; u n d e r, h a z e . 2 7 1 -5 3.23 64 0 .0 0 8 0 .0 1 5 B r ig h t a t high c u r r e n t d e n s ity edge. H aze. 2 7 1 -6 3.85 65 0 .0 1 6 0 .0 3 1 E x fo lia te at h ig h c u r r e n t d e n s ity edge. H aze. 2 7 1 -7 . 4 .5 5 64 0 .0 3 2 0 .0 6 3 E x fo lia te at h ig h c u r r e n t d e n s ity edge. B r ig h t above 11.8 a m p ./ s q .d m .; u n d e r, haze. B r ig h t above 14.0 a m p ./ s q .d m .; u n d e r, h a z e . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 119 T a b le 48 (C o n tin u ed ) 3 ,5 , 3 ' , 5 'T e tr a n itr o 4 ,4 ' - d ih y Panel No. pH Tem p. d ro x y b ip h e n y l C ath o d e A p p e a ra n c e ( “ C .) A d d i­ tio n (g.) T o ta l A d d i­ tio n (g.) 2 7 1 -8 3.62 63 0 .0 6 4 0 .1 2 7 E x fo lia te a t h ig h c u r r e n t d e n s ity e d g e . B r ig h t above 10.8 a m p ./s q .d m .; u n d e r, haze. 2 7 1 -9 3.20 63 0 .1 2 8 0 .2 5 5 T r a c e e x fo lia tio n . B r ig h t above 1 0.8 a m p ./s q .d m .; u n d e r, h a z e . 2 7 1 -1 0 3.72 65 0 .2 5 6 0 .5 1 1 E x f o lia t e . H a z e - b r ig h t above 8 .6 a m p ./s q .d m .; unde r , h a z e . 2 7 1 -1 1 3.00 67 - 0 .5 1 1 T r a c e e x fo lia tio n . B r ig h t above 1 0 .8 a m p ./s q .d m .; u n d e r, h a z e . E f f e c t of T e m p e r a tu r e a t .C o n c e n tra tio n of P a n e l 2 7 1 - 10 2 7 1 -1 2 4 .4 5 47 B r ig h t , e x fo lia te . 2 7 1 -1 4 3.20 24 D u ll above 3 .2 a m p ./s q . d m .; u n d e r, b r ig h t. 3.60 35 E x fo lia te . H a z e - b r ig h t above 3.2 a m p ./s q .d m .; u n d e r, b r ig h t . 2 7 1 -1 5 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 120 T a b le 48 (C o n tin u ed ) 3 ,5 ,3 ',5 » Te t r a n it r o 4 , 4 '- d i h y ^ Panel N o. „ pH ^ _ Tem p. (° ^ r o x y b ip h e n y l , C .) _ . C a th o d e A p p e a ra n c e tio n 2 7 1 -1 6 3 .60 56 E x fo lia te , H a z e - b r ig h t above 6 ,5 a m p ./s q .d m .; u n d e r, h a z e . 2 7 1 -1 7 3 .7 2 75 E x fo lia te . H a z e - b r ig h t above 1 1 .8 a m p ./s q .d m .; u n d e r, h aze . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 121 T a b le 49. S o lu tio n 411; the e ffe c t of 5.0 g . / I . o f 2 ,7 -n a p h th a le n e d is u lfo n ic a c id and in c r e a s in g c o n c e n tra tio n s o f p h e n o l on the a p p e a ra n c e o f W atts n ic k e l s o lu tio n d e p o s its . Phenol Panel N o. pH Tem p. r c .) A d d i­ tio n (g.) T o ta l A d d i­ tio n C atho de A p p e a ra n c e (g.) 4 1 1 -4 3.50 63 0 .0 0 1 0 .0 0 1 B r ig h t above 14.0 a m p . / s q. d m .; u n d e r, h a z e . p itte d . 4 1 1 -5 3.50 65 0 .0 0 2 0 .0 0 3 B r ig h t above 14.0 a m p . / s q. d m .; u n d e r, h a z e . p itte d . 4 1 1 -6 3 ,6 5 65 0 .0 0 4 0 .0 0 7 B r ig h t above 11.8 a m p ./ sq. d m .; u n d e r, h a z e . p itte d . 4 1 1 -7 3.80 65 0 .0 0 8 0 .0 1 5 B r ig h t above 1 1 .8 am p ./s q . d m .; u n d e r, h a z e . p itte d . 4 1 1 -8 3.60 66 0 .0 1 6 0 .0 3 1 B r ig h t above 14.0 am p ./s q . d m .; u n d e r, h a z e . p itte d . 4 1 1 -9 3 .68 66 0 .0 3 2 0.063 B r ig h t above 14.0 am p . /s q . d m .; u n d e r, h a z e . p itte d . 4 1 1 -1 0 3 .8 2 64 0.064 0 .1 2 7 B r ig h t above 14.0 am p ./s q . d m .; u n d e r, h a z e . p itte d . 4 1 1 -1 1 3 .85 66 0 .1 2 8 0 .2 5 5 B r ig h t above 14.0 am p ./s q . d m .; u n d e r, h a z e . p itte d . 4 1 1 -1 2 3.80 65 0.256 0 .5 1 1 B r ig h t above 11.8 a m p ./s q. d m .; u n d e r, h a z e . p itte d . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 12?- F ig u r e 2 2 . T h e effect o f in c r e a s in g c o n c e n tra tio n s o f d yes and of p h e n o ls and 2 ,7 -n a p h th a le n e d is u lfo n ic a c id on th e a p p e a r, a n c e o f W a tts n ic k e l d e p o s its . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 123 T a b le 50. S o lu tio n 421; the e ffe c t of 5.0 g . / I . o f 2 ,7 -n a p h th a le n e d is u lfo n ic a c id and in c r e a s in g c o n c e n tra tio n s of o - n i t r o p h e n o l on the a p p e a ra n c e of W atts n ic k e l s o lu tio n d e ­ p o s its . o - N itr o p h e n o l Panel No. pH Tem p. (° c . ) A d d i­ tio n (g.) T o ta l A d d i­ tio n C atho de A p p e a ra n c e (g.) 4 2 1 -4 3,60 63 0 .0 0 1 0 .0 0 1 B r ig h t above 11.8 a m p ./s q . d m ,; u n d e r, h a z e , p itte d . 4 2 1 -5 3 .8 0 , 65 0 .0 0 2 0 .0 0 3 B r ig h t above 8 .6 a m p ./s q . d m .; u n d e r, h a z e , p itte d . 4 2 1 -6 3.65 65 0 .0 0 4 0 .0 0 7 B r ig h t above 5 .4 a m p ./s q . d m .; u n d e r, h a z e , p itte d . 4 2 1 -7 3.50 65 0 .0 0 8 0 .0 1 5 B r ig h t. 4 2 1 -8 3.65 66 0 .0 1 6 0 .0 3 1 B r ig h t. 4 2 1 -9 3.80 66 0 .0 3 2 0 .0 6 3 H a z e - b r ig h t , p itte d . 4 2 1 -1 0 3.75 64 0 .0 6 4 0 .1 2 7 H a z e -b r ig h t , p itte d . 4 2 1 -1 1 3.82 66 0 .1 2 8 0 .2 5 5 H a z e , p itte d . 4 2 1 -1 2 3 .7 5 65 0 .2 5 6 0 .5 1 1 H a z e , p itte d . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 124 T a b le 51. S o lu tio n 47; the e f fe c t o f 5.0 g . / I . of 2 ,7 -n a p h th a le n e d is u lfo n ic a c id and in c r e a s in g c o n c e n tra tio n s o f p - n i t r o p h e n o l on the a p p e a ra n c e of W a tts n ic k e l s o lu tio n d e p o sits, p - N itr o p h e n o l Panel No. pH Tem p. ( “ C .) A d d i­ tio n (g.) T o ta l A d d i­ tio n C ath o d e A p p e a ra n c e (g.) 4 7 -1 3 .5 5 65 - - B r ig h t aboVe 14.0 a m p ./s q . d m .; u n d e r, h a ze . 4 7 -2 3.85 65 0 .0 0 1 0 .0 0 1 B r ig h t above 1 1.8 a m p ./s q . d m .; u n d e r, h a z e . 4 7 -3 3 .55 65 0 .0 0 2 0 .0 0 3 B r ig h t above 11.8 a m p ./s q . d m . ; unde r , h a z e . 4 7 -4 3.80 65 0 .0 0 4 0 .0 0 7 B r ig h t above 11.8 a m p ./s q . d m .; u n d e r, h a z e , p itte d . 4 7 -5 3.80 64 0 .0 0 8 0 .0 1 5 B r ig h t above 11.8 a m p ./s q . d m .; u n d e r, h a z e , p itte d . 4 7 -6 3 .8 8 64 0 .0 1 6 0 .0 3 1 B r ig h t above 10.8 a m p ./s q . d m .; u n d e r, h a z e , p itte d . 4 7 -7 3.50 65 0 .0 3 2 0 .0 6 3 B r ig h t above 9.0 a m p ./s q . d m .; u n d e r, h a z e -b r ig h t. 4 7 -8 3 .8 6 64 0 .0 6 4 0 .1 2 7 H a z e above 11.8 a m p . / sq. d m .; h a z e - b r ig h t 11.8 to 2 .1 am p. / sq .d m .; u n d er, h a z e , p itte d . 4 7 -9 3.20 66 0 .1 2 8 0 .2 5 5 H a z e above 11.8 am p ./s q . d m .; u n d e r, b r ig h t, e x fo lia te 4 7 -1 0 3.80 66 0 .2 5 6 0 .5 1 1 • B r ig h t , e x fo lia te . % Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 125 T a b le 52. S o lu tio n 481; the e f fe c t o f 5.0 g . / I . o f 2 , 7 -n a p h th a le n e d is u lfo n ic a c id and in c r e a s in g c o n c e n tra tio n s o f p -a m in o p h e n o l h y d ro c h lo r id e on the a p p e a ra n c e of W a tts n ic k e l s o lu tio n d e p o s its . p - A m inop he no 1 H y d r o c h lo r id e Panel No. pH Tem p. ( “ C .) A d d i­ tio n (g.) T o ta l .A d d i­ tio n C ath o d e A p p e a ra n c e (g.) 4 8 1 -1 3.8 0 65 - - 4 8 1 -2 3 .8 2 64 0 .0 0 1 0 .0 0 1 B r i g h t abo ve 5 .4 a m p ./s q . d m .; u n d e r, h a z e . 4 8 1 -3 3.7 8 65 0 .0 0 2 0 .0 0 3 B r i g h t above 4 .3 a m p ./s q . d m .; u n d e r, h a z e . 4 8 1 -4 3.80 65 0 .0 0 4 0 .0 0 7 B r ig h t . 4 8 1 -5 3.80 65 0 .0 0 8 0 .0 1 5 B r ig h t . 4 8 1 -6 3 ,8 2 64 0 .0 1 6 0 .0 3 1 B r ig h t . 4 8 1 -7 3.86 65 0 .0 3 2 0.0 6 3 B r ig h t . 4 8 1 -8 3.80 64 0 .0 64 0 .1 2 7 S e m ib r ig h t to h a z e . 4 8 1 -9 3 .7 5 65 0 .1 2 8 0 .2 5 5 S e m ib r ig h t to h a z e , c ra c k e d , 4 8 1 -1 0 3.80 65 0 .2 5 6 0 .5 1 1 S e m ib r ig h t to h a z e , c ra c k e d , B r i g h t above 14.0 a m p ./s q . d m .; u n d e r, h a z e . The E f f e c t of T e m p e r a tu r e a t C o n c e n tr a tio n of • P a n e l 4 8 1 -1 0 4 8 1 -1 1 3.5 0 35 H aze. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 126 T a b le 52 (C o n tin u ed ) p - A m in o p h e n o l H y d r o c h lo r id e Panel No. pH Tem p. C C a th o d e A p p e a ra n c e C .) Id S tio n <«•> (g .) 4 8 1 -1 2 3.75 49 H a z e , c ra c k e d . 4 8 1 -1 3 3.80 59 H a z e , c ra c k e d . a Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 127 Table 53. S o lu tio n 491; the e f fe c t of 5 .0 g . / l . o f 2 ,7 -n a p h th a le n e d is u lfo n ic a c id and in c r e a s in g c o n c e n tra tio n s of o -a m in o p h e n o l h y d r o c h lo r id e on the a p p e a ra n c e of W a tts n ic k e l s o lu tio n d e p o s its . 0 - A m in o p h en o l H y d r 0 c h lo r ide Panel No. pH Tem p. C ath o d e A p p e a ra n c e ( “ C .) tio n , . z t tio n (g.) 491 -1 3.65 65 - - 4 9 1 -2 3.80 64 0 .0 0 1 0 .0 0 1 B r ig h t above 14.0 a m p ./s q . d m .; u n d e r, h a z e . 4 9 1 -3 3.75 65 0 .0 0 2 0 .0 0 3 B r ig h t above 10.8 a m p ./s q . d m .; u n d e r, h a z e . 4 9 1 -4 3.80 65 0 .0 0 4 0 .0 0 7 B r ig h t above 4 .3 a m p ./s q . d m .; u n d e r, h a z e -b r ig h t . 4 9 1 -5 3.75 65 0 .0 0 8 0 .0 1 5 B r ig h t . 4 9 1 -6 3.75 64 0 .0 1 6 0 .0 3 1 B r ig h t . 4 9 1 -7 3.84 65 0 .0 8 2 0.063 H a z e - b r ig h t above 4 .3 a m p ./s q .d m .; u n d e r, b r ig h t. 4 9 1 -8 3.75 64 0.064 0 .1 2 7 B r ig h t above 3 .8 a m p ./s q . d m .; u n d e r, h a z e . 4 9 1 -9 - 3.79 65 0 .1 2 8 0 .2 5 5 S e m ib r ig h t to h a z e . 4 9 1 -1 0 3.75 65 0 .2 5 6 0 .5 1 1 H a z e , c ra c k e d . B r ig h t a t h ig h c u r r e n t d e n s ity ed g e. H aze. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 128 T a b le 53 (C o n tin u e d ) o - A m in o p h e n o l H y d r o c h lo r id e Panel No. pH Tem p, C ath o d e A p p e a ra n c e (° C .) tio n T h e E f f e c t o f T e m p e ra -tu re a t C o n c e n tr a tio n o f P a n e l 4 9 1 -1 0 49 1 -1 1 3.60 . 35 H a z e , e x f o lia te , c r a c k e d . 491-12 3.80 49 H a z e , e x f o lia te , c r a c k e d . 491-13 3.80 59 H a z e , c ra c k e d . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 129 T ab le 54. S o lu tio n 501; the e f fe c t of 5 .0 g . / l . o f 2 , 7 -n a p h th a le n e . d is u lfo n ic a c id and in c r e a s in g c o n c e n tra tio n s of c a te c h o l on the a p p e a ra n c e o f W a tts n ic k e l s o lu tio n d e p o s its . C a te c h o l Panel No. pH Tem p. (° C .) A d d i­ tio n (g.) T o ta l A d d i­ tio n C ath o d e A p p e a ra n c e 1 (g.) 5 0 1 -1 3.70 65 - - B r ig h t a t h ig h c u r r e n t d en ­ s ity ed g e. H aze. 5 0 1 -2 3 .8 3 64 0 .0 0 1 0 .0 0 1 B r ig h t a t h ig h c u r r e n t den­ s ity ed g e. H aze. 5 0 1 -3 3.70 65 0 .0 0 2 0 .0 0 3 B r ig h t a t h ig h c u r r e n t den­ s ity edg e. H aze. 5 0 1 -4 3 .8 2 65 0 .0 0 4 0 .0 0 7 B r ig h t ; p itt e d above 15.1 a m p ./s q .d m .; u n d e r, h a z e . 5 0 1 -5 3 .8 5 65 0 .0 0 8 0 .0 1 5 B r ig h t , p itte d above 15.1 a m p ./ s q .d m .; u n d e r, h a z e . 5 0 1 -6 3 .7 4 64 0.016 0 .0 3 1 B r ig h t , p itte d above 14.0 a m p ./s q .d m .; u n d e r, h a z e . 5 0 1 -7 3 .8 3 65 0 .0 3 2 0 .0 6 3 B r ig h t above 15.1 a m p ./ s q .d m .; u n d e r, h a z e . 5 0 1 -8 3 .7 5 64 0 .0 6 4 0 .1 2 7 B r ig h t above 15.1 a m p ./ s q .d m .; u n d e r, h a z e . 5 0 1 -9 3.80 65 0 .1 2 8 0 .2 5 5 B r ig h t , p itte d above 15.1 a m p ./s q .d m .; u n d e r, h a z e . 5 0 1 -1 0 3.80 65 0 .2 5 6 0 .5 1 1 B r ig h t , p itte d above 15.1 a m p ./s q .d m .; u n d er, h a ze . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 130 T a b le 54 (C o n tin u ed ) : C a te c h o l Panel No. pH Tem p. i° C .) A d d i­ tio n (g.) 5 0 1 -1 4 3.80 65 0 .5 1 2 T o ta l A d d i­ tio n C ath o d e A p p e a ra n c e (g.) 1 .0 2 3 H a z e - b r i g h t a t h ig h c u r r e n t d e n s ity e d g e. H aze. The E f f e c t o f T e m p e r a tu r e a t C o n c e n tr a tio n of P a n e l 5 0 1 -1 0 5 0 1 -1 1 3.50 35 B r ig h t , p itte d above 3.2 a m p ./s q .d m .; u n d e r, h a ze . 5 0 1 -1 2 3.50 49 H a z e - b r ig h t above 7 .6 a m p ./ s q .d m .; u n d e r, h a z e . 5 0 1 -1 3 3.70 59 H a z e - b r i g h t above 9.0 a m p ./s q .d m .; u n d er, h a z e . lu s Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 131 Table 55. S o lu tio n 511; the e f fe c t of 5.0 g . / l . o f 2 ,7 -n a p h th a le n e d is u lfo n ic a c id and in c r e a s in g c o n c e n tra tio n s o f r e s o r c in o l on the a p p e a ra n c e of W a tts n ic k e l s o lu tio n d e ­ p o s its . R e s o r c in o l Panel No. pH Tem p. (° C .) C ath o d e A p p e a ra n c e tio n , . tio n '* • ’ (g.) 511 -1 3.70 65 - - B r ig h t a t h ig h c u r r e n t d e n s ity edge. H aze. 5 1 1 -2 3.85 64 0 .0 0 1 0 .0 0 1 B r ig h t a t h ig h c u r r e n t d e n s ity edg e. H aze. 5 1 1 -3 3.8 5 65 0 .0 0 2 0 .0 0 3 B r ig h t a t hig h c u r r e n t d e n s ity ed g e. H aze. . 5 1 1 -4 3.80 65 0 .0 0 4 0 .0 0 7 B r ig h t a t hig h c u r r e n t d e n s ity ed g e. H aze. 5 1 1 -5 3 .75 65 0 .0 0 8 0 .0 1 5 B r ig h t a t h ig h c u r r e n t d e n s ity edg e. H aze. 5 1 1 -6 3.75 64 0 .0 1 6 0 .0 3 1 B r ig h t above 1 0.8 a m p ./s q . d m .; u n d e r, h a z e . 5 1 1 -7 3.80 65 0 .0 3 2 0 .0 6 3 B r ig h t above 14.0 a m p ./s q . d m .; u n d e r, h a z e . 5 1 1 -8 3.70 64 0 .0 6 4 0 .1 2 7 B r ig h t above 11 .8 a m p ./s q . d m . ; unde r , h a z e . 5 1 1 -9 3 .6 0 65 0 .1 2 8 0 .2 5 5 B r ig h t above 1 0 .8 a m p ./s q . d m .; u n d e r, h a z e . 5 1 1 -1 0 3.70 65 0 .2 5 6 0 .5 1 1 B r ig h t above 9 .7 a m p ./s q . d m .; u n d e r h a ze . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 132 T a b le 55 (C o n tin u e d ) R e s o r c in o l Panel No. 5 1 1 -1 4 __ pH 3.60 Tem p. ( C .) 65 A d d itio n 0 .5 1 2 T o ta l ^ C a th o d e A d d i­ 1 .0 2 3 A p p e a ra n c e B r ig h t a-^ove dm .; T he E f f e c t o f T e m p e r a tu r e 14.0 a m p ./s q . haze. a t C o n e e n tr ^ ^ o n of P a n e l 5 1 1 -1 0 5 1 1 -1 1 3.50 35 5 1 1 -1 2 3,70 49 H a ze at s ity edg6. B r ig h t abo-ve d m .; 5 1 1 -1 3 3.80 59 c u r r e n t den­ H a z e - b r ig h t . 8.6 a m p ./s q . haze. B r ig h t abo^ve 9.7 a m p ./s q . d m .; under^ haze. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 133 Tab le 56, S o lu tio n 521; th e e ffe c t of 5.0 g . / l . o f 2 , 7 -n a p h th a le n e d is u lfo n ic a c id and in c r e a s in g c o n c e n tra tio n s o f b e t a n a p th o l on the a p p e a ra n c e o f W a tts n ic k e l s o lu tio n d e ­ p o s its . b e ta -N a p th o l Panel N o. pH Tem p. r c.) A d d i­ tio n (g .) T o ta l A d d i­ tio n C ath o d e A p p e a ra n c e (g.) 5 2 1 -1 3.80 68 - - B r ig h t a t h ig h c u r r e n t d e n s ity ed g e. H aze. 5 2 1 -2 3.8 2 65 0 .0 0 1 0 .0 0 1 B r ig h t a t h ig h c u r r e n t d e n s ity ed g e. H aze. 5 2 1 -3 3.80 65 0 .0 0 2 0 .0 0 3 B r ig h t above 10 .8 a m p ./s q . d m .; u n d e r, h a z e , p itte d . 5 2 1 -4 3.80 . 65 0 .0 0 4 0 .0 0 7 B r ig h t above 8 .6 a m p ./s q . d m .; u n d e r, h a z e , p itte d . 5 2 1 -5 3.80 65 0 .0 0 8 0 .0 1 5 B r ig h t above 8 .6 a m p ./s q . d m .; u n d e r, h a z e , p itte d . 5 2 1 -6 3.80 65 0 .0 1 6 0 .0 3 1 B r ig h t above 6 .5 a m p ./s q . d m .; u n d e r, h a z e , p itte d . 5 2 1 -7 3.80 65 0 .0 3 2 0 .0 6 3 H a z e a t h ig h c u r r e n t d e n s ity ed g e. B r ig h t , p itte d above 4 .3 a m p ./s q .d m .; u n d e r, h a ze , p itte d . 5 2 1 -8 3.80 65 0 .0 6 4 0 .1 2 7 H a z e above 15.1 a m p . /s q . d m .; b r ig h t 15.1 to 2 .6 a m p ./s q .d m .; u n d e r, h a z e b r ig h t. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 134 T a b le panel No. 56 (C o n tin u e d ) b e ta -N a p th o l pH Tem p. (° C .) A d d i­ tio n (g-) T o ta l A d d i­ tio n C athode A p p e a ra n c e (g.) 5 2 1 -9 3.80 65 0 .1 2 8 0 .2 5 5 H a z e above 9 .7 a m p ./s q . d m .; u n d e r. h a z e -b r ig h t . 52 1 -1 0 3.60 65 0 .2 5 6 0 .5 1 1 H a z e above 8,1 a m p ./s q . d m .; u n d e r. h a z e -b r ig h t . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. F ig u r e 2 3 . T h e e f fe c t o f in c r e a s in g c o n c e n tra tio n s o f p h e n o ls and 2 , 7 -n a p h th a le n e d is u lfo n ic a c id on th e a p p e a ra n c e o f W a tts n ic k e l d e p o s its . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 136 ÜF 10| F ig u r e 2 4 . T h e e ffe c t o f in c r e a s in g c o n c e n tra tio n s o f phenols and 2 ,7 n a p h th a le n e d is u lfo n ic a c id on th e a p p e a ra n c e o f W a tts n ic k e l d e p o s its . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 137 Table 57, S o lu t io n 18; the e f f e c t of 45 g . / l . n ic k e l f o r m a t e , 15 g . / l . c o b a l t s u l f a t e , and in c r e a s in g c o n c e n tra tio n o f c in n a m a ld é ­ h y d e o n th e a p p e a ra n c e o f W a tts n ic k e l s o lu tio n d e p o s its . C in n a m a ld é h y d e P anel No. pH Tem p. r c.) T o ta l A d d i­ tio n (m l.) A d d i­ tio n (m l./ C atho de A p p e a ra n c e g-) 181 3.80 65 - H a z e above 2.1 a m p ./s q . d m .; u n d e r. b r ig h t. 182 3.80 65 - H a z e above 3 .2 a m p ./s q . d m .; u n d e r. b r ig h t. 183 3.80 65 0 .5 0 .5 / 0 .5 5 » H a z e above 5 .4 a m p ./s q . d m .; u n d e r. b r ig h t. * W e ig h ts c a l c u l a t e d u s in g handbook v a lu e f o r s p e c ific g r a v ­ ity of c in n a m a ld e b y d e 1 .1 1 0 20° / 2 0 ° . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 138 Tab le 58. S o lu tio n 19: the e f fe c t of 45 g . / l . n ic k e l f o r m a t e , 15 g . / l . c o b a lt s u lfa te , a d d itio n of a m m o n iu m s u lfa te , and in c r e a s ­ ing c o n c e n tra tio n s o f c h lo r a l on the a p p e a ra n c e o f W a tts n ic k e l s o lu tio n d e p o s its . C h lo r a l Panel No. pH Tem p. ( “ C .) A d d i­ tio n ( m l.) T o ta l A d d i­ tio n (m l./ C athode A p p e a ra n c e g.) 191 3.80 55 - - H aze. 192 3.80 65 - - H a z e above 3.2 a m p ./s q . d m ,; u n d e r. b r ig h t. 193 3.80 65 1 g- - H a z e above 3 .2 a m p ./s q . d m .; u n d e r. b r ig h t. 194 3.80 65 0 .5 0 .5 / 0 .7 5 * H a z e above 6.5 a m p ./s q . d m .; u n d e r. b r ig h t. 195 - 65 0 .5 1 .0 / 1.50 H a z e above 6.5 a m p ./s q . d m .; u n d e r. b r ig h t. 196 - 65 0 .5 1 .5 / 2 .2 5 B r ig h t. 197 - 65 0 .5 2 .0 / 3.01 H a z e above 3.2 a m p ./s q . d m .; u n d e r. b r ig h t. 198 - 65 - 2 .0 / 3.01 H a ze above 3.2 a m p ./s q . d m .; u n d er. b r ig h t. * W e ig h ts c a lc u la te d using handbook v a lu e f o r s p e c ific g r a v ­ ity o f c h lo r a l 1 .5 0 5 2 5 ° / 4 ° . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 139 Table 59. S o lu tio n 20; the e f fe c t of 4 5 g . / l , o f n ic k e l f o r m a t e , 15 g . / l . of c o b a lt s u lfa te , and in c r e a s in g c o n c e n tra tio n s o f c h lo r a l h y d ra te on the a p p e a ra n c e o f W a tts n ic k e l s o lu ­ tio n d e p o s its . C h lo r a l H y d r a te Panel No, pH Tem p. r c.) T o ta l A d d i­ tio n (m l.) A d d i­ tio n (m l./ C atho de A p p e a ra n c e g -)* 201 3.83 63 - - H a z e above 1 .6 a m p ./s q . d m ,; u n d e r, b r ig h t. 202 3.80 65 0 .5 0 ,5 / 0 .7 5 H a z e above 7 .6 a m p ./s q . d m ,; u n d e r, b r ig h t. 20 3 3.85 63 0 ,5 1 .0 / 1.51 H a z e above 1 1 .8 a m p . /s q . d m .; u n d e r, b r ig h t. 204 3.90 66 0 ,5 1 .5 / 2 .2 5 B r ig h t. 20 5 4.05 63 - 1 .5 / 2 .2 5 B r ig h t. 20 6 3.78 65 - 1 .5 / 2 .2 5 H a z e above 9 .7 a m p ./s q . d m .; u n d er, b r ig h t. 20 7 3.87 65 - 1 .5 / 2 .2 5 H a ze above 10,8 a m p ./s q , d m .; u n d e r, b r ig h t. 208 3.90 65 0 ,5 2 .0 / 3.01 H a ze a t h ig h c u r r e n t den­ s ity edge. B r ig h t. * W e ig h ts c a lc u la te d u sin g handbook v a lu e f o r s p e c ific g r a v ­ ity of c h lo r a l 1.50 5 2 5 ° / 4 “ , Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 140 Tab le 60, S o lu tio n 24; the e ffe c t o f 45 g . / l . o f n ic k e l f o r m a t e , 15 g . / l . of c o b a lt s u lfa te , and in c r e a s in g c o n c e n tra tio n of a c e ta ld e h y d e on the a p p e a ra n c e of W atts n ic k e l s o lu tio n d e p o s its . A c e ta l de h y de Panel No. pH Tem p. {° C .) T o ta l A d d i­ tio n ( m l.) A d d i­ tio n (m l./ C ath o d e A p p e a ra n c e g -)* 241 3.85 66 - - H a z e above 1 .6 a m p ./s q . d m .; u n d e r. b r ig h t . 242 3 .8 5 63 0 .5 0 .5 / 0 .3 9 H a z e above 1 .6 a m p ./s q . d m .; u n d e r. b r ig h t . 243 3.90 64 0 .5 1 .0 / 0 .7 8 H a z e above 3 .2 a m p ./s q . d m .; u n d e r. b r ig h t. 244 3.83 72 0 .5 1 .5 / 1.17 H a z e above 1.0 a m p ./s q . d m .; u n d er. h a z e -b r ig h t . 245 3.82 67 0 .5 2 .0 / 1 .5 6 H a z e above 5 .4 a m p ;/s q . d m .; u n d er. h a z e -b r ig h t . 246 3,80 65 0 .5 2 .5 / 1 .95 H a z e above 7 .6 a m p ./s q . d m .; u n d er. b r ig h t. 65 0 .5 3 .0 / 2 .3 5 H a z e above 8 .6 a m p ./s q . d m .; u n d er. b r ig h t. 65 0 .5 3 .5 / 2 .7 4 H a z e to d u ll above 8 .6 a m p ./s q .d m . ; u n d e r, b r ig h t. 66 0 .5 4 .0 / 3 .1 3 H a z e to d u ll above 7.6 a m p ./ sq. dm . ; u n d e r, b r ig h t. 247 - 248 3.9 2 - 249 - * W e ig h ts c a lc u la te d using handbook v a lu e f o r s p e c ific g r a v ­ ity of a c e ta ld e h y d e 0 .7 8 3 1 8 */4 ° . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 141 Table 6 l . S o lu tio n 29; the e f fe c t o f 45 g . / l . o f n ic k e l f o r m a t e , 15 g . / l . of c o b a lt s u lfa te , and in c r e a s in g c o n c e n tra tio n of e th y l p y r u v a te and g ly o x a l on the a p p e a ra n c e o f W a tts n ic k e l s o lu tio n d e p o s its . E th y l P y ru v a te Panel No. pH Tem p. ( “ c.) A d d i­ tio n ( m l.) T o ta l A d d i­ tio n (m l./ C ath o d e A p p e a ra n c e g-) 291 3.50 63 - 292 3.50 67 0 .5 0 .5 / 0 .5 3 * H a z e above 1.0 a m p ./s q . d m .; u n d e r, b r ig h t. 293 3.60 67 0 .5 1 .0 / 1 .0 6 H a z e above 1 .6 a m p ./s q . d m .; u n d e r, b r ig h t. 67 0 .5 1 .5 / H a z e above 1 .6 a m p ./s q . d m .; u n d e r, b r ig h t. 294 - - 1.59 295 296 297 3.82 - 3.8 2 67 - 1 .5 / H a z e above 1.0 a m p ./s q . d m .; u n d e r, b r ig h t. 1.59 H a z e above 2 .6 a m p ./s q . d m .; u n d e r, b r ig h t. 67 0 .5 2 .0 / 2 .1 2 H a z e above 2 .6 a m p ./s q . dm .; u n d e r, b r ig h t. 68 - 2 .0 / 2 .1 2 H a z e above 2 .6 a m p ./s q . d m .; u n d e r, b r ig h t. S o lu tio n T r e a t e d w ith 15.0 e r ./l. o f A c tiv a te d C a rb o n , F i l t e r e d 30% G ly o x a l 298 3.70 68 1 1/ 0 .3 1 * * H a z e above 2 .6 a m p ./s q . d m .; u n d e r, bi-ig h t. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 142 T a b le 6l (C o n tin u ed ) 30% G ly o x a l Panel No. pH Tem p. (° C .) A d d itio n (m l.) T o ta l A d d i­ tio n (m l./ C ath o d e A p p e a ra n c e g.) 299 3.70 67 1 2/ 0.62 H a z e above 2 .6 a m p ./s q . d m .; u n d e r, b r ig h t. 2910 3.8 2 63 2 4/ 1.2 4 H a z e above 3 .2 a m p ./s q . d m .; u n d e r, b r ig h t . 2911 3.80 65 2 6/ 1.85 H a z e above 2 .6 a m p ./s q . d m .; u n d e r, b r ig h t. 2912 3.75 65 2 8/ 2 .4 7 H a z e - b r ig h t above 2 .6 a m p ./s q .d m .; u n d e r, b r ig h t. 2913 3 .6 2 • 65 2 10/ 3 .0 9 H a z e - b r ig h t a b o v e '2 .6 a m p ./s q .d m .; u n d e r, b r ig h t 2914 4 .00 66 2 12/ 3.71 H a z e - b r ig h t above 2 .6 a m p ./s q .d m .; u n d e r, b r ig h t. 2915 4 .0 5 67 2 14/ 4 .3 3 H a z e - b r ig h t to h a z e . 2916 3.90 67 2 16 / 4 .9 5 H a z e above 2 .6 a m p ./s q . d m .; u n d er, b r ig h t. 2917 3.90 66 4 20/ H a z e -b r ig h t . 6.1 9 2918 - 65 - 20/ H a z e -b r ig h t . 6.1 9 * W e ig h ts c a lc u la te d using handbook v a lu e f o r s p e c ific g r a v ­ ity o f e th y l p y r u v a te of 1 .060 1 6 ° / 4 ° . * * W e ig h ts c a lc u la te d usin g handbook v a lu e f o r s p e c ific g r a v ity o f g ly o x a l 1 .1 4 2 0 ° . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 143 'M r F ig u r e 2 5 . N i c k e l - c o b a l t d e p o s its and th e e ffe c t o f in c r e a s in g con- c e n tr a tio n s o f c a rb o n y l com pounds. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 144 Table 62. S o lu tio n 39; the e f fe c t o f 45 g . / l . of n ic k e l f o r m a te , 15 g . / l . of c o b a lt s u lfa te , and in c r e a s in g c o n c e n tra tio n s of b u ty l c h lo r a l h y d ra te on the a p p e a ra n c e of W a tts n ic k e l s o lu tio n d e p o s its . B u ty l C h lo r a l H y d r a te Panel No. pH Tem p. C ath o d e A p p e a ra n c e ( “ C .) tio n l i t 391 3.70 6,5 - - H aze. 392 3.75 65 0.1 0.1 H aze. 393 3.65 67 0 .2 0 .3 H aze. 394 3.70 67 0 .2 0 .5 H a z e above 1 .6 a m p ./s q . d m .; u n d e r, b r ig h t. 395 3.72 66 0.5 1.0 H a z e above 2 .6 a m p ./s q . d m .; u n d e r, b r ig h t. 396 3.75 68 0 .5 1.5 H a z e above 3 .8 a m p ./s q . d m .; u n d e r, b r ig h t. 397 3.78 68 1.0 2.5 H a z e a t h ig h c u r r e n t d e n ­ s ity edge. B r ig h t. 67 1.0 3.5 H a z e above 1 .6 a m p ./s q . d m .; u n d e r, b r ig h t. 70 - 3.5 H a z e - b r ig h t . 398 399 - 3.60 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 145 Table 63, S o lu tio n 4 4 ; the e f f e c t o f 75 g . / l . of n ic k e l c h lo ro a c e ta te , a d d itio n o f c o b a lt s u lfa te , and in c r e a s in g c o n c e n tra tio n s o f c h lo r a l on the a p p e a ra n c e of W a tts n ic k e l so lu tio n d e p o s its . C h lo r a l Panel No. pH Tem p. r c .) A d d i­ tio n ( m l.) T o ta l A d d i­ tio n (m l./ C atho de A p p e a ra n c e g .)* 441 2.5 0 63 - - 442 3.80 65 - - D u ll. 443 3.95 65 15 g. CoSO^ 4 - D u ll. 444 4 .0 3 66 0 .1 0 .1 / 0 .1 5 D u ll to h a z e above 14.0 a m p ./s q .d m .; h aze 14.0 to 4 .3 a m p ./s q .d m .; u n d e r, b r ig h t. 446 4 .0 3 66 0 .2 0 .3 / 0 .4 5 D u ll to h a ze above 11 .8 a m p ./s q .d m .; u n d er, b r ig h t. 445 4 .1 0 64 0 .4 0 .7 / 1 .0 5 3 D u ll to h a ze a t h ig h c u r ­ r e n t d e n s ity edge. B r ig h t . 447 4 .1 2 66 0 .8 1 .5 / 2 .2 6 D u ll to h a ze h ig h c u r r e n t d e n s ity ed g e. B r ig h t, 448 4 .1 5 65 1.0 2 .5 / 3 .7 6 B r ig h t. 449 4 .3 0 65 1.0 3 .5 / 5 .2 7 B r ig h t. B r ig h t above 14.0 a m p . / s q. d m .; u n d e r, d u ll, d a r k . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 146 T a b le ' P a n el No. pH C h lo r a l Tem p. r 63 ( Contii;iued) c.) A d d i­ tio n ( m l.) T o ta l A d d i­ tio n (m l./ C atho de A p p e a ra n c e g .)* 4410 4 .3 8 65 1.0 4 .5 / 6 .7 7 B r ig h t . 4411 4 .4 8 66 1.0 5 .5 / 8 .2 7 B r ig h t . 4412 4 .6 9 65 1.0 6 .5 / B r ig h t above 11.8 a m p ./s q . d m .; u n d e r, h a z e . 9.77 * W e ig h ts c a lc u la te d u s in g handbook v a lu e f o r s p e c ific g r a v ­ ity of c h lo r a l 1 .5 0 5 2 5 ° / 4 ° . AM* Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 147 Ta.ble 64. S o lu tio n 45, the e f fe c t o f 55.0 g . / l , of n ic k e l 3-cryla.te, a d d itio n o f c o b a lt s u lfa te , and in c r e a s in g c o n c e n tra tio n s of c h lo r a l on the a p p e a ra n c e of W a tts n ic k e l s o lu tio n d e p o s its . C h lo r a l Panel No. pH Tem p. r c .) A d d i­ tio n (m l.) T o ta l A d d i­ tio n (m l./ C atho de A p p e a ra n c e g -)* 451 4 .0 0 63 - - E x fo lia te above 14.0 a m p ./ s q ./d m . G re e n d e p o s it above 5 .4 a m p ./s q .d m .; u n d e r, b r ig h t. 452 4.10 65 - - E x fo lia te above 0 .8 am p . s q .d m .; u n d e r, b r ig h t. 453 4 .3 0 65 15 g. CoSO^ 4 - E x fo lia te above 10.8 a m p ./ s q .d m .; u n d e r, h a z e -b r ig h t. 454 4.50 66 0.1 0 .1 / 0 .1 5 G re e n above 4 .3 a m p ./s q . d m .; u n d e r, h a z e -b r ig h t . 456 4 .5 5 66 0 .2 0 .3 / 0 .4 5 G re e n , e n t ir e 455 4 .8 5 64 0 .4 0 .7 / 1.05 P o w d e r y g re e n d e p o s it. 457 5 .1 5 66 0 .8 1 .5 / 2 .2 6 P o w d e ry g re e n d e p o s it. 458 5 .2 8 65 1.0 2 .5 / 3 .7 6 P o w d e ry g re e n d e p o s it. 459 5 ,4 8 65 1.0 3 .5 / 5 .2 7 P o w d e ry g re e n d e p o s it. ra n g e . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 148 T a b le 64 (C o n tin u ed ) C h lo r a l Panel No. pH Tem p, r C .) T o ta l A d d i­ tio n (m l.) A d d i­ tio n (m l./ C athode A p p e a ra n c e g .)* 4510 5.50 65 1.0 4 .5 / 6 .7 7 P o w d e r y g r e e n d e p o s it. * W e ig h ts c a lc u la te d u s in g handbook v a lu e s f o r s p e c ific g r a v ­ ity of c h lo r a l 1 .5 0 5 2 5 * / 4 ° . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. F ig u r e 2 6 . N ic k e l- c o b a lt d e p o s its and th e e ffe c t o f in c r e a s in g con­ c e n tr a tio n s o f c a rb o n y l com pounds. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 150 Tab le 65. S o lu tio n 21; th e e f f e c t of 1 2.5 g / . l . of f e r r o u s s u lfa te and in c r e a s in g c o n c e n tra tio n s of c h lo r a l on the a p p e a ra n c e o f W a tts n ic k e l s o lu tio n d e p o s its . C h lo r a l Panel No. pH Tem p. r c .) A d d i­ tio n (m l.) T o ta l A d d i­ tio n (m l./ C ath o d e A p p e a ra n c e g .)* 211 3.87 63 - - D u ll above 5 .4 a m p ./s q . d m .; u n d e r, h a z e -b r ig h t . 212 3.67 65 0 .5 0 .5 / 0 .7 5 H a z e above 1 .6 a m p ./s q . d m .; u n d e r, h a z e -b r ig h t . 213 4.00 63 0 .5 1 .0 / 1.50 B r i g h t above 9 .7 a m p ./s q . d m .; u n d e r, h a z e . 214 3 .73 66 0 .5 1 .5 / 2 .2 5 B r i g h t above 10.8 a m p ./ s q .d m .; u n d e r, h a z e . 215 3.25 63 1 .5 / 2 .2 5 ' B r ig h t a t h ig h c u r r e n t d e n s ity edge. H a z e above 6 .5 a m p ./s q .d m .; u n d e r, 45 g. . N ic k e l F o rm a te b r ig h t . 216 2.70 65 10 g. T a r t a r ic A c id 1 .5 / 2 .2 5 H a z e , c ra c k e d . 217 3.85 65 - 1 .5 / 2 .2 5 H aze, 218 3.90 65 10 g. F e rro u s S u lfa te * W e ig h ts . 1 .5 / 2 .2 5 c ra c k e d . H a ze , c ra c k e d . • c a lc u la te d usin g handbook v a lu e f o r s p e c ific g r a v ­ it y of c h lo r a l 1 .5 0 5 2 5 ° / 4 ° . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 151 Table 66. S o lu tio n 22; the e f f e c t o f a d d itio n s of f e r r o u s s u lfa te , t a r t a r i c a c id , and c h lo r a l on the a p p e a ra n c e of W a tts n ic k e l s o lu tio n d e p o s its . F e rro u s P an el No. pH Tem p. r c.) A d d i­ tio n (g.) S u lfa te T o ta l A d d i­ tio n C atho de A p p e a ra n c e (g.) 221 3 .5 2 68 5 5 222 3.80 66 5 10 D u ll above 1 0.2 a m p ./s q . d m .; u n d e r, h a z e . 223 3.72 62 5 15 D u ll, p itte d above 3.2 a m p ./s q .d m .; u n d e r, h a z e . 224 3 .72 70 5 20 D u ll, p itt e d above 9.7 a m p ./s q .d m .; u n d e r, h a z e b r ig h t, p itte d . 225 3.80 65 5 25 H a z e , p itte d above 4.3 a m p ./s q .d m .; u n d e r, h a z e b r ig h t, p itte d . 226 3.55 67 227 3 .28 65 - - D u ll, d a r k . 228 3 .74 65 10 g. T a r t a r ic A c id - D u ll, d a r k , c ra c k e d . 229 3.75 64 H a z e a t h ig h d e n s ity edg e. D u ll and p itte d . H a z e , p itte d above 3.2 a m p ./s q .d m .; u n d er, h a z e b r ig h t, p itte d . D u ll, d a r k above 9 .7 a m p ./ 1 m l./ 1 m l. C h lo r a l 1 .5 0 5 g .» s q .d m .; u n d e r, h a z e -b r ig h t, c ra c k e d . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 152 T a b le Panel No. pH Tem p, C c .) F e rro u s S u lfate A d d i­ tio n T o ta l A d d i­ tio n (g.) 2210 — 62 66 (C ontinued) C athode A p p e a ra n c e (g.) 1 m l. / D u ll a t h ig h c u r r e n t d en ­ 1.50 5 g . . s ity edge. H a z e - b r ig h t above 13.0 a m p ./s q .d m .; u n d e r, h a z e , d a r k . * W e ig h t c a lc u la te d usin g handbook v a lu e f o r s p e c ific g r a v ­ ity o f c h lo r a l 1 .5 0 5 2 5 ° / 4 ° . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 153 Table 67. S o lu tio n 25; the e f f e c t of 1 2 .5 g . / l . o f f e r r o u s s u lfa te , 50 g . / l . of n ic k e l p r o p io n a te , and in c r e a s in g c o n c e n tr a ­ tio n s o f c h lo r a l on the a p p e a ra n c e of W a tts n ic k e l so­ lu tio n d e p o s its . C h lo r a l A d d i­ tio n (m l.) T o ta l A d d i­ tio n (m l./ 66 - - 4 .5 0 66 0 .5 0 .5 / 0 .7 5 D u ll, c r a c k e d . 253 4 .4 8 64 0 .5 1 .0 / 1.50 H a z e a t h ig h c u r r e n t den­ s ity ed g e. H a z e - b r ig h t above 5 .4 a m p ./s q .d m .; u n d e r, h aze. 254 4.60 72 - Panel N o. pH 251 4 .5 0 252 Tem p. r * W e ig h ts C .) - C ath o d e A p p e a ra n c e D u ll, d a r k . H aze, c ra c k e d . c a lc u la te d u s in g handbook v a lu e f o r ity of c h lo r a l 1 .5 0 5 ZS° / 4 ° . s p e c ific g r a v ­ , Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 154 F ig u r e 2 7 . N i c k e l - i r o n d e p o s its and th e e f ­ f e c t o f v a r io u s a d d itio n s . Reproduced w ith permission o f the copyright owner. Further reproduction prohibited without permission. 155 T a b le 68. S o lu tio n 23; the e ffe c t on the cathode of f i l t e r p a p e r in c lo se c o n ta c t and p r e d ip p in g in c in n a m a ld é h y d e . Tem p. P a n e l* No. ( “ C .) T r e a t m e n t of C athode C athode A p p e a ra n c e 231 68 None D u ll. 232 66 W ra p p e d in tw o th ic k ­ n e s s e s o f W h a tm a n N o . 1, 11 c m . f i l t e r p a p e r . P it t e d , m o r e r e fle c ta n t th a n c o n tr o l. 233 60 S am e as ab o ve. P it te d , m o r e th an c o n tr o l. r e f le c ta n t 234 70 S am e as ab o ve. P it t e d , m o r e th a n c o n tr o l. r e f le c ta n t 235 65 D ip p e d once in a le n s o f c in n a m a ld é h y d e f lo a t ­ ing on a W a tts s o lu tio n . H a z e - b r ig h t , lig h t i n t e r ­ fe r e n c e p a tte r n . 238 78 S am e as above (s o lid fo r m a tio n in le n s ) . H a z e - b r ig h t , e x fo lia te above 2 .1 a m p ./s q .d m .; u n d e r, no d e p o s it. 237 49 S am e as ab o ve. H a z e , t r e e d above 4 .3 a m p ./s q .d m .; u n d er, b r ig h t w ith in te r f e r e n c e . 236 26 S am e as ab o ve. H ig h c u r r e n t d e n s ity , b u rn e d , d u ll. * The p H o f the s o lu tio n w as 3.8 and d e p o s itio n s w e r e c a r ie d out " fo r tw e n ty m in u te s . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 156 T ab le 69. S o lu tio n 312; the e ffe c t of p re d ip p in g the cathode in a n ic k e l s o lu tio n c o n ta in in g C la y to n Y e llo w on the a p p e a r­ ance o f W a tts n ic k e l s o lu tio n d e p o s its (p H , 3.2; dipped tw e n ty t im e s ; 20 m in u te s d e p o s itio n ; 3 a m p e r e s ). Tem p. P a n e l* No. (° C .) D ip S o­ lu tio n D ip So­ lu tio n Tem p. C athode A p p e a ra n c e ( “ c .) 3 1 2 -1 60 31 25 D u ll. 3 1 2 -2 ** 57 31 25 H a z e - b r ig h t . 3 1 2 -3 55 31 60 D u ll above 1 1 .8 a m p ./s q .d m .; h a z e 11.8 to 1.0 a m p ./s q .d m .; unde r , d u ll. 3 1 2 -4 24 31 64 E x fo lia te a t h ig h c u r r e n t d en ­ s ity edge. H a z e - b r ig h t above 6.5 a m p ./s q .d m .; u n d e r, h a ze . 3 1 2 -5 25 311 57 E x fo lia te a t h ig h c u r r e n t den­ s ity ed g e. H a z e - b r ig h t above 8.6 a m p ./s q .d m .; u n d e r, h a ze . 3 1 2 -6 60 311 58 D u ll. * T h e p H o f the W a tts n ic k e l s o lu tio n w as 3 .2 , the cathode w as d ip p ed tw e n ty tim e s and d e p o s itio n s w e re c a r r i e d out f o r 20 m in u te s . * * D e p o s ite d f r o m S o lu tio n 311. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 157 Tab le 70. S o lu tio n 332; the e f fe c t o f dip p in g the cathode in a n ic k e l s o lu tio n c o n ta in in g M e th y le n e B lu e on the a p p e a ra n c e of W a tts n ic k e l s o lu tio n d e p o s its . D ip So­ Panel No. Tem p. r c .) pH D ip S o­ lu tio n lu tio n Tem p. C atho de A p p e a ra n c e ( “ C .) 3 3 2 -1 ^ 60 3 .1 5 - - D u ll a t h ig h c u r r e n t d e n s ity ed g e. H aze above 1.0 a m p ./s q .d m .; u n d e r, d u ll. 3 3 2 -2 ^ 60 3.30 33 25 D u ll a t h ig h c u r r e n t d e n s ity e d g e. H aze above 1 .6 a m p ./s q .d m .; u n d e r, d u ll. 3 3 2 -3 ^ 62 3 .4 5 331 60 D u ll. 3 3 2 -4 64 3 .4 5 33 66 D u ll a t h ig h c u r r e n t d e n s ity edg e. H a ze above 2 .6 a m p ./s q .d m .; u n d e r, d u ll. 3 3 2 -5 61 4 .0 5 33 31 D u ll a t h ig h c u r r e n t d e n s ity edg e. H aze above 2 .6 a m p ./s q .d m .; u n d e r, d u ll. 3 3 2 -6 61 4 .1 0 33 45 D u ll a t h ig h c u r r e n t d e n s ity edg e. H aze above 2 .6 a m p ./s q .d m .; u n d e r, d u ll. 3 3 2 -7 60 4 .2 1 33 63 D u ll a t h ig h c u r r e n t d e n s ity edg e. H aze above 4 .3 a m p ./s q .d m .; u n d e r, d u ll. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 158 T a b le 70 (C o n tin u ed ) Tem p. Panel No. r c .) pH D ip So­ lu tio n D ip So­ lu tio n Tem p. C Cathode A p p e a ra n c e C .) 3 3 2 -8 61 5.1 0 33 57 D u ll, p itte d a t h ig h c u r ­ r e n t d e n s ity edge. H a ze abo ve 1.0 a m p ./s q .d m .; u n d e r, d u ll. 3 3 2 -9 62 3 .5 2 ^ 33 43 H a z e a t h ig h c u r r e n t d e n s ity ed g e. B r ig h t. 3 3 2 -1 0 60 3 .5 0 ^ - - H a z e a t h ig h c u r r e n t d e n s ity ed g e. B r ig h t . 4.5.0 - - D u ll. 25 5 .4 0 33 61 25 5.40 000 3 3 2 -1 1 62 4 3 3 2 -1 2 E x fo lia te a t h ig h c u r r e n t d e n s ity edg e. H azeb r ig h t above 4 .3 a m p ./ s q .d m .; u n d e r, h a z e . E x fo lia te a t hig h c u r r e n t d e n s ity edge. H azeb r ig h t above 6.5 a m p ./ s q .d m .; u n d e r, h a z e . 1 T h e p H o f the s o lu tio n w as 3 .2 , th e cathode w as dipped tw e n ty t im e s , and d e p o s itio n s w e r e c a r r i e d o u t f o r 10 m in u te s . 2 D e p o s ite d 20 m in u te s . D e p o s ite d f r o m S o lu tio n 331, C ath o d e d r ie d a f te r dip. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 159 F ig u r e 2 8 . T h e e ffe c t o f p re d ip p in g o r f i l t e r p a p e r in c lo s e c o n ta c t w ith th e cath o d e, on th e a p p e a ra n c e o f W a tts n ic k e l d e p o s its . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. l6o T a b le 71, R M S s u r fa c e ro u g h n ess of W a tts p a n e ls . R M S R oughness (m ic r o inches) Panel N o, 9.0 a m p ./s q .d m . 6.5 a m p ./s q .d m . p H 2 .2 12 3 .2 1.8 13 3.8 4 .2 14 7 .2 6 .6 15 4 .4 3 .6 pH 3.8 22 2 .6 3.4 23 2 .8 2.8 24 4 .4 4 .8 25 8.0 8 .4 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. .161 T a b le 7 2 . R M S s u rfa c e rou g h n ess e ffe c ts o f c a rb o h y d ra te s . R M S R oughness (m ic r o in c h e s ) Panel No. 9.0 a m p ./ s q .d m . R M S Roughness (m ic ro in c h e s ) Panel N o. 6 .5 am p. / s q .d m . . 9 .0 am p. / s q .d m . G ly c e r ald eh y d e D e x t r in [0 .5 g . / l . , p H 2 .2 ] [0 .5 g . / l . , p H 2 .2 ] 6.5 am p. / sq .d m . 740 2 .8 1.8 840 4 .0 4.0 730 0 .7 1.4 830 5 .8 4.8 720 6.0 4.0 820 2 .2 1.9 [p H 3 .8] [p H 3 .8] 71 3.2 3.0 81 2 .9 2.2 72 2 .6 1.0 82 6.0 4.0 73 2 .2 1.4 83 7 .6 6.0 74 3.2 2 .4 84 7 .4 6.0 [2 .0 g . / l . / p H ‘ 2 .2 ] [2 .0 g . / l - . pH 2 .2 ] 2 .4 1.4 ■ 850 5 .2 4.2 3.6 2 .4 860 5 .8 3.8 770 2 .8 2.0 870 5 .6 4.6 780 0 .9 2.0 880 9 .2 8.6 750 760 ' [p H 3 .8] [p H 3 .8] 78 4 .2 7 .5 88 3.8 4 .4 77 2 .6 3.2 87 5 .2 5.2 76 2 .6 3 .6 86 5.2 4.2 75 8 .4 8 .4 85 5 .2 6.0 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 162 T a b le 72 (C o n tin u ed ) R M S R oughness ( m ic r o inches) Panel N o. 9 .0 a m p ./ s q .d m . 6 .5 am p. / s q .d m . R M S R oughness ( m ic r o inches) Panel No. 9 .0 am p. / s q .d m . X y lo s e G lu c o s e [0 .5 g . / l . , p H 2 .2 ] [0 .5 g . / l . , p H 2 .2 ] 6.5 a m p ./ s q .d m . 330 .3.6 4.2 430 3.4 2 .8 340 2 .4 3.6 440 2 .8 3.6 320 8 .4 7.2 420 8 .4 8 .4 310 4 .2 4 .4 410 9.0 7.2 [p H 3.8] 350 2 .6 360 ' . [p H 3 .8 ] 1.2 450 2 .3 2 .4 3 .8 3.4 460 3 .8 4 .4 370 3.2 2 .6 470 4 .4 4.0 380 4 .2 4.6 480 4 .2 3.6 L a c to s e R a ffin o s e [0 .5 g . / l . , p H 2 .2 ] [0 .5 g . / l . , p H 2 .2 ] 530 3.2 3.8 630 2 .2 3.2 540 3 .8 4 .4 640 1.6 0 .8 520 6 .8 7.0 620 3.2 . 3,6 5 .6 5.8 610 4.0 3.4 510 . [p H 3 .8 ] [p H 3.8] 550 5 .4 3.2 650 2.0 1.2 560 4 .8 4 .4 66o 1.4 1.2 570 4 .0 4.0 670 1.2 1.2 586 7 .2 8.2 680 4 .4 2 .2 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 163 u 0 0 ui 7 0 w I S 6 0 01 0 Ü 5 0 0 i 3 0 2 0 1 0 0 25 35 55 T E M PE R A T U R E , «C, 75 F I G U R E 29 . S U R F A C E R O U G H N E S S VS. T E M P E R A T U R E A T p H 2 . 2 . 9 . 0 A M P . / S Q . D M . , A ND 2 . 0 G . / L . F O R : 1 . # WATTS 2 .A G L Y C E R A L D E H Y D E 3 . 0 XYLOSE 4. A GLUCOSE 5 . * LACTOSE HYDRATE 6 . 0 RAFFINOSE HYDRATE 7 . B DEXTRIN ••--"0,5 G . / L . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 164 p 5.0 ^ 4.0 25 35 55 T E M P E R A T U R E , ®C. F I G U R E 30. S U R F A C E R O U G H N E S S VS. T E M P E R A T U R E A T p H 2 . 2 , E. 5 A M P . / S Q . D M . , AND 2 . 0 G . / L . F O R ; 1.* w atts 2 .A GLYCERALDEHYDE 3 . 0 XYLOSE 4.AGLUCOSE 5 . * LACTOSE HYDRATE 6 . 0 RAFFINOSE HYDRATE 1M DEXTRIN 0. 5 G. / L . Reproduced with permission o f the copyright owner. Further reproduction prohibited without permission. 165 11) .0 0 0 X U 0 § 0 .0 2 od 0 0 0 .0 25 35 55 TEMPERATURE, °C. 75 F I G U R E 31. S U R F A C E R OU GHNE S S VS. T E M P E R A T U R E A T p H 3 . 8 . 9 . 0 A M P . / S Q . D M . , AND 2 . 0 G . / L . F O R : 1 . # WATTS 2. A G L Y C E R A L D E H Y D E 3 . 0 XYLOSE 4.A GLUCOSE 5 . # L AC TO SE HYDRATE 6 . 0 R A F F IN OS E HYDRATE 7 . B DEXTRIN ' — - 0.5 G . / L . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 166 l) 0 0 u 0 X u 0 o a 0 t/1 s « 0 .0 .0 0 0 25 35 55 T E M P E R A T U R E , °C. F I G U R E 32. S U R F A C E R O U G H N E S S VS. T E M P E R A T U R E A T p H 3 . 8 , 6 . 5 A M P . / S Q . D M . , AND 2 . 0 G . / L . F O R : ! . # WATTS 2. A G L Y C E R A L D E H Y D E 3 . 0 XYL OS E 4 . A GL UCOS E 5 . # LACTOSE HYDRATE 6 . 0 RAFFIN OSE HYDRATE 7 . B DEXTRIN 0.5 G ./L . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 167 Tab le 73. R M S s u rfa c e ro u g h n ess e ffe c ts o f p o ly m e r s and un s a t­ u r a te d a lip h a tic co m p o u n d s. R M S R o ughness (m ic r o in ch es) Panel No. 9 .0 am p. / s q .d m . 6.5 R M S Roughness (m ic r o inches) Panel No. a r n p ./ s q .d m . 9.0 am p. / s q .d m . M e th y l C e llu lo s e P o l v in y l A lc o h o l [0 .5 g . / l . , p H 2 .2 ] [0 .5 g . / l . , p H 2 .2 ] 6.5 a m p ./ sq .d m . 910 3 .8 4.0 1640 9.8 6.0 920 5 .6 5 .6 1630 3.8 2 .4 930 8.6 8 .8 1620 4 .8 6.0 940 7 .6 6 .6 1610 4 .2 3.4 [p H 3 .8 ] [p H 3 .8] 94 3.8 5.0 164 3.4 4.0 93 6.2 5 .8 163 7.0 5.2 92 5 .0 5.2 162 3.6 4.0 91 > 1 0 .0 > 1 0 .0 161 5 .8 6.0 A c r y li c A c id 1,4 -B u ty n e d io l [0 .5 g . / l . , p H 2 .2 ] [0 .5 g . / l . , p H 2 .2 ] 4310 4 .0 3.2 5310 4.0 2.8 4320 2 .2 2 .8 5320 3.8 3.8 4330 5 .6 4 .4 5330 > 1 0 .0 8.4 4340 7 .6 8.0 5340 8.0 6.0 - [p H 3 .8 ] [p H 3.8] 431 3.2 4 .0 531 3.4 3.0 432 4.0 3.0 532 3.8 3.6 433 8.0 6 .6 533 6.4 6.2 434 > 1 0 .0 > 1 0 .0 534 > 10.0 8.0 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 168 T a b le 7 3 (C o n tin u ed ) R M S R oughne s s (m ic ro in ch e s) Panel No. 9.0 am p. / s q .d m . 6 .5 am p. / s q .d m . R M S R oughness (m ic ro in c h e s ) Panel No. [2 .0 g . / l . , p H 2 .2 ] 9.0 am p. / s q .d m . 6.5 am p. / sq .d m . [2 .0 g . / l . , p H 2 .2 ] 4350 6.2 8.0 5 3.50 2 .2 2.0 4360 4 .6 4 .0 5360 2 .6 2 .8 4370 8.0 7 .4 5370 0 .8 0 .8 4380 6.0 6.0 5380 1.2 1.2 [p H 3.8] [p H 3 .8 ] 435 4.0 3.8 535 2 .4 2 .4 436 7 .4 6 .6 536 4.0 3.4 437 > 1 0 .0 > 1 0 .0 537 > 1 0 .0 4.0 438 > 1 0 .0 > 1 0 .0 538 9.0 5.0 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 169 m.o 5.0 25 35 55 TEMPERATURE, °C. 75 F I G U R E 33. S U R F A C E R O U G H N E S S VS. T E M P E R A T U R E A T p H 2 . 2 . 9 . 0 A M P . / S Q . D M . , AND 0 . 5 G . / L , F O R : 1 . # WATTS 2.AM ETHYLCELLULOSE 3. ■ P O L Y V I N Y L A L C O H O L 4 . • A C R Y L I C ACI D 5.A1.4-BUTYNEDIOL ----2. 0 G ./L . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 170 u s 0 o; y 1 to* 5 c: 0..0 25 35 55 TEMPERATURE, °C. 75 F I G U R E 34. S U R F A C E R OU GHNE S S VS. T E M P E R A T U R E A T p H 2 . 2 , 6 . 5 A M P . / S Q . D M . , AND 0. 5 G , / L . F O R : ! . • WATTS z .A m ethylcellulose 3. ■ POLYVINYL ALCOHOL 4 . # A C R Y L I C ACI D 5 .A 1 ,4 -B U T Y N E D IO L * -----2 . 0 G . / L . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 171 10. 0 25 35 55 T E M P E R A T U R E , *C. 75 F I G U R E 35. S U R F A C E R O U G H N E S S VS. T E M P E R A T U R E A T p H 3 . 8 . 9 . 0 A M P , / S Q . D M , , AND 0 . 5 G . / L . F O R ; 1. # W A T T S 2. A M E T H Y L C E L L U L O S E 3. ■ P O L Y V I N Y L A L C O H O L 4 . « A C R Y L I C ACI D 5 .A 1,4-BUTYNEDIOL 2 . 0 G. / L . Reproduced with permission o f the copyright owner. Further reproduction prohibited without permission. 172 w 4.0 2,0 25 35 55 T E M P E R A T U R E , ®C. 75 F I G U R E 3 6. S U R F A C E R O U G H N E S S VS, T E M P E R A T U R E AT pH 3 . 8 , 6 . 5 A M P , / S Q . D M , . AND 0 . 5 G . / L . FOR: 1. # W A T T S 2. A M E T H Y L C E L L U L O S E 3. « P O L Y V I N Y L A L C O H O L 4 . « A C R Y L I C ACI D 5. A 1 , 4 - B U T Y N E D I O L - - - - 2 . 0 G , / L, Reproduced with permission o f the copyright owner. Further reproduction prohibited without permission. 173 T ab le 74. R M S ro u g h n e s s e ffe c ts of c a r b o n y l compounds, R M S Roughness ( m i c r o inches) P anel No. 9.0 a m p ,/ s q .d m . R M S Roughness (m ic r o in c h e s ) Panel No. 6.5 a m p ./ s q .d m . — Camphor 6.5 amp. / s q .d m . 9.0 amp. / s q .d m . p - B r o m o a c e t o p henone ' [0 .5 g . / l . , p H 2 .2 ] [0 .5 g . / l . , p H 2.2] 1110 2 .4 4.0 1210 2.0 1.8 1120 3.6 4 .6 1220 5.0 7.4 1130 9 .2 8.6 1230 7.0 6.8 1140 9.5 6.6 1240 7 .8 6.8 [p H 3.8] [p H 3.8] 114 3.6 3.4 124 5.2 1.8 113 6.0 5.6 123 3.0 2.4 112 6.8 7.0 122 3.2 1.8 111 5.8 6.0 121 9 .6 9.8 C in n a m a l dehyde Ac e ta l dehyde [ 0 .5 g . / l . , p H 2 .2 ] [0 .5 g . / l . , p H 2.2] 2610 2.0 1.6 > 10.0 2620 1.6 2.0 8.0 3.6 2630 8.4 4.6 5 .4 2.0 2640 4 .8 7.2 1340 7.0 4 .6 1330 > 1 0 .0 1320 1310 ' [p H 3.8] [p H 3.8] 261 10.0 >10.0 2.0 262 7.0 9.6 4.0 4.0 263 8.2 8.0 4 .8 4 .8 264 3.2 6.0 134 * 3.8 133 2.0 132 131 ' Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 174 T a b le 74 (C o n tin u ed ) R M S Roughness ( m i c r o inches) Panel No. 9 .0 a rn p ./ sq.drn. 6 .4 a m p ./ s q .d m . R M S Roughness ( m ic r o in c h e s ) Panel No. 9.0 am p. / sq .d m . C h lo ra l P y r u v i c A c id [0.5 g . / L , p H 2.2] [0 .5 g . / l , , p H 2.2] 6.5 a m p ./ s q .d m . 1740 4 .8 4.0 1440 3.6 3.2 1730 6.0 4.0 1430 3.8 4 .2 1720 8 .6 > 1 0 .0 1420 4 .6 3.6 1710 6 .6 5,0 1410 3.2 4.0 [ p H 3.8] [p H 3.8] 174 4 .5 5.0 144 3.4 2 .8 173 7 .4 6.0 143 4 .4 4 .6 172 8.5 8.0 142 4.0 4.0 171 > 1 0 .0 >1 0 .0 141 4.0 4.8 B u ty l C h lo ra l b e t a - M e t h y l U m b e ll if e r o n e [0 .5 g . / l . , p H 2 .2 ] [0 .5 g . / l . , p H 2.2] 4010 2 .6 4.0 1540 6.6 6.6 4020 0 .8 3.0 1530 5.4 6.6 40 30 4 .6 3.4 1520 8.0 8.0 4040 6.6 4.8 1510 9 .6 8.6 [p H 3.8] [ p H 3.8] 401 3.0 4.0 154 - 8.0 402 4.0 2 .6 153 7.0 7.0 40 3 2 .4 3.6 152 8 .6 9.6 40 4 3.4 4.0 151 >1 0 .0 9.6 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 175 T a b le 74 (C ontinued) R M S R o ughness (m ic ro in c h e s ) P a n el 9.0 am p. / s q .d m . No. 6.5 a m p ./ s q .d m . R M S Roughness (m ic r o in c h e s ) Panel No . 9.0 amp. / s q .d m . 6.5 am p . / s q .d m . [2.0 g . / l . , p H 2 .2 ] 4050 1.6 1.2 40 60 1.0 1.4 4070 1.6 1.0 4080 1.2 2.0 [ p H 3.8] 405 3.6 3.0 40 6 2 .8 3.2 407 1.8 2 .4 3.6 3.8 408 , Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 176 10.0 4 .0 3 .0 2.0 0. 0 25 35 55 T E M P E R A T U R E , ®C. 75 F IG U R E 37. S U R F A C E ROUGHNESS VS. T E M P E R A T U R E A T pH 2 .2 . 9 .0 A M P ./S Q .D M ., A N D 0 .5 G . / L . FOR: 1. # W A T TS 2 .A C A M P H O R 3 .H p-B R O M O A C E T O PH EN O N E 4 . 0 C IN N A M A L D E H Y D E 5 .0 A C E TA LD EH Y D E 6 . 0 CHLORAL HYDRATE 7 . 0 P Y R U V IC A C m 8. A B U T Y L C H L O R A L 9 . 0 b eU -M E T H Y L U M B E L L IF E R O N E - - - - 2 . 0 G. /L . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 177 in. 0 25 35 55 T E M P E R A T U R E , ®C, 75 F I G U R E 3 8 . S U R F A C E R O U G H N E S S VS. T E M P E R A T U R E AT pH 2 . 2 , 6 .5 A M P , / S Q . D M . , AND 0 .5 G . / L . FOR: 1 . » WATTS 2. A C A M PH O R 3. ■ p - B R O M O A C E T O P H E N O N E 4 . 0 CR IN A M A L D E H Y D E 5 .B ACETALDEHYDE 6 . # CHLORAL HYDRATE 7 . 0 P Y R U V I C C ACID 8. A b u t y l C H L O R A L 9. O b cta-M E T 'H Y L U M B E L L IF E R O N E 2 .0 G ./L . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 178 10.0 -â e 25 35 55 T E M P E R A T U R E , ®C. 75 F I G U R E 3 9 . S U R F A C E R O U G H N E S S VS. T E M P E R A T U R E A T p H 3 . 8 , 9 .0 A M P ./S Q .D M . FOR: 1. # W A T T S 2.A C A M P H O R 3. ■ p - B R O M O A C E T O P H E N O N E 4 . 0 CIN N A M A LD EH Y D E 5 .U A CETALDEHYDE 6 . 0 CHLORA L HYDRATE 7 . 0 P Y R U V I C A CID 8 .A b u t y l - c h l o r a l 9 .0 b e ta -M E T H Y L U M B E L L IF E R O N E - - - - 2 . 0 G . / L. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 179 10. 0 25 35 55 T E M P E R A T U R E , «>C. F I G U R E 4 0 . S U R F A C E R O U G H N E S S VS. T E M P E R A T U R E A T pH 3 .8 . 6 . 5 A M P , / S Q . D M , , AND 0 .6 G . / L . F O R : 1 .» 2. A 3. ■ 4 .0 5 .0 6 .0 7 .0 b. A 9. o WATTS CAM PHOR p-B R O M O A C E T O P H E N O N E CIN N A M A LD EH Y D E ACETALDEHYDE CHLORA L HYDRATE P Y R U V I C AC ID butyl chloral beta-M E T H Y L U M B E L L IF E R O N E - - - " 2 .0 G. /L . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 180 T a b le 75. RMS ro u g h n ess e ffe c ts of dyes. R M S Roughness ( m ic r o in c h e s ) Panel No. 9 .0 a m p ./ s q .d m . R M S Roughness (m ic r o in c h e s ) Panel No. 6.5 am p. / s q .d m . 9.0 a m p ./ s q .d m . C la y to n Y e llo w P r im u lin e Y e llo w [ 0 .5 g . / l . , p H 2 .2 ] [ 0 .5 g . / l . , p H 2.2] 6.5 am p . / sq.dm . 3110 4 .0 5.4 3210 2 .8 4.2 3120 2 .2 2 .6 3220 5 .6 3.2 3130 > 1 0 .0 9 .5 3230 6.8 6.0 3140 2 .6 3.4 3240 3.4 3.0 [p H 3.8] [ p H 3.8] 311 2 .2 3.6 321 2 .6 3.4 312 6.0 5 .6 322 5 .6 4 .2 313 5 .8 2 .6 323 3.0 4.4 314 3 .8 5.0 324 5.0 5.6 M o n a s t r a l B lu e [ 0 .5 g . / l . , p H 2.2] 2810 4.0 4.0 2820 3.2 3.8 2830 9.0 8.5 2840 9.0 > 1 0 .0 - [ p H 3.8] 284 4.0 5 .4 283 9.0 9.0 282 > 1 0 .0 > 1 0 .0 281 > 1 0 .0 > 10.0 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 181 10.0 2.0 25 35 55 T E M P E R A T U R E , ®C. 75 F I G U R E 41 . S U R F A C E R O U G H N E S S VS . T E M P E R A T U R E A T pH 2 . 2 , 9 . 0 A M P , / S Q . D M . , AND 0 . 5 G . / L . F O R : I O WATTS 2 . # MONASTRAL BLU E 3 .A CLAYTON YELLOW 4 . a PRIM U L IN E YELLOW Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 182 10,0 35 25 55 TEM PERATURE, °C . 75 F I G U R E 42. S U R F A C E R O U G H N E S S VS. T E M P E R A T U R E A T pH 2 . 2 . 6 . 5 A M P . / S Q . D M . , AND 0 . 5 G . / L . F O R : 1 O 2 .# 3.A 4.B WATTS MONASTRAL BLUE CL A Y T O N YELLOW PR IM U L IN E YELLOW Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 183 10.0 8.0 _ 25 35 55 TEM PERATURE, °C , 75 F I G U R E 4 3 . S U R F A C E R O U G H N E S S VS . T E M P E R A T U R E A T p H 3 . 8 , 9 . 0 A M P . / S Q . D M , , AN D 0 . 5 G . / L . F O R ; 1 . 0 WATTS 2. # MO NASTRAL BL U E 3 .A C L A Y T O N YELLOW 4. « P R I M U L I N E YELLOW Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 184 10. 0 2 4 .0 3.0 2.0 25 35 55 TEM PERATURE, °C . 75 F I G U R E 4 4 . S U R F A C E R O U G H N E S S VS . T E M P E R A T U R E A T p H 3 . 8 . 6. 5 A M P . / S Q . D M . , A N D 0. 5 G . / L . F O R : 1. O W A T T S 2. « M O N A S T R A L B L U E 3 .A C L A Y T O N YELLOW 4. « P R IM U L IN E YELLOW Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 185 T a b le 7 6 , R M S ro ugh ness e ffe c ts of p henols. R M S Roughness ( m ic r o in c h e s ) Panel No. 9.0 amp. / s q .d m . 6.5 a m p ./ s q .d m . R M S Roughness ( m i c r o inches) Panel No. 9.0 a m p ./ sq.dm . 6.5 a m p ./ s q .d m . 3 ,5 ,3 , ' 5 - T e t r a n i t r o 4 , 4 - d ih y d ro x y b ip h e n y l [0 .3 3 g /1 ., p H 2 .2 ] 4 , 4 - D ih y d r o x yb ip h e n y l [ 0 .3 3 g . / l . , p H 2 .2 ] 3010 2 .8 3.4 2710 2 .3 3.2 .3020 2 .8 3.4 2720 3.8 5.0 30 30 6.0 7.6 2730 4.6 4.0 3 .6 3.4 2740 3.6 3.0 ‘ 3040 [p H 3.8] [p H 3.8] 301 2 .4 2 .2 271 9.0 5.0 302 4.0 4 .4 272 - 8.5 30 3 9.0 7.6 273 6.0 6.0 304 10.0 10.0 274 - - Phenol o - N it r o p h e n o l [0 .5 g . / l . , p H 2.2] [0 .5 g . / l . , p H 2.2] 4110 5.0 4.8 4210 3.4 3.8 4120 3.0 3.6 4220 3.2 2.4 4130 9.4 8.0 4230 3.8 3.8 4140 9.6 9.0 4240 3.8 3.2 [p H 3.8] [p H 3.8] 411 3.4 3.2 421 4.0 4.4 412 4.0 5.2 422 4.8 4.0 413 3.8 ' 3.8 423 4 .4 4.2 414 > 1 0 .0 > 10.0 424 3.4 3.8 , Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 186 T a b le 76 (C o ntinued) R M S Roughness ( m i c r o inches) Panel No. 9.0 am p. / s q .d m . 6.5 am p . / s q .d m . R M S Roughness ( m i c r o inches) Panel No. 9.0 a m p ./ s q .d m . 6.5 am p. / sq .d m . p - A m in o p h e n o l H y d r o c h l o r id e o -A m in o p h e n o l H y d r o c h lo r id e [ 0 .5 g . / l . / p H 2 .2 ] [0 .5 g . / l . , p H 2.2] 4810 2 .6 3.4 4910 3 .6 4 .4 4820 5 .2 4.6 4920 3.0 2.8 4830 7.0 7.0 4930 3.4 2.8 4840 4 .8 5.0 4940 6.4 4 .6 [p H 3.8] [p H 3.8] 481 3 .6 2 .4 491 2.8 3.0 482 3.4 2.8 492 5.2 4.0 483 - - 493 2.8 2.6 484 - - 494 6.2 5.2 [2 .0 g . / l . , p H 2.2] [2 .0 g . / l . , p H 2 .2 ] 4850 > 1 0 .0 4.4 4950 8.0 6.2 4860 - - 4960 6.5 5.0 4870 7 .6 5.2 4970 4 .2 3.4 4880 5 .4 6.0 4980 3.8 2.8 [p H 3.8] [ p H 3.8] 485 5 .4 486 _ 5 .4 495 6.4 5.2 - 496 6.8 6.0 487 - - 497 5.2 6.0 488 - - 498 6.6 5.0 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 187 T a b le 76 (C ontinued) R M S Roughness ( m i c r o inche s) Panel No. 9.0 am p./ . s q .d m . 6 .5 a m p ./ s q .d m . R M S Roughness ( m ic r o in c h e s ) Panel No. 9.0 am p. / sq .d m . C a te c h o l R e s o r c in o l [ 0 .5 g . / l . , p H 2 .2] [0 .5 g . / l . , p H 2.2] 6.5 a r n p ./ sq.dm . 5010 6.0 5.0 5110 3.4 2.6 5020 3.0 3.6 5120 3.2 2 .6 50 30 9.0 8 .8 5130 9.8 8.6 5040 > 1 0 .0 9 .6 ' 5140 >10.0 9.5 [p H 3.8] [ p H 3.8] 501 4 .0 5 .4 511 3.0 3.4 502 3 .6 3 .8 512 4 .4 5.0 50 3 7.0 6 .4 513 6.4 6.0 50 4 6.2 5.0 514 8.0 7.0 [2.0 g . / l . , p H 2.2] [2 .0 g . / l . , p H 2 .2 ] 5050 5.0 3.4 5150 2 .4 2.4 5060 4 .8 4.0 5160 6.6 3.8 5070 > 1 0 .0 9.0 5170 8.6 7.0 5080 > 1 0 .0 > 1 0 .0 5180 8 .6 7.2 [p H 3.8] [ p H 3.8] 505 4 .4 4 .0 515 4.0 3.6 506 4 .0 4 .4 516 5.6 3.8 50 7 6.0 7.0 517 4 .2 4.0 508 > 1 0 .0 > 1 0 .0 518 9.5 7.0 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 188 T a b le 76 (C ontinued) R M S Roughness ( m i c r o inches) Panel No . 9.0 a m p ./ s q .d m . R M S Roughness ( m i c r o inches) Panel No. 6.5 am p . / s q .d m . b e t a - N aphtho 1 9.0 am p. / s q .d m . 6.5 am p. / sq.dm . ' [0 .5 g . / l . , p H 2 .2 ] 5210 3.0 3.8 5220 5.0 3.8 5230 5.0 3.6 5240 3.6 2 .4 ' [ p H 3.8] 521 - 3.2 522 4 .2 2 .8 523 3.2 3.2 524 4.0 2 .6 - Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 189 10,0 to w X u S su 5 C/Î i 0.0 25 35 55 T EM PE R A T U R E , °C . 75 F I G U R E 4 5 . S U R F A C E RO U G H N E S S V S . T E M P E R A T U R E A T p H 2 . 2 . 9 . 0 A M P . / S Q . D M . , AND 0 . 5 G . / L . F O R : 1. # W A T T S 2 . A 4 , 4 ' - D I H Y D R 0 X Y B I P H E N Y L 0. 3 G. / L . 3. □ P H E N O L 4. A CATECHOL 5. « R E S O R C IN O L 6. • b e t a - N A P H T H O L 2 .0 G ./L . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 190 10. 0 9 .0 8.0 —4 .0 6.0 5 .0 M 4 .0 3 .0 2.0 0 0. 0 25 35 55 T E M P E R A T U R E , ®C. 75 F I G U R E 4 6 . S U R F A C E R O U G H N E S S VS . T E M P E R A T U R E A T pH 2 . 2 . 6. 5 A M P . / S Q . D M . , A N D 0 . 5 G . / L . F O R ; 1 . # WATTS 2 . A 4 , 4 ' . D I H Y D R O X Y B I P H E N Y L 0. 3 G . / L . 3. n P H EN O L 4 .A C A T E C H O L 5. ■ R E S O R C I N O L 6. # b e t a - N A P H T H O L ----2 .0 G ./L . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 191 10.0 (/) w X U s s u 2 w* 25 55 35 75 T E M P E R A T U R E ,°C . F I G U R E 47 . S U R F A C E R O U G H N E S S V S. T E M P E R A T U R E A T p H 3 . 8 , 9 .0 A M P . / S Q . D M . , A N D 0 . 5 G . / L . FOR; 1. # WATTS 2. A 4 . 4 ' - D I H Y D R 0 X Y B I P H E N Y L 3. □ P H E N O L 4. A C A T E C H O L 5. ■ R E . S O R C I N O L 6. • b e t a - N A P H T H O L 0.3 G . / L . 2.0 G . / L . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 192 10.0 7 .0 35 25 TEM PERATURE. 55 ®C. 75 F I G U R E 4 8. S U R F A C E RO U G H N ES S V S . T E M P E R A T U R E A T p H 3 . 8 , 6 . 5 A M P , / S Q . D M . , AND 0 . 5 G . / L . F O R : 1. 2. 3. 4. 5. 6. # WATTS A 4 . 4 ' - D IH Y D R O X Y B I P H E N Y L 0 . 3 G . / L . □ PHENOL A catechol ■ RESO R C IN O L # beta-N A PH T H O L 2 .0 G ./L . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 193 10.0 CO W S s § z CO i 25 35 55 T E M P E R A T U R E , ®C. 75 F I G U R E 4 9 . S U R F A C E RO U G H N ES S VS. T E M P E R A T U R E A T pH 2 . 2 , 9 . 0 A M P . / S Q . D M . , A N D 0 . 5 G . / L . F O R : 1. • W A T T S 2. O o - N I T R O P H E N O L 3. ■ o - A M I N O P H E N O L H Y D R O C H L O R I D E 4 . A p-A M IN O P H E N O L HYDROCHLORIDE 5. O 3, 5, 3 ' , 5 ' - T E T R A N I T R O - 4 , 4 ' - D I H Y D R O X Y BIPH EN Y L 0 . 3 G . / L . • ---- 2 , 0 G u / L . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 194 10.0 ■ A - U5 4 , 0 25 35 55 T E M P E R A T U R E , ®C. 75 F I G U R E 50 . S U R F A C E R O U G H N E S S VS . T E M P E R A T U R E AT pH 2 . 2 , 6 .5 A M P , / S Q . D M , , AND 0 . 5 G . / L . FO R : 1. « W A T T S 2 .® o-N IT R O PH E N O L 3 .B o -A M IN O P H E N O L HY D R O CH LO RID E 4 . A p -A M IN O P H E N O L H YDROCHLORIDE 5 . 0 3, 5. 3 ' , 5 ' - T E T R A N l T R O - 4 . 4 ' - D l H Y D R O X Y BIPH EN Y L 0 .3 G . / L . 2 .0 G ./L . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 195 10. 0 in 4 . 0 25 35 55 TEM PE R A T U R E , °C, 75 F I G U R E 5 1 . S U R F A C E R O U G H N E S S VS . T E M P E R A T U R E A T p H 3. 8, 9 . 0 A M P . / S Q . D M . , AND 0 . 5 G . / L . F O R : 1 .# WATTS 2 .0 o-N IT R O P H E N O L 3 .B o -A M IN O P H E N O L H YDROCHLORIDE 4 . A p -A M IN O P H E N O L HYDROCHLORIDE 5 . 0 3. 5, 3 ' , 5 ' - T E T R A N I T R O - 4 , 4 ' - D I H Y D R O X Y B IPH EN Y L 0 .3 G M ./L . ---- 2 . 0 G . / L . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 196 10.0 25 35 55 TEM PERA TU RE, °C. 75 F I G U R E 5 2. S U R F A C E R O U G H N E S S VS. T E M P E R A T U R E A T p H 3 . 8 . 6 . 5 A M P . / S Q . D M . , AND 0 . 5 G . / L . F O R : 1. • W A T T S 2 .® o -N IT R O P H E N O L 3 . B o -A M IN O P H E N O L HY D RO CH LO RIDE 4.A p - A M I N O P H E N O L H Y D R O C H L O R I D E 5 . 0 3 , 5 , 3 ',5 'rT E T R A N IT R O -4 ,4 '-D IH Y D R O X Y BIPH EN Y L 0 .3 G M ./L . 2 .0 G. /L . Reproduced with permission o f the copyright owner. Further reproduction prohibited without permission. 197 T ab le 77. R M S s u rfa c e ro u g h n ess e ffe c ts f o r 2 , 7 - n a p h th a le n e d is u lfo n ic a c id and in c r e a s in g c o n c e n tr a tio n s * of g lu c o s e . R M S Ro ughne s s ( m i c r o inches) Panel No. Tem p. 9.0 a m p ./ s q .d m . 6 .5 amp. / s q .d m . 3 7 1 -1 2 .6 3 .4 3 7 1 -2 3.2 2 .6 3 7 1 -3 2 .6 2 .4 3 7 1 -4 3.2 2 .2 3 7 1 -5 3.0 2 .8 3 71 -6 1.8 1.8 3 7 1 -7 3.0 2 .6 3 7 1 -8 1.6 1.8 3 7 1 -9 2.0 2 .4 3 7 1 -1 0 1.8 1.9 3 7 1 -1 1 2.0 3.8 25 3 7 1 -1 2 2 .6 2 .8 38 3 7 1 -1 3 3.0 2 .6 52 3 7 1 -1 4 3.0 3.2 60 3 7 1 -1 5 3.4 2 .6 60 (° (:.) * R e f e r to T a b le s 37 to 67 f o r c l a r i f i c a t i o n of add ition s r e ­ f e r r e d to in r e m a i n d e r of ro u g h n e s s ta b le s . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 198 Tab le 78. R M S s u rfa c e ro u g h n e s s e ffe c ts f o r 2 ,7 -n a p h th a le n e d is u lfo n ic a c id and in c r e a s in g c o n c e n tra tio n s o f c h lo r a l. R M S Roughness ( m i c r o inches) Panel No. Tem p. 9.0 am p. / s q .d m . 6.5 amp. / s q .d m . 3 8 1 -1 3.0 2 .9 3 8 1 -2 3.8 4.0 38 1 -3 1 ,6 5.0 38 1 -4 2 .8 5.0 3 8 1 -5 9.0 9.0 38 1 -6 9.0 9.5 3 8 1 -7 4.0 7.0 3 8 1 -8 3.0 3.0 3 8 1 -9 7.0 7.0 3 8 1 -1 0 3.0 3.0 3 8 1 -1 1 1.9 1.8 28 381 -1 2 > 1 0 .0 > 1 0 .0 38 381 -1 3 2 .2 2 .6 52 3 8 1 -1 4 2 .6 3.2 60 3 8 1 -1 5 3.6 2 .6 60 r c .) \ Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 199 10. 0 0.0 8. 0 6. 0 4.0 2.0 CO N CEN TR A TIO N , 10.0 12.0 G ./L . F IG U R E 5 3. S U R F A C E R O U G H N E S S V S . C O N C E N T R A T IO N O F C H L O R A L A N D 5 .0 G . / L . O F 2 ,7 - N A P H T H A L E N E D IS U L F O N IC A C ID AT 65 ® C . FOR CURRENT D E N S I T IE S : 1 . # 9 .0 A M P . /S Q .D M . 2 . O 6 .5 A M P . /S Q .D M . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 200 T able 79. ' R M S s u r fa c e ro u g h n e s s e f f e c t s f o r 2 , 7 -n a p h th a le n e d i s u l fo n ic a c id and i n c r e a s i n g c o n c e n tr a tio n s of r e p r e s e n t a t i v e p o l y m e r and u n s a tu r a te d a l ip h a t ic com po unds. R M S Roughness ( m i c r o inches) Panel No. 9.0 a m p ./ 6 .5 am p. / s q .d m . s q .d m . R M S Roughness ( m ic r o in c h e s ) Panel No. 9.0 am p. / s q .d m . 6.5 amp. / s q .d m . P o ly m e t h y l V i n y l E t h e r M a l e i c A n h y d r id e 2 .6 3 61 -1 2 .4 4 6 -1 3.0 3.0 3 6 1 -2 2.0 1.7 4 6 -2 2 .6 2 .6 3 6 1 -3 2 .2 2 .2 4 6 -3 3.8 3.6 3 6 1 -4 2.0 2.0 46- 4 3.2 3.0 3 6 1 -5 2.2 2 .2 46 -5 4.0 4.0 36l - 6 2 .6 2 .4 4 6 -6 3.4 4.0 3 6 1 -7 7 .6 7 .8 4 6 -7 2 .6 3.2 3 6 1 -8 4.0 2.7 4 6 -8 4 .2 3.8 3 6 1 -9 4 .0 4.0 4 6 -9 3.0 3.8 3 6 1 -1 0 8.0 9.0 46-10 4.0 5.0 4 6-11 3 .6 5 .4 4 6-12 3 .6 2.2 Panel N o ./ Tem p. A c r y lic A c id (° C.) 1 , 4 - B u t y n e d io l 3 6 1 -1 1 /2 8 2 .6 3.2 5 3 1 -1 5.0 4 .6 3 6 1 -1 2 /3 8 2 .8 4.0 5 3 1 -2 6.0 5.0 3 6 1 -1 3 /5 2 5 .4 3.8 5 3 1 -3 5 .6 5.6 3 6 1 -1 4 /6 0 5.0 3.0 5 3 1 -4 4 .8 5.2 3 6 1 -1 5 /6 0 2 .8 3.2 5 3 1 -5 5 .4 5.0 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 201 T a b le 79 (C ontinued) R M S R o ughne ss ( m i c r o inches) P a n el No. 9 .0 am p./ s q .d m . 6 .5 am p. / s q .d m . R M S R oughness ( m ic r o in c h e s ) Panel No. 9.0 amp. / s q .d m . 6.5 am p. / s q .d m . 53 1 -6 5.0 5.0 531 -7 6.2 5 .4 5 3 1 -8 6.0 5.2 5 3 1 -9 4.0 5.0 531 -1 0 6.0 6.0 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 202 10.0 0.0 0. 1 0. 3 0.2 C O N C E N T R A T I O N , G. / L . 0 .4 0.5 F I G U R E 5 4. S U R F A C E R O U G H N E S S VS . C O N C E N T R A T I O N O F A D D I T I O N A G E N T A N D 5 . 0 G . / L . O F 2. 7 - N A P H T H A L E N E D I S U L F O N I C A C I D A T 9 . 0 A M P . / S Q . D M . AND 65 * C , F O R : 1 , 0 GLUCOSE 2. • P V M / M A 3. A A C R Y L I C ACID 4. ■ 1 ,4 -B U T Y N E D IO L Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 203 u 0 0 0 0 0 0 .0 0 0 0 0.0 0.1 0 .3 0. 2 CON CEN TRA TIO N , G , / L . 0 .4 0 .5 F I G U R E 5 5. S U R F A C E R O U G H N E S S VS . C O N C E N T R A T I O N O F A D D IT IO N A G E N T A N D 5 . 0 G . / L . O F 2 , 7 - N A P H T H A L E N E D I S U L F O N I C A C I D A T 6 . 5 A M P . / S Q . D M . A N D 65 » C . F O R : I . O GLUCOSE 2. • P V M /M A 3. A A C R Y L I C ACID 4 .B 1,4-B U T Y N E D IO L Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 204 Table 80. R M S s u r fa c e ro u g h n e s s e ffe c ts f o r 2 ,7 -n a p h th a le n e fo n ic a c id and in c r e a s in g c o n c e n tra tio n s of d y e s . R M S R o ughness ( m ic r o in ch es) Jr’anei No. 9.0 am p. / R M S R oughness (m ic r o in c h e s ) ±^anei No. 6 .5 am p. / s q .d m . s q .d m . 2 .6 3 1 1 -2 ■ 9.0 am p. / 6.5 am p. / s q .d m . s q .d m . • C la y to n Y e llo w 311-1 d is u l- P r i m u li n e Y e llo w 3.4 3 2 1 -1 3.0 4.0 3 .6 4 .4 3 2 1 -2 3 .8 6.0 3 1 1 -3 3.2 2 .8 3 2 1 -3 3.2 3.8 3 1 1 -4 3 .6 3.0 3 2 1 -4 3.2 2 .4 3 1 1 -5 2 .6 3.0 3 2 1 -5 3.4 3.8 3 1 1 -6 2 .6 4 .8 3 2 1 -6 3.2 3.0 31 1 -7 2 .2 1.8 3 2 1 -7 3.6 3.2 3 1 1 -8 3.2 4.0 3 2 1 -8 2 .8 3.0 3 1 1 -9 3 .6 3.8 3 2 1 -9 4 .8 3.0 3 1 1 -1 0 2 ,6 2 .2 3 2 1 -1 0 3 .2 3.2 3 1 1 -1 1 3.0 3.0 3 2 1 -1 1 4.0 4.0 3 1 1 -1 3 3.6 2.2 3 2 1 -1 3 3.6 4.0 • T o lu id in e B lu e M e th y le n e B lu e 3 3 1 -1 3.8 4 .2 3 4 1 -1 2 .2 2 .0 3 3 1 -2 4.0 4.2 3 4 1 -2 2.0 3.4 3 3 1 -3 3.6 3.8 3 4 1 -3 2 .6 2 .2 3 3 1 -4 3.4 3.2 3 4 1 -4 2 .6 2 .4 3 3 1 -5 3.0 4 .0 3 4 1 -5 2 .6 3.2 3 3 1 -6 2 .4 2 .8 3 4 1 -6 1.0 1.8 3 3 1 -7 2 .4 1.8 3 4 1 -7 2.8 2.2 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 205 T a b le 80 (C o n tin u e d ) R M S R o ughness ( m ic r o in ch es ) Panel No. 9.0 a m p ./ s q .d m . 6 .5 am p. / s q .d m . 33 1 -1 1 2 .6 2.0 3 3 1 -1 3 ; 4.0 3.8 R M S R oughness (m ic r o in c h e s ) Panel No. 9 .0 am p. / s q .d m . 6.5 am p. / s q .d m . 3 4 1 -1 1 6.0 4,5 3 4 1 -1 3 2 .0 3.0 M o n as t r a l B lu e 3 5 1 -2 2 .4 3.2 3 5 1 -3 4 .4 2 .2 3 5 1 -4 1 .6 2 .2 3 5 1 -5 1.8 2.0 3 5 1 -6 2 .4 2 .4 3 5 1 -7 3 .6 1.8 3 5 1 -8 2.0 2 .4 3 5 1 -9 2 .4 5.0 Tem p. 3 5 1 -1 0 2.0 2 .4 (° 3 5 1 -1 1 3.0 2 .4 28 3 5 1 -1 2 3.0 4.0 38 3 5 1 -1 3 1.6 2.0 52 3 5 1 -1 4 1.2 0 .8 60 3 5 1 -1 5 2 .2 2 .4 60 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 206 10. 0 in W X u S § 2 CO* 0.0 0.1 0.3 O.Z CO N C EN TR A TIO N , O .'/L . 0 .4 0.5 F I G U R E 5 6 . S U R F A C E R O U G H N E S S VS . C O N C E N T R A T I O N O F A D D I T I O N A G E N T A N D 5 . 0 G . / L . O F 2. 7 - N A P T H A L E N E D I S U L F O N I C A C ID A T 9 . 0 A M P . / S Q . D M . AND 65 ®C. F O R : 1. O MONASTRAL BL U E 2. ■ CLAYTON YELLOW 3. ▲ P R I M U L I N E Y E L L O W 4. • T OLUIDINE B L U E 5. * M E T H Y L E N E B L U E Reproduced with permission o f the copyright owner. Further reproduction prohibited without permission. 207 10.0 CON CEN TRA TIO N , G ./L . F I G U R E 57 . S U R F A C E R O U G H N E S S VS. C O N C E N T R A T I O N O F ADDITION A G E N T A N D 5 . 0 G . / L , O F 2 . 7 - N A P T H A L E N E D I S U L F O N I C A C I D A T 6 . 5 A M P . / S Q . D M , AND 65 ®C. F O R : 1. O M O N A S T R A L B L U E 2. ■ CLA Y T O N Y ELLO W 3. A P R I M U L I N E Y E L L O W 4. # T O LU ID IN E B L U E 5. • M E T H Y L E N E B L U E Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 208 T a b le 81. R M S s u r fa c e ro u g h n ess e ffe c ts f o r 2 ,7 -n a p h th a le n e d is u lfo n ic a c id and in c r e a s in g c o n c e n tra tio n s of p h e n o ls . R M S R o ughness (m ic r o in c h e s ) Panel N o. 9.0 am p. / s q .d m . 6.5 am p. / s q .d m . R M S R oughness (m ic r o in c h e s ) Panel N o. 1 -u /iiiy u r o x y u ip iie n y i 9.0 am p. / s q .d m . ' 6.5 am p. / s q .d m . 3 ,5 , 3 ,5 - T e t r a n i t r o ^ -a in y a r o x y o ip n e n y i 3.6 3.0 3 01 -1 4.0 3 .4 2 7 1 -1 3 0 1 -2 2 .6 2 .8 2 7 1 -2 2 .6 2.4 3 0 1 -3 2 .8 2 .8 2 7 1 -3 3.0 3.0 3 0 1 -4 2 .6 3.6 2 7 1 -4 2 .6 2.6 3 0 1 -5 2 .2 2 .6 2 7 1 -5 2 .4 3.8 3 0 1 -6 3 .4 2.2 2 7 1 -6 2 .6 3.0 3 0 1 -7 3.0 3.0 2 7 1 -7 3.0 2.8 3 0 1 -8 4.0 3.0 2 7 1 -8 2 .4 3.2 3 0 1 -9 2.0 2.0 2 7 1 -9 4.0 4.0 3 0 1 -1 0 2.0 3.0 2 7 1 -1 0 > 1 0 .0 > 1 0 .0 Panel N o ./ Tem p. Panel N o ./ Tem p. (° {“ C .) C.) 3 0 1 - 1 2 /4 7 3.6 1.6 2 7 1 -1 1 4.0 4.0 (p i 3 0 1 - 1 4 /2 4 2 .8 2 .2 2 7 1 - 1 2 /4 7 4.0 3.6 3 0 1 - 1 5 /3 5 3.0 3.0 2 7 1 - 1 4 /2 4 > 1 0 .0 > 1 0 .0 3 0 1 - 1 6 /5 5 2.0 2 .4 2 7 1 - 1 5 /3 5 > 1 0 .0 > 1 0 .0 3 0 1 - 1 7 /7 5 5.0 3.8 2 7 1 - 1 6 /5 5 > 1 0 .0 > 1 0 .0 2 7 1 - 1 7 /7 5 4.0 5.2 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 209 T a b le 81 (C o n tin u ed ) R M S R oughness ( m ic r o inches) Panel No. 9.0 a m p ./ s q .d m . R M S R oughness (m ic r o in ch es) 6.5 a m p ./ s q .d m . Panel No. Phenol 9 .0 a m p ./ s q .d m . 6.5 a m p ./ s q .d m . o -N itr o p h e n o l 4 1 1 -4 2 .2 4.0 4 2 1 -4 1.8 1.8 4 1 1 -5 1.8 2 .6 4 2 1 -5 1.9 1.5 3.0 2.2 421-.6 2 .8 5 .2 4 1 1 -7 3.2 3.6 4 2 1 -7 2 .2 2.2 4 1 1 -8 3.2 3.0 4 2 1 -8 3.8 3.0 4 1 1 -9 3.0 2 .8 4 2 1 -9 3 .8 5.2 4 1 1 -1 0 4:0 1.8 4 2 1 -1 0 3.6 2 .6 4 1 1 -1 1 3.6 3.0 4 2 1 -1 1 2 .8 2 .8 4 1 1 -1 2 2 .4 3.6 4 2 1 -1 2 3 .6 3.8 4 1 1 -6 . p - N itr o p h e n o l , p -A m in o p h e n o l H y d r o c h lo r id e 4 7 -1 5.0 4.2 4 8 1 -1 5.0 5.0 4 7 -2 4 .8 5 .6 4 8 1 -2 4 .0 3 .6 4 7 -3 5 .6 5.0 4 8 1 -3 5.0 5 .4 4 7 -4 5 .2 5 .8 4 8 1 -4 4 .2 4.0 4 7 -5 5 .4 4 .8 4 8 1 -5 3 .4 3.8 4 7 -6 7.0 7 .6 4 8 1 -6 3.6 5 .2 4 7 -7 5 .4 5.2 4 8 1 -7 3 .8 4 .6 4 7 -8 6,2 5 .4 4 8 1 -8 4 .6 4 .8 4 7 -9 - - 4 8 1 -9 2 .4 3.0 4 8 1 -1 0 3.0 2 .4 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 210 T a b le 81 (C o n tin u ed ) R M S R o ughness ( m ic r o in ch es) Panel 9.0 am p. / s q .d m . N o. 6 .5 am p. / s q .d m . R M S R oughness ( m ic r o inches) Panel No. / 9.0 a m p ./ s q .d m . 6.5 am p. / s q .d m . Panel N o ./ Tem p. (° 4 8 1 - 1 1 /3 5 4 .4 4.0 4 8 1 - 1 2 /4 9 4 .4 4.4 4 8 1 - 1 3 /5 9 4 .4 4.8 o -A m in o p h e n o l H y d r o c h lo rid e C a te c h o l 491-1 4 .6 5.0 5 0 1 -1 6.0 5.8 49 1 -2 5.2 4.0 5 0 1 -2 6.0 5.8 5.0 4:0 5 0 1 -3 5 .4 4.8 491-4 4 .6 4.0 5 0 1 -4 6.0 5.0 49 1 -5 3.0 3 .6 5 0 1 -5 5.0 5.6 4 9 1 -6 4 .4 3.4 5 0 1 -6 4 .6 4.4 49 1 -7 4.0 4.0 5 0 1 -7 5.4 5.8 49 1 -8 4 .6 4 .2 5 0 1 -8 4 .4 4.4 49 1 -9 3 .4 3 .6 5 0 1 -9 7 .4 7.4 49 1 -1 0 3.5 3.8 5 0 1 -1 0 4.0 4.2 5 0 1 -1 4 5.0 4.0 491-3 ' . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 211 T a b le 81 (C o n tin u e d ) R M S R o ughness (m ic r o in ch es ) Panel No. 9.0 a m p ./ s q .d m . 6 .5 am p. / s q .d m . R M S R oughness (m ic ro in ch es ) Panel N o. Panel N o ./ Tem p . Panel N o ./ Tem p. (° (:.) (° c.) 9.0 a m p ./ s q .d m . 6.5 am p. / s q .d m . 491- 11/35 4 .0 6.0 5 0 1 - 1 1 /3 5 5.0 5.0 491 - 1 2 / 4 9 4 .0 4 .6 5 0 1 - 1 2 /4 9 5.0 5.0 491- 1 3 / 5 9 4.0 4 .2 5 0 1 - 1 3 /5 9 5.0 4.0 R e s o r c in o l b e ta -N a p h th o l 511 -1 7.0 6 .2 5 2 1 -1 6.0 5 .4 5 1 1 -2 5 .6 5 .6 5 2 1 -2 6.0 5 .6 5 1 1 -3 6.0 6 .4 5 2 1 -3 5 .4 6.0 5 1 1 -4 5 .8 5 .2 5 2 1 -4 3.8 4 .2 5 1 1 -5 5 .8 6 .2 5 2 1 -5 5 .2 4 .8 5 1 1 -6 4 .6 4 .0 5 2 1 -6 6 .8 5 .2 5 1 1 -7 5 .6 5 .2 5 2 1 -7 3.0 3 .8 5 1 1 -8 4 .8 5 .2 5 2 1 -8 6.0 6.0 5 1 1 -9 4 .8 4 .4 5 2 1 -9 9.0 9.0 5 1 1 -1 0 4 .6 4.0 5 2 1 -1 0 9.0 8.2 5 1 1 -1 4 4 .0 4 .6 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 212 T a b le 81 (Continued.) R M S R oughness (m ic r o in c h e s ) Panel No. 9.0 am p. / s q .d m . 6 .5 a m p ./ s q .d m . '5 1 1 -1 1 /3 5 5.0 5.0 5 1 1 -1 2 /4 9 3.2 3.8 5 1 1 -1 3 /5 9 4 .0 3.6 R M S R oughness (m ic r o inches) Panel No. 9.0 am p . / s q .d m . 6 .5 am p. / s q .d m . Panel No./ Tem p . (° C.) Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 213 10. 0 0 0 0 0 r 0 0 .0 .0 0 0 0.1 0.0 0.2 0 .3 C O N C E N T R A T IO N , G . / L . 0 .4 0.5 F IG U R E 5 8 . S U R F A C E R O U G H N E S S V S . C O N C E N T R A T IO N O F A D D IT IO N A G E N T A N D 5 .0 G . / L . O F 2 , 7 - N A P H T H A L E N E D IS U L F O N IC A C ID A T 9 . 0 A M P . / S Q . D M . A N D 65 * C , F O R ; 1 . B 4 , 4 '- D I H Y D R O X Y B I P H E N y L 2 . # 3 , 5 , 3 ', 5 '- T E T R A N I T R O - 4 , 4 '- D I H Y D R O X Y B IP H E N Y L 3 . A b e ta - N A P H T H O L 4. e PHENOL Reproduced with permission of the copyright owner. Further reproduction prohibited without permission 214 10.0 0. 0 0 . 10.1 0.2 0. 3 CONT C E N T R A T IO N . 0 .4 0 .5 G . /L . F I G U R E 59. SURFACE 3 1 G U G H N E S S V S . C O N C E N T R A T I O N OF A D D I T I O N AGENT V ^ N D 5.0 G . / L . O F 2 , 7 - N A P H T H A L E N E D I S U L F O N I C ACID AT G . 5 A M P . / S Q . D M . AND 65 ® C , FOR; 1 . 1 4 , 4 '. D I H Y I = 3 R 0 X Y B I P H E N Y L 2 . # 3 , 5 , ) i, 5 ' - T E T R A N I T R O - 4 , 4 ' - D I H Y D R O X Y BIPHENYL^ 3. A 4. 9 b e ta .N A P « 'X H O L PHENOL Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 215 10.0 8. 0 2.0 0.0 0.1 0.2 0 .3 C O N C E N T R A T IO N , G . / L . 0 .4 0 .5 F IG U R E 60. S U R F A C E ROUGHNESS VS. C O N C E N T R A T IO N O F A D D IT IO N A G E N T A N D 5 .0 G . / L . O F 2, 7 - N A P H T H A L E N E D IS U L F O N IC A C ID A T 9 .0 A M P ./S Q .D M . A N D 65 * C . FOR : 1. ■ o -N IT R O P H E N O L 2. # p -N IT R O P H E N O L 3. O o -A M IN O P H E N O L H YD R O C H LO R ID E 4 . A p -A M IN O P H E N O L HYDROCHLORIDE 5. O C A T E C H O L 6. • R ES O R C IN O L Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 216 1 0 .0 9 .0 8.0 U g s § ü 2 (O 0.0 0.1 0.2 CON CEN TRA TIO N , 0 .3 G. / L . 0 .4 0 .5 F I G U R E 61. S U R F A C E R O U G H N E S S V S . C O N C E N T R A T I O N O F A D D I T I O N A G E N T A N D 5 . 0 G . / L . O F 2, 7 - N A P H T H A L E N E D I S U L F O N I C A C I D A T 6. 5 A M P . / S Q . D M . AND 65 ° C . F O R : 1. A o -N IT R O P H E N O L 2 . • p-N IT R O P H E N O L 3. O o -A M IN O P H E N O L H Y D R O CH LO RID E 4 . ■ p -A M IN O P H E N O L HYDROCHLORIDE 5. □ CA TECH O L 6. # RE SO RC IN O L Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 217 Tab le 82. R M S s u rfa c e ro u g h n e s s e ffe c ts f o r n ic k e l c o b a lt d e p o s i­ tio n s in the p r e s e n c e of n ic k e l f o r m a t e and in c r e a s in g c o n c e n tra tio n s o f c a r b o n y l co m p o u n d . R M S R o ughness R M S R oughness (m ic ro in c h e s ) ( m ic r o in ch es ) Panel No. 9 .0 a m p ./ s q .d m . 6 .5 Panel No. a m p ./ s q .d m . C in n a m a ld é h y d e 9 .0 am p. / s q .d m . 6.5 am p . / s q .d m . C h lo r a l w ith ( N H .) .,S O . — 181 6 .4 8.0 191 3 .6 5.0 182 5.0 4 .6 192 7.0 5.0 183 3.8 4 .4 193 > 1 0 .0 8.5 194 7 .6 6.0 195 > 1 0 .0 > 1 0 .0 196 8 .5 8.0 197 > 1 0 .0 > 1 0 .0 198 > 1 0 .0 9.0 C h lo r a l. A c e ta ld e h y d e 201 4.0 3.2 241 4 .6 5.2 202 4.0 3 .4 242 1.8 2.8 20 3 2 .8 4.0 243 4 .6 3.4 204 4 .2 4.0 244 3 .6 3.2 205 6 .4 6.0 245 5.0 2 .4 206 3.8 4 .0 246 2 .8 3.0 207 3 .8 3.2 247 6 .6 3.2 208 4 .0 4 .6 248 5 .8 5.0 249 3 .6 3.8 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 218 T a b le 82 (C o n tin u e d ) R M S R o ughness (m ic ro in ch es) R M S R oughness (m ic ro in c h e s ) Panel Panel No. 9.0 am p. / s q .d m . 6 .5 a m p ./ s q .d m . No. 9.0 am p. / s q .d m . 6.5 am p. / s q .d m . 291 3 .6 1.8 2 98 2 .8 2.2 292 5.0 3.8 299 4 .6 4.0 293 3.2 2 .6 2910 5 .6 5.0 294 1.8 3.8 2911 5.0 5.4 295 2 .6 6.5 2912 4 .0 296 5.5 4 .6 2 91 3 5 .4 6.0 297 3 .8 5.0 29 1 4 7.2 8.0 29 1 5 9.0 4.0 29 1 6 5.0 5.4 2917 4 .4 5.2 2918 5.0 5.6 , , 4.8 B u ty l C h lo r a l 391 4.2 3 .6 392 2 .2 2 .8 393 1.8 4.0 394 1.6 3.2 395 1.8 2.0 396 4.0 3 .4 397 5 .4 4.0 398 3.0 3 .6 399 5.0 3.6 T '- Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 219 10.0 2.0 1.0 0.0 F IG U R E 6 2 . SU R FA C E 4 .0 3. 0 C O N C E N T R A T IO N , ROUGHNESS 5 .0 G ./L , VS. C O N C E N T R A T IO N O F A D D I T I O N A G E N T F O R N I C K E L - C O B A L T D E P O S IT IO N IN T H E P R E S E N C E O F N I C K E L F O R M A T E A T 9 . 0 A M P . / S Q .D M , AND 1. • 65 ® C . FO R: c h l o r a l w it h a m m o n iu m s u l f a t e P R ES E N T 2. 3. O C H LO R A L O C HLO RAL A C E T A T E IN PR ESEN C E OF N IC K E L CHLO RO - Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 220 1 0 . 0 9 .0 3 .0 2.0 0.0 1.0 2.0 3 .0 C O N C E N T R A T IO N , G . / L . 4 .0 5 .0 F IG U R E 63. S U R FA C E ROUGHNESS VS . C O N C E N T R A T IO N O F A D D IT IO N A G E N T F O R N IC K E L -C O B A L T D E P O S IT IO N IN T H E P R E S E N C E O F N IC K E L F O R M A T E A T 6 .5 A M P . / S Q .D M . A N D 6 5 » C . F O R : 1. e C H L O R A L W IT H A M M O N IU M S U L F A T E PRESENT 2. 9 C H L O R A L 3. O C H L O R A L IN T H E P R E S E N C E O F N IC K E L CHLO RO ACETATE Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 221 /T a b le 83. R M S s u rfa c e ro u g h n e s s e ffe c ts f o r n ic k e l- c o b a lt d e p o s i­ tio n s w ith in c r e a s in g c o n c e n tra tio n s of c h lo r a l in the p re s e n c e of o rg a n ic n ic k e l s a lts . R M S R oughness ( m ic r o in ch es) Panel No. 9 .0 am p. / s q .d m . 6.5 am p. / s q .d m . R M S R oughness ( m ic r o inche s) Panel No. N ic k e l C h lo r o a c e ta te 9.0 am p. / s q .d m . - 6.5 am p. / s q .d m . N ic k e l A c r y la te 441 4 .2 4 .6 451 7 .6 2 .6 442 6.2 6.6 452 2 .2 1.8 443 5 .8 6.0 453 4 .2 3.6 444 3.0 2 .6 454 3 .6 3.0 445 3.8 446 5.0 7.0 447 4.0 4.2 448 2 .6 4.0 449 4 .4 3.4 4410 2 .8 2.2 4411 4.0 3.6 4412 2 .4 2.8 . 4.2 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 222 1 0 . 0 6. 0 0.0 1.0 3 .0 2.0 CO N CEN TRA TIO N , G. 4 .0 5 .0 F I G U R E 6 4. S U R F A C E R O U G H N E S S VS . C O N C E N T R A T I O N O F AD DITIO N A G E N T F O R N I C K E L - C O B A L T D E PO SIT IO N IN T H E P R E S E N C E O F N I C K E L F O R M A T E A T 9 . 0 A M P , / S Q . D M . A ND 65® C. F O R : 1. O A C E T A L D E H Y D E 2 . A ETHYL PYRUVATE 3. • G L Y O X A L 4. O BU TYL CHLORAL 5. A CIN N A M A LD EH Y D E Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 2 23 1 0 . 0 9 .0 2.0 0.0 1. 0 3.0 2.0 CON CEN TRA TIO N , G . / L . 4 .0 5.0 F IG U R E 65. S U R F A C E ROUGHNESS VS. C O N C E N T R A T IO N O F ADDITION A G E N T F O R N IC K E L -C O B A L T D E PO SIT IO N IN T H E P R E S E N C E O F N I C K E L F O R M A T E A T 6 . 5 A M P . / S Q . D M . A N D 65 ®C. F O R : 1. O A C E T A L D E H Y D E 2 . A ETHYL PYRUVATE 3. # GLYOXAL 4. 9 BU TY L CHLORAL 5. A C IN N A M A L D E H Y D E Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 224 T a b le 8 4 . R M S s u rfa c e ro u g h n ess e ffe c ts f o r n i c k e l - i r o n d e p o s itio n s w ith v a r io u s a d d itio n s . R M S R oughness ( m ic r o in c h e s ) Panel No, 211 9.0 a m p ./ s q .d m . F e S O , and C h lo r a l 4 5.0 R M S R oughness (m ic ro inches) Panel No. 6.5 am p. / s q .d m . 9.0 am p. / s q .d m . 6.5 am p. / s q .d m . FeSO ^ 3 .6 221 3 .6 3.0 212 7.8 4 .6 222 5 .6 6,5 213 8.0 7.0 223 3.0 2 .2 214 4.0 3.8 224 3.8 3.6 215 4 .0 4 .4 225 8.0 4.0 216 3.6 3 .6 226 5.0 2 .8 217 3.8 3.2 227 7.0 3.0 218 3.2 4 .2 228 4.0 3.2 229 3 .6 5 .4 2210 3.8 2 .6 , N ic k e l P r o p io n a te , F e S q ^ , and C h lo r a l 251 6.0 6.4 252 3.2 3.0 253 4 .2 2.0 254 1.6 2 .2 Reproduced with permission o f the copyright owner. Further reproduction prohibited without permission. 225 F ro m the a p p e a ra n c e and s u rfa c e ro u g h n ess d a ta , i t is im m e d i ­ a te ly a p p a re n t th a t th e s e p r o p e r t ie s a r e fu n c tio n s of t e m p e r a t u r e , pH , and c u r r e n t d e n s ity f o r n ic k e l d e p o s its o b tain ed f r o m n ic k e l s o lu tio n . 50 to 65 W h ile n o r m a l o p e ra tin g co n d itio n s a r e fre q u e n tly C . and 1.6 to 5 .4 a m p ./s q . d m . f o r th is be g e n e r a lly a p u re W a tts s o lu tio n , i t m a y s ta te d th a t t e m p e r a tu r e s le s s than 3 5 ° C ., a p H of 3 .8 , and c u r r e n t d e n s itie s g r e a t e r th an 6 .5 a m p ./s q . d m . a r e n e c e s ­ s a ry in o r d e r to o b ta in the g r e a te s t m o d ific a tio n o f the W a tts n ic k e l d e p o s it to w a rd th e b r ig h t a p p e a ra n c e ra n g e , F ro m the ro u g h n ess d ata, the s m o o th e s t d e p o s its w e r e o b ta in e d in the s am e g e n e r a l ra n g e , but w e r e n o t so pH d ep en d en t. in the pure. W a tts p la tin g A s , a r e s u lt of th ese tre n d s e x is tin g s o lu tio n and s in c e th is s o lu tio n w as used as the r e f e r e n c e n ic k e l s o lu tio n f o r o b s e rv in g the e ffe c ts of v a r io u s o r ­ gan ic s u b s titu e n ts w h ic h w e r e added in known c o n c e n tra tio n p r i o r to e le c tr o d e p o s itio n , i t s e e m e d a d v is a b le to c o m p a re a l l e ffe c ts on the n ic k e l e le c tr o d e p o s its of s in g le o rg a n ic com pounds added to the W a tts n ic k e l s o lu tio n w ith those e ffe c ts o b s e rv e d on n ic k e l d ep o s its ob tain ed fro m the p u re s o lu tio n . T h u s , the n ic k e l d ep o sits o b tain ed f r o m the p u re W a tts n ic k e l s o lu tio n a r e fre q u e n tly r e f e r r e d to as c o n tro l d e ­ p o s its , the p a n e ls as c o n tro l p a n e ls . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 2 26 W hen a re d u c in g c a r b o h y d ra te w as added to the W atts p la tin g s o lu tio n , an im m e d ia te w id e n in g o f the c u r r e n t d e n s ity ran g e f o r the m o d ific a tio n to w a r d a b r ig h t d e p o s it w as n o te d and, f u r t h e r , th is w id e n in g w as d ir e c t ly r e la t e d to c o n c e n tra tio n . X y lo s e , g lu c o s e , la c ­ to se, h y d ra te , an d r a ffin o s e h y d ra te in c r e a s e d the b r ig h t c u r r e n t den­ s ity ra n g e at 2 5 ° C . and p H .3.8 and m o r e m a r k e d ly a t 2 .0 g . / l . a t 0 .5 g . / l . In c r e a s in g the te m p e r a tu r e the b r ig h t ran g e than to 3 5 ° C . d e fin ite ly n a r r o w e d so th a t o n ly g lu c o s e and la c to s e h y d ra te gave s ig ­ n if ic a n t ly b r i g h t e r ra n g e s than the c o m p a ra b le c o n tro l p a n e l. c r e a s e d te m p e r a tu r e s In ­ d e s tro y e d an y b rig h te n in g ten d en cy f o r these su g a rs as d e p o s its c o m p a re d f a v o r a b ly w ith the c o n tro l p a n e ls . At p H 2 .2 the sam e g e n e r a l tr e n d w as o b s e rv e d , but the b rig h te n in g p o w e r w as c o n s id e ra b ly d im in is h e d . D e x t r in d e m o n s tra te d s o m e w h a t ano m o lous e ffe c ts . In the f i r s t p la c e , d e x tr in w as the o n ly substance of th is group w h ic h y ie ld e d b r ig h t d e p o s itin g ran g e s on p an els o b s e rv e d . ran g es a t the lo w p H . S ig n ific a n tly b r ig h t 820 and 870, d e p o s ite d a t 5 5 ° C. and p H 2.2 w e re T h e re w as no d e v e lo p m e n t o r lo s s of the b r ig h t ran g e d u rin g th e te m p e r a tu r e v a r ia t io n w h ic h w o u ld a p p a re n tly p o in t to the r a t h e r s p e c ific n a tu re of th is p h e nom enon. S econdly, w hen the p H w as in c r e a s e d to 3 .8 , a b r ig h t ran g e d e v e lo p e d a t the lo w c u r r e n t Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 227 d e n s ity a r e a o f th e p a n e l and m ig r a te d to th e h ig h c u r r e n t d e n s ity a r e a as th e t e m p e r a t u r e in c r e a s e d to 5 5 ° C . ra n g e d is a p p e a r e d . A t 7 5 ° C . the b r ig h t F i n a l ly , w hen the s u r fa c e ro u g h n e s s c u rv e s w e r e r e f e r r e d to , a t p H 2 .2 , th e ro u g h n ess o f m e t a l s u rfa c e s p la te d in th e p re s e n c e of d e x t r in te n d e d to w a rd a lo w e r v a lu e a t 3 5 ° C . and a con­ c e n tr a tio n o f 0.5 g . / l . and c o n s id e ra b ly m o r e ro u g h n e s s a t 2 .0 g . / l . was o b s e rv e d . T h is w as in d ir e c t o p p o s itio n to th e tre n d s o b s e rv e d f o r x y lo s e , g lu c o s e , la c to s e h y d r a te , r a ffin o s e h y d r a te , and th e lo w e r c o n c e n tra tio n o f g ly c e r a ld e h y d e . A t pH 3 .8 , h o w e v e r, the ro u g h n ess c u rv e o f d e x t r in ten d ed to a p p ro a c h m o r e c lo s e ly the g e n e r a l tre n d of in c r e a s in g ro u g h n e s s w ith in c r e a s in g te m p e r a t u r e . W h ile g ly c e r a ld e h y d e d e m o n s tra te d s i m il a r e ffe c ts to those d is c u s s e d f o r x y lo s e , g lu c o s e , la c to s e h y d ra te and r a ffin o s e h y d ra te , it s m o r e p o w e r fu l b r ig h te n in g p r o p o e r tie s w e r e m o r e a p p a r e n t a t the lo w e r c o n c e n tr a tio n o f 0 .5 g . / l . A g a in a t pH 3 .8 , a w id e b r ig h t ra n g e r a p id ly a tte n u a te d w ith in c r e a s in g te m p e r a t u r e . W hen the pH was lo w e re d to 2 .2 , th e b rig h te n in g s tre n g th w as a p p re c ia b ly re d u c e d . W hen th e c o n c e n tra tio n w as r a is e d to 2 .0 g . / l . , w as r e d u c e d . the b r ig h te n in g e ffe c t R o ughness in c r e a s e d w ith c o n c e n tra tio n , a lth o u g h at pH 2 .2 and lo w t e m p e r a t u r e g r e a t e r ro u g h n e s s w as n o ted f o r th e lo w e r c o n c e n tr a tio n of g ly c e ra ld e h y d e . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 228 T h e in c lu s io n o f a n o n re d u c in g s u g a r, r a ffin o s e , in th is s e r ie s o f a d d itio n s w ith o u t s ig n ific a n t in t e r r u p t io n o f th e tre n d o f the d a ta is n o te w o rth y . T h is w o u ld ten d to in d ic a te th a t th e re d u c in g n a tu re o f the c a r b o h y d r a te c o u ld n o t be s in g le d o u t as a n e c e s s a ry p r o p e r ty f o r m o d ify in g n ic k e l d e p o s its . In a d d itio n to th e p r o p e r t ie s d is c u s s e d , th e use o f a c a r b o h y d r a te a d d itiv e in v o lv e s a t le a s t th r e e b a s ic c o n ­ s id e r a tio n s o f fu n c tio n a lity . T h e y a r e (1 .) th e c o llo id a l a s p e c ts , (2 .) the r o le o f the c a r b o n y l g ro u p , and (3 .) the r o le of th e h y d ro x y l g ro u p . I n o r d e r to study so m e o f the c o llo id a l a s p e c ts , th e e ffe c ts of som e w a t e r s o lu b le p o ly m e r s w e r e o b s e rv e d . M e th y l c e llu lo s e w as of p a r t ic u la r i n t e r e s t b e c a u s e i t n o t only s a tis fie d the p a r t ic le co n cept, b u t i t a ls o c o u ld be c o m p a re d w ith d e x tr in on the b a s is o f r e p la c in g the h y d r o x y l g ro u p w ith a m e th o x y 1 g ro u p . W hen m e th y l c e llu lo s e w as added to a p u re W a tts n ic k e l s o lu tio n , d e p o s its m a d e f r o m m e d iu m w e r e n o t m o d ifie d to w a rd th e b r ig h t r a n g e . th is R a th e r , con­ v e r s e ly , th e r e s u lt w as to s h ift the d e p o s it to a d u lle r ra n g e th an is n o r m a lly o b ta in e d f r o m a t the lo w e r t e m p e r a t u r e . a p u re W a tts n ic k e l s o lu tio n , p a r t ic u la r ly T h is is c o n tr a r y to th e tre n d o b s e rv e d in the c a s e o f d e x tr in . ' R o ughness m e a s u r e m e n ts tend to s u p p o rt th is tr e n d . In a l l c as es d e p o s its m a d e a t te m p e r a tu r e s o f 5 5 ° C . o r Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 229 le s s w e r e r o u g h e r th an the c o m p a ra b le W a tts d e p o s it, b u t. abo ve 55 o C . th e ro u g h n ess of th e W a tts d e p o s it and th a t m a d e in the p r e ­ sence of m e th y l c e llu lo s e b e c a m e m o r e c o m p a ra b le . W h en p o ly v in y l a lc o h o l w as added to a W a tts n ic k e l s o lu tio n and e le c tr o d e p o s its m a d e , a s ig n ific a n t m o d ific a tio n to w a rd th e b r ig h t ra n g e w as d e m o n s tra te d a t 25 pH 2 .2 . o C . and pH 3 .8 and a ls o a t 55 o C. and In th e f o r m e r c a s e , i t w as a s o m e w h a t con tinuous m o d if i­ c a tio n w h ic h w as spent a t both h ig h and lo w c u r r e n t d e n s itie s w ith in c r e a s e in t e m p e r a t u r e , w h ile in th e l a t t e r cas e th e m o d ific a tio n a p p ro a c h e d f r o m the lo w e r c u r r e n t d e n s itie s a t 3 5 ° the lo w e r c u r r e n t d e n s itie s a t 7 5 ° C . ro u g h n ess m e a s u r e m e n ts C\ and sp en t a t A ls o , i n the f o r m e r ca s e , show no change c o m p a re d to the W a tts d e ­ p o s it w h ile , in th e l a t t e r ca s e , th e d e p o s it is c o rre s p o n d in g W a tts d e p o s it. s m o o th e r than the T h e g e n e r a l shape of th e ro ugh ness c u rv e s f o r m e t h y l c e llu lo s e and p o ly v in y l a lc o h o l w e r e c o m p a ra b le to th e p u re W a tts n ic k e l s o lu tio n d e p o s it, b u t th e o r d e r of m a g n itu d e of ro u g h n ess w as g e n e r a lly g r e a t e r in the c a s e o f m e th y l c e llu lo s e , w h ile i t w as g e n e r a lly le s s in th e cas e of p o ly v in y l a lc o h o l. T h e m o s t n o ta b le p o ly m e r ic e ffe c t w as o b ta in e d f r o m tio n o f th e c o p o ly m e r o f m e th y l v in y l e th e r and m a le ic ( P V M / M A ) to th e p u re n ic k e l s o lu tio n . the a d d i­ a n h y d rid e B r ig h t n ic k e l d ep o sits w e re d e m o n s tra te d o v e r th e e n t ir e te m p e r a t u r e ra n g e a t a pH as lo w as 2 .2 . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 230 In s o lu b ilit y o f th e c o p o ly m e r in th e n ic k e l s o lu tio n a t a p H g r e a t e r th an 3 .0 p re v e n te d e v a lu a tio n ab o ve th is p o in t, b u t w hen th e pH e x c e e d e d 2 .7 5 , a d is t in c t n a r r o w in g of. th e b r ig h t ra n g e b e c a m e a p p a re n t. T h e c o p o ly m e r d e p o s ite d w ith th e n ic k e l m e t a l. b e w ip e d f r o m I t co u ld th e w e t m e t a l s u r fa c e and d r ie d in a d h e re n t w h ite fle c k s ra n d o m ly d is t r ib u t e d o v e r th e c a th o d e s u r fa c e . S in c e P V M / M A is a good s iz in g a g e n t f o r p a p e r, a p ie c e o f W h a tm a n N o . 2 f i l t e r p a p e r w as p la c e d o v e r th e cath o d e and d e p o s itio n c a r r ie d m a n n e r p r e v io u s ly d e s c r ib e d . out in the T h e p a p e r w as d r ie d and d e m o n s tra te d s iz in g to such a s tiffn e s s th a t b en d in g on ce s h a tte re d the p a p e r . The d e p o s it b rig h tn e s s w as s o m e w h a t re d u c e d by th e p re s e n c e o f the p a p e r. B e c a u s e th e m e t a l s u r fa c e w as v is ib ly c o v e re d w ith p o ly m e r , no ro u g h n ess m e a s u r e m e n ts w e r e c a r r i e d o u t on p a n e ls w h e r e P V M / M A was th e o n ly a d d itio n to a p u re W a tts n ic k e l s o lu tio n . B e c a u s e of the in flu e n c e o f P V M / M A the r e l a t i v e on th e d e p o s itin g n ic k e l, e ffe c t of m o le c u la r w e ig h t on th e d e p o s it w as in v e s tig a te d . T h r e e c o p o ly m e rs of P V M / M A w ith s p e c ific v is c o s itie s o f 0 .4 , 2 .6 , and 3 .2 w e r e added in aqueous s u s p en sio n to a p u re W a tts n ic k e l s o lu tio n in in c r e a s in g c o n c e n tra tio n . E a c h c o p o ly m e r d e m o n s tra te d a te n d en cy to b r ig h te n th e d e p o s it in c o n c e n tra tio n s o f 0.5 to 0 .6 g . / l . H o w e v e r , th e s tro n g e s t te n d e n c y f o r m o d ific a tio n w as d e m o n s tra te d in the c a s e of P V M / M A , s p e c ific v is c o s ity , 2 .6 . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 231 O b s e r v a tio n s w ith r e s p e c t to a c r y li c a c id and 1 ,4 -b u ty n e d io l h a v e b ee n in c lu d e d in th is g ro u p . B o th su b stances in d ic a te d t h e ir s tro n g e s t te n d e n c y to b r ig h te n th e n ic k e l d e p o s it a t pH 3 .8 . The s tr o n g e r a g e n t a t lo w e r c o n c e n tra tio n s w as 1 ,4 -b u ty n e d io l, b u t the in itia l p an el fr o m s o lu tio n 43, T a b le 10 and th e f in a l p a n e ls f r o m s o lu tio n 46, T a b le 40 ten d to i l l u s t r a t e an a p p r e c ia b le b rig h te n in g p r o p e r ty f o r a c r y lic a c id in h ig h e r c o n c e n tra tio n s . H o w e v e r , as a s in g le a d d itio n to th e p u re W a tts n ic k e l s o lu tio n a t c o n c e n tra tio n s 0.5 to 2 .0 g . / l . , the m o d ify in g e ffe c t of a c r y lic a c id w as lim i t e d to the h ig h c u r r e n t d e n s ity a r e a s and h ig h e r p H v a lu e . R oughness m e a s u r e m e n ts do n o t p a r t ic u la r ly b e a r th is out, s in c e the e ffe c t w as m o s t a p p a r e n t a t c u r r e n t d e n s itie s ab o ve 9 .0 a m p ./s q . d m . - - t h e h ig h e s t c u r r e n t d e n s ity a t w h ic h s u r fa c e e v a lu a tio n s w e r e c a r r ie d out. O n th e o th e r h an d , 1 ,4 -b u ty n e d io l w as a v e r y s tro n g b r ig h t e n e r w ith a w id e c u r r e n t d e n s ity ra n g e and, f r o m s tr o n g e r a t pH 3 .8 th a n 2 .2 . th is . th e v ie w p o in t o f c o n c e n tra tio n , In g e n e r a l, s u rfa c e e v a lu a tio n s p a r a lle le d T h e a n o m a lity o f th is tr e n d , found in F ig u r e s 33 and 35 m a y be e x p la in e d b y p ittin g e ffe c ts . F o r th e in v e s tig a tio n of. th e c a rb o n y l g ro u p , th e im p o r ta n c e o f its o x id iz in g te n d e n c y w as stu d ie d . A gro u p of com pounds th e p o ten ­ t ia ls of w h ic h a r e lis t e d in T a b le 85 was s e le c te d and f i r s t added to I Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 232 T a b le 85. O x id a tio n p o te n tia ls of c a rb o n y l com pounds (36 ). E Cam phor o , m .v . 82 p -B ro m o a c e to p h e n o n e 129 C in n a m a ld é h y d e 186 A c e ta ld e h y d e 2 26 F o r m a ld e h y d e 2 5 7 -2 7 0 C h lo r a l 277 P y r u v ic A c id B u ty l C h lo r a l E th y l P y ru v a te 297 b e t a - M e t h y l u m b e llife r o n e G ly o x a l Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 233 the p u r e W a tts n ic k e l s o lu tio n . F i n a l ly , the e ffe c t o f in c r e a s in g con­ c e n tr a tio n s o f s e le c te d c a r b o n y l com po unds w as o b s e rv e d on an a llo y d e p o s it, p a t te r n e d a f t e r th e m a n n e r o f W e ls h e rg and S to d d a rd (3 4 ). T h is a llo y d e p o s itin g s o lu tio n , w a s m a d e up, i n g e n e r a l, o f th e c o m ­ pounds c o n ta in e d i n th e W a tts s o lu tio n , as w e ll as s u ita b le c o n c e n tr a ­ tio n s o f c o b a lt s u lfa te and , u s u a lly , n ic k e l fo r m a te . T h e e f f e c t o f c a r b o n y l com p o u n d s ad d ed to th e W a tts n ic k e l s o lu tio n a t p H 2 .2 g e n e r a lly fo llo w e d th e tre n d s of th e p u r e W a tts n ic k e l s o lu tio n d e p o s its w ith s o m e e x c e p tio n s . F ir s t, c in n a m a ld é ­ hyde c a u sed m a r k e d g e n e r a l p ittin g o v e r th e e n t ir e t e m p e r a t u r e ra n g e . S eco n d ly, b u t y l c h lo r a l m a r k e d ly b rig h te n e d the d e p o s it a t 2 g . / l . , w h ile a t 0 .5 g . / l i t did n o t e x te n d th e b r ig h t ra n g e m o r e th an any of the o th e r c a r b o n y ls . T h i r d ly , a l l o f the c a rb o n y ls ten d ed to exten d the m o d ifie d r a n g e b eyond th e c o n tr o l p a n e l a t th e lo w e r t e m p e r a t u r e s . F in a lly , b e t a - m e t h y lu m b e llif e r o n e , b u ty l c h lo r a l, p y r u v ic a c id , c h lo r a l, and c in n a m a ld é h y d e in c r e a s e d b u rn in g of th e d e p o s it a t th e h ig h c u r ­ r e n t d e n s ity e d g e . In th e c a s e o f a l l b u t c in n a m a ld é h y d e th e b u rn t a r e a h ad a te n d e n c y to d e p o s it a g r e e n p o w d e ry su b sta n ce in s te a d of the m e t a l. R o u g h n e ss e v a lu a tio n s show ed a m ix e d tr e n d c o m p a re d w ith c u r r e n t d e n s ity , b u t g e n e r a lly a ro u g h e r d e p o s it th an the con­ t r o l p a n e l, u n le s s s ig n ific a n t m o d ific a tio n o c c u r re d as in the c a s e o f b u ty l c h lo r a l f o r p H 2 .2 and 3 .8 . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 234 A t pH 3 .8 the s a m e g e n e r a l a p p e a ra n c e tre n d s w e r e o b s e rv e d . H o w e v e r , the c in n a m a ld é h y d e e ffe c t w as le s s a p p a re n t. A d a rk e n in g of the lo w e r c u r r e n t d e n s ity a r e a s by p -b ro m o a c e to p h e n o n e , a c e ta ld e ­ hyd e, and p y r u v ic a c id , becam e m uch m o re s u b tly p r e s e n t in the pH 2 .2 p a n e ls a t 7 5 ° C . a p p a r e n t a t pH 3 .8 . C in n a m a ld é h y d e w as added to the l is t , b u t the e ffe c t d is a p p e a r e d in the case of a c e ta ld e h y d e and b u ty l c h lo r a l. lim ite d a t 35 C. T h e m a r k e d b rig h te n in g by b u ty l c h lo r a l w as H o w e v e r , a c e ta ld e h y d e and p y r u v ic a c id tended to ex te n d the b r ig h t m o d ific a t io n in the 2 5 ° C . p a n e ls and c h lo r a l d e m o n s tra te d m a r k e d b r ig h t m o d ific a tio n as hig h as 5 5 ° C . F in a lly , the h ig h c u r r e n t d e n s ity b u rn in g a t 2 5 ° C . b e c a m e m o r e a p p a re n t a t pH 3.8 th a n a t p H 2 .2 . W hen n ic k e l- c o b a lt d e p o s its w e r e m a d e w ith in c r e a s in g c e n tra tio n s the o p tim u m co n ­ of c a r b o n y l com po und, in the p re s e n c e of n ic k e l fo r m a te , ra n g e s of the b rig h tn e s s o b tain ed a r e lis te d in T a b le 86. E v e n w hen the la c k of b r ig h t ra n g e of c in n a m a ld é h y d e and e th y l p y r u v a te a r e e x p la in e d by the l i m i t of s o l u b i li t y - - f o r in both cases s o lu b ility had b e e n e x c e e d e d s lig h tly a t the c o n c e n tra tio n i n ­ d ic a te d in T a b le 8 6 - - i t is d if f ic u lt to con clu de th a t the o x id a tio n p o te n tia l is b r ig h t e n e r . lin k e d w ith the s tre n g th of the c a rb o n y l com pound as a H o w e v e r , w h e re s o lu b ility is n o t a p r o b le m , th e re seem s Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 235 T a b l e 86 Am ount A d d ed M o la r it y of ( m l./g .) C a rb o n y l S o lu ­ tio n C a rb o n y l C o m ­ pound A d d ed 18 C in n a m a ld é h y d e 0 .5 /0 .5 5 0 .0 0 3 7 u n d e r 5 .4 C h lo r a l w ith 1 .5 /2 .2 5 0 .0 1 4 9 e n t ir e 19 B r ig h t R ange ( a m p ./s q .d m .) ra n g e A m m o n iu m S u lfa te 20 C h lo r a l 1 .5 /2 .2 5 0 .0 1 4 9 e n t ir e ra n g e 24 A c e ta ld e h y d e 3 . 0 / 2 .3 5 0 .0 5 2 3 u n d e r 8 .6 29 E t h y l p y r u v a te 1 .5 /1 .5 9 0 .0 1 3 8 u n d e r 2 .6 G ly o x a l 4 .0 /1 .2 4 0 .0 2 0 7 u n d e r 3.2 B u ty l c h lo r a l 2 .5 to 3.5 0 .0 1 4 2 under 15.1 3 . 5 / 5 .2 7 to 5 . 5 / 8 .2 7 0 .0 3 5 7 0.0561 e n tir e ra n g e 39 44 C h lo r a l * 45 C h lo r a l* * - 0 .0 1 9 9 ■■ - * In p re s e n c e of n ic k e l c h lo r o a c e ta te . ** In p re s e n c e of n ic k e l a c r y la t e . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 236 to e x is t som é lim i t e d c o r r e la t io n . C h lo r a l w h ic h has a lm o s t th e s a m e o x id a tio n p o te n tia l as fo r m a ld e h y d e y ie ld s a v e r y w id e b r ig h t ra n g e w h e re th e a llo y is d e p o s ite d . A c e ta ld e h y d e e v e n in m o r e so lu tio n d id n o t g iv e as w id e a b r ig h t r a n g e . B u ty l c h lo r a l, th e o x i ­ d atio n p o te n tia l o f w h ic h is n o t know n, gave a p p r o x im a te ly b r ig h t ra n g e a t th e s a m e m o la r be som e lim it e d c o n c e n tr a tio n . c o n c e n tra te d T h u s th e r e e q u iv a le n t s e e m s to c o r r e la t io n b e tw e e n the o x id a tio n p o te n tia l o f the c a rb o n y l and it s b rig h te n in g p r o p e r t ie s . G ly o x a l w a s in c lu d e d , though its p o te n tia l is a ls o u nknow n , b ecause i t e x h ib its h y d ra tin g p r o p e r t ie s w h ic h h av e b e e n c o m p a re d f a v o r a b ly . w ith th o se o f the h ig h ly h a lo g e n a te d a ld e h y d e s c h lo r a l and b u ty l c h lo r a l. T h e fa c t, th a t i t y ie ld s ran g e a t c o m p a ra b le m o la r c o n c e n tra tio n s , p r o p e rty of the c a r b o n y l com pound f r o m such as such a p o o r b r ig h t se e m s to e lim in a t e th is c o n s id e r a tio n . T h e im p o r ta n c e o f the a c id io n s p e c ie s p r e s e n t w as c o n s id e re d . A s w e ll as n ic k e l f o r m a te , e q u im o la r c o n c e n tra tio n s of n ic k e l c h lo r o ­ a c e ta te and a c r y la t e w e r e added to the a llo y p la tin g s o lu tio n s and the e ffe c t o f c h lo r a l in in c r e a s in g la tiv e a c id e q u ilib r iu m c o n c e n tra tio n a ls o o b s e rv e d . The r e ­ co n stan ts of the p a r e n t a c id s a r e f o r m ic 4 (4 6 ), 2 .1 X. lO ” , c h lo r o a c e tic a c id (4 6 ), 1 .5 2 x 10 a c id - 3 , and a c r y lic (4 7 ), 5 .6 X l O '^ . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. a c id 237 F ro m T a b le 86 i t is shown th a t m o r e c h lo r a l is n e c e s s a ry w hen c h lo r o a c e tic a c id is p r e s e n t th a n w hen f o r m ic a c id is p r e s e n t in the p la tin g s o lu tio n . W h en the u n s a tu ra te d a c r y lic the w h o le b r ig h te n in g m e c h a n is m is r e a l o p tim u m ra n g e is o b s e rv e d . a c id is p re s e n t, c o m p le te ly in te r r u p te d and no A s c h lo r a l c o n c e n tra tio n w as i n ­ c re a s e d in th is l a t t e r c a s e , th e d e p o s itio n g r e w s te a d ily m o r e u n d e s ira b le . In the cas e o f n ic k e l- c o b a lt a llo y d e p o s itio n s ,, s u rfa c e ro u g h ­ ness m e a s u r e m e n ts d id n o t p o in t out any s ig n ific a n t tre n d s w h ic h is o la te th e b rig h te n in g com po unds. c a r b o n y l com po unds fr o m the n o n b rig h te n in g I t is n o te w o rth y th a t r o u g h e r s u rfa c e s w e r e o b ta in e d f r o m S o lu tio n 19 c o n ta in in g s m a ll a m o u n ts o f a m m o n iu m s u lfa te th an fr o m S o lu tio n 20 w h ic h y ie ld e d the s am e o p tim 'o m l im i t s of c h lo r a l co n ­ c e n tr a tio n b u t s m o o te r d e p o s its w ith o u t a m m o n iu m s u lfa te . T h e r e la tio n s h ip in c o n c e n tra tio n b e tw e e n the o rg a n ic a c id , w h ic h w as u sed to a d ju s t the pH o f the s o lu tio n , and the ald eh y d e a p p e a rs to be im p o r ta n t. S o lu tio n 2 0, T a b le 2 05 . F o r m ic 59 w h e re a f u ll b r ig h t ra n g e was a c h ie v e d on P a n e l a c id w as add ed to th e s o lu tio n to r e a d ju s t to the p r o p e r pH and im m e d ia t e ly re d u c e d . T h is can be p o in te d out be r e f e r r in g to the b r ig h t ra n g e o f the next p a n e l was n o ta b ly S u c c e s s iv e a d d itio n s of c h lo r a l r e tu r n e d the b r ig h t ra n g e Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 238 th a t h a d b e e n o b ta in e d p re v io u s ly . p h en o m en o n and is Solution 39 gave a s i m i l a r d e m o n s tra te d in Panels 397, 398, an d 399. W h ile c o n tr o llin g the p H o f the solution s, a tte m p t w a s m ade to m in im iz e this e f fe c t by e l im i n a t io n of acid a d d itio n d u r in g the c o u rs e of i n ­ c re a s in g the c o n c e n tr a tio n of the c a rb o n y l co m p o u n d . W h e n the a llo y in g c o n s titu e n t is ch an g ed f r o m c o b a lt to ir o n a m o re l im i t e d b r i g h t ran g e is o b s e rv e d f o r the o p tim u m tio n of c h lo r a l n o te d in n ic k e l-c o b a lt d e p o sitio n . 215 w i l l p o in t th is o u t. A d dition o f t a r ta r ic c o n c e n tr a ­ S o lu tio n 2 1 , P a n e l a c id im m e d ia t e ly i n t e r ­ ru p te d the b r ig h te n in g e ffe c t, h o w e v e r, as P a n e l 216 d e m o n s tr a te d , and c a u s e d a b n o r m a l s tre s s in g in th e d ep o sit. T a r t a r ic a c id w o u ld not c o n tr o l the f o r m a t i o n of a copious y e llo w -o .ra n g e p r e c ip it a t e w h ich f o r m e d in th e and c h lo r a l w e r e ir o n -n ic k e l s o lu tio n s . W h e n n ic k e l p ro p io n a te a d d e d to the ir o n -n ic k e l p la t in g s o lu tio n , a m o d i f i ­ catio n to w a r d a b r i g h t d e p o sit was ob served , b u t s tr e s s in g and p r e c ip ita tio n c o u ld n o t be c o n tro lle d . It is n o te w o r th y th a t the s o lu ­ tio n c o u ld n o t be r e d u c e d in pH b e lo w 4.4, w h e n n ic k e l p ro p io n a te was p r e s e n t. E . R aub a n d M . W ittu m (45) in v e s tig a te d the e ffe c ts of a l i ­ p h a tic a lc o h o ls in c lu d in g p o ly h y d ro x y l types a n d found th a t these c o m ­ pounds h a d no r e a l b rig h te n in g s tre n g th even a t v e r y h ig h c o n c e n ­ tr a tio n s . T h e re fo re , in o r d e r to stu d y some e ffe c ts of th e h y d ro x y l Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 239 g ro u p , i t s e e m e d d e s ir a b le to use a g ro u p o f is o m e r ic p h en o ls. types: T h e s e r ie s and s u b s titu te d s e le c te d can be s u b d iv id e d fu n c tio n a lly in to two (1.) r in g s w h ic h c o n ta in the h y d ro x y l g ro u p o n ly , and ( 2 .) rin g s w h ic h c o n ta in n it r o o r a m in o g ro u p s as w e ll as the h y d ro x y l g ro u p . T h e f i r s t ty p e in c lu d e s p h e n o l, 4 , 4 - d ih y d r o x y -b ip h e n y l, b e ta -n a p h th o l, c a te c h o l, and r e s o r c in o l. A t p H 2 .2 , the g e n e r a l tre n d o f the W a tts c o n tro l p a n e ls c a r r i e d o v e r to d e p o s its m a d e in the p re s e n c e o f th is type w ith fe w c o m p a r a tiv e ly m in o r v a r ia t io n s , e x c e p t f o r b e ta -n a p th o l w hich m o d ifie d th e d e p o s it to w a rd the b r ig h t ra n g e m o r e n o ta b ly and caused m a r k e d b u rn in g and e x fo lia tio n of the d e p o s it a t the h ig h c u r ­ r e n t d e n s ity edge up to 5 5 ° C . S u rfa c e ro u g h n ess m e a s u r e m e n ts , p lo tte d in F ig u r e 45 and F ig u r e 46 p a r a l l e l the tre n d s o f the W a tts p an els m a r k e d ly e x c e p t f o r b e ta -n a p h th o l w h ic h y ie ld e d s m o o th e r d e p o s its . A t p H 3 .8 , the f i r s t ty p e p a r a lle le d the W a tts p a n e ls s o m e w h a t le s s . A s w e ll as b e ta -n a p h th o l, p h e n o l and r e s o r c in o l a t the h ig h e r c o n c e n tra tio n of 2 .0 g . / l . h ig h as 5 5 ° C. e x e r te d m o d ify in g e ffe c ts w h ic h e xten d ed as N o ta b le s m o o th in g o f the d e p o s its is o b s e rv e d i n the s u rfa c e ro u g h n e s s d ata by th e s e th r e e co m p o u n d s. The second type of p h e n o lic cofnpounds in c lu d e d 3 , 5 , 3 ', 5 ' - t e t r a n i t r o - 4 , 4 '—d ih y d ro x y b ip h e n y l, o -n itr o p h e n o l, o -a m in o p h e n o l Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 240 h y d ro c h lo r id e and p -a m in o p h e n o l h y d r o c h lo r id e . A t p H 2 .2 a l l of these p h e n o ls m o d ifie d the d e p o s it to w a rd the b r ig h t ra n g e . In the case o f the n it r o g ro u p , 3 , 5 , 3 ' , 5 ' - t e t r a n i t r o - 4 , 4 ' -d ih y d r o x b ip h e n y l e x e rte d a s tr o n g e r e ffe c t th a n o - n i t r o p h e n o l w h ile i n the c a s e of the a m in o g ro u p , p -a m in o p h e n o l h y d ro c h lo r id e e x e r te d a s tr o n g e r e ffe c t th a n o -a m in o p h e n o l h y d r o c h lo r id e . pH 3 ,8 . T h is a ls o h o ld s t r u e at R o ughness m e a s u r e m e n ts do h o t p a r a l l e l th e g e n e r a l b r ig h t ­ ening e ffe c t. F o r o - and p -a m in o p h e n o l h y d r o c h lo r id e a t p H 2 .2 ., th e re is in v e r s io n o f the tre n d s w ith in c r e a s e d c o n c e n tra tio n and a t pH 3 .8 For e x fo lia tio n by p -a m in o p h e n o l p re v e n ts c o m p a ris o n . both the a m in o p h e n o ls and th e n itro p h e n o ls th e r e is an in c r e a s e in rou g h n ess w ith s tr o n g e r b rig h te n in g te n d e n c y . In a d d itio n to the f a c to r s a lr e a d y d is c u s s e d , a g ro u p of r e p r e ­ s e n ta tiv e dyes w e r e in c lu d e d s in c e t h e ir use w ith a n a r o m a tic a c id in n ic k e l d e p o s itio n is c la s s ic a l (7 ,9 ). s u lfo n ic T h e e ffe c ts of the p h th a lo c y a n in e d ye M o n a s t r a l B lu e , o f the th ia z o le dyes C la y to n Y e llo w and P r i m u li n e Y e llo w , and o f the th ia z in e dyes M e th y le n e B lu e and T o lu id in e B lu e , w e r e o b s e rv e d . A s s in g le a d d itio n s to a W atts n ic k e l s o lu tio n , M o n a s t r a l B lu e w as th e le a s t e ffe c tiv e ag e n t a t 0.5 g . / l . T h e th ia z o le dyes w e r e m o s t e ffe c tiv e a t p H 3 . 8 - - l o w te m p e r a tu r e s w ith P r i m u li n e Y e llo w a p p e a rin g to be th e s tr o n g e r of Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 241 the tw o in v e s tig a te d . th ese o b s e r v a tio n s . I n g e n e r a l, s m o o th n e s s o f th e d e p o s it p a r a lle le d A w id e n in g o f th e m o d ific a tio n a t 7 5 ° C . and pH 2 .2 by b o th t h ia z o le dyes is n o te w o rth y . B o th th ia z in e dyes m a r k e d ly in h ib ite d m e t a l d e p o s itio n a t a l l te m p e r a tu r e s and p H v a lu e s . T h e dyes s e le c t iv e ly d e p o s ite d and c o lo re d th e c a th o d e w ith th e c h a r a c t e r is t ic c o lo r of each d ye . B u rn in g and e x fo lia tio n w as p a r t ic u la r l y a p p a re n t a t h ig h c u r r e n t d e n s itie s and lo w t e m p e r a t u r e s in both c a s e s and e x te n d e d to 7 5 ° C . in the case of M e th y le n e B lu e . H o w e v e r , w h e r e v e r n ic k e l did d e p o s it, a b rig h tn e s s w as n o te d on the m e t a l s u r fa c e . S u rfa c e e v a lu a tio n s w ould be of no v a lu e f o r th e s e d e p o s its and w e r e not e x e c u te d . T h e e ffe c ts o f th e com pounds d is c u s s e d abo ve, o r o f r e p r e ­ s e n ta tiv e s o f eac h g ro u p , in in c r e a s in g pH 3 .8 , in th e p r e s e n c e o f 5 g . / l . c o n c e n tra tio n a t 6 5 ° C . and o f 2 , 7 -n a p a th o le n e d is u lfo n ic a c id , w e re n e x t o b s e rv e d in a W a tts n ic k e l s o lu tio n . T a b le 87 lis t s a ll of the com pounds stu d ie d u n d e r th e s e c o n d itio n s , to g e th e r w ith th e f i r s t o p tim u m c o n c e n tra tio n p ro d u c in g the w id e s t b r ig h t ra n g e o f d e p o s itio n and th e c o m p a r a tiv e m o l a r c o n c e n tra tio n s o f each . T h ir t e e n o f the tw e n ty com pounds p ro d u c e d a b r ig h t ra n g e o v e r th e f u ll c u r r e n t d e n s ity ra n g e o f th e c a th o d e . B a s e d on the m o la r c o n c e n tra tio n and the b r ig h t ra n g e p ro d u c e d , the com pounds w e r e lis te d in d e c re a s in g Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 242 T a b l e 87 M in im u m O p tim u m C o n c e n tr a ­ tio n ( g . / l . ) M o la r C oncen­ t r a t io n B r ig h t C u r r e n t D e n s ity R ange ( a m p ./ s q .d m .) 371 G lu c o s e 381 C h lo r a l 1 .9 0 361 P V M /M A 0 .0 6 3 A c r y li c A c id 0 .5 1 1 531 1 ,4 -B u ty n e d io l 0 .2 5 5 351 M o n a s t r a l b lu e B G 0 .511 311 C la y to n y e llo w 0 .0 6 3 0 .0 0 0 0 9 0 6 e n t ir e ra n g e 321 P r i m u li n e y e llo w 0 .0 6 3 0 .0 0 0 1 3 2 e n t ir e ra n g e 331 M e th y le n e b lu e 0 .0 7 0 0 .0 0 0 0 2 1 9 e n t ir e ra n g e 341 T o u id iiie b lu e 0 .0 0 7 0 .0 0 0 0 2 2 9 e n t ir e ra n g e 301 4 , 4 ' - JDihy d r o x y b i phenyl 0 .2 5 5 0 .0 0 1 3 7 ab o ve 4 . 3 * 271 3 ,5 ,3 ',5 '- T e t r a n i t r o - 4 , 4 '- d i h y d r o x y b ip h e n y l 0 .0 0 3 0 .0 0 0 0 0 8 3 above 3 .2 411 Phenol 0 .0 1 5 0 .0 0 0 1 5 9 abo ve 1 1 .8 * 421 o -N itr o p h e n o l 0 .0 1 5 0 .0 0 0 1 0 8 e n t ir e ra n g e 47 p -N itr o p h e n o l 0 .0 6 3 0 .0 0 0 4 5 3 above 9 .0 481 p - A m in o p h e n o l h y d ro c h lo r id e 0 .0 0 7 0 .0 0 0 0 4 8 1 e n t ir e ra n g e 491 o -A m in o p h e n o l h y d ro c h lo r id e 0 .0 1 5 0 .0 0 0 1 0 3 e n t ir e ra n g e 501 C a te c h o l 0 .0 3 1 0 .0 0 0 2 8 1 above 1 4 .0 511 R e s o r c in o l 0 .0 3 1 0 .0 0 0 2 8 1 above 10.8 521 b e ta -N a p h th o l 0 .0 6 3 0 .0 0 0 4 3 7 above 6.5 46 ab o ve 1 4 .0 e n t ir e ra n g e e n t ir e ra n g e 0 .0 0 7 0 9 ab o ve 1.6 0 .0 0 2 9 6 e n t ir e ra n g e 0 .0 1 2 9 - - e n t ir e ra n g e * H a z e b r ig h t. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 243 s tre n g th as b rig h te n e r s in T a b le 88. s o m e w h a t in doubt, s in c e its F ro m The p o s itio n of P V M / M A is e x a c t m o le c u la r w e ig h t is n o t know n. the p lo ts of ro u g h n ess d a ta , a ll com pounds th ro u g h the dyes lis t e d in Tab le 88 show m in im u m p o in ts o f R M S roughness v a lu e a t the o p tim u m b rig h te n in g c o n c e n tra tio n e x c e p t a c r y lic a c id . M e th y le n e B lu e , and T o lu id in e B lu e . v a lu e In the case of a c r y lic a c id , the m a x im u m is o b s e rv e d , b u t i t is v e r y c lo se in m a g n itu d e to the s u rfa c e v a lu e of the b asis m e t a l so is n o t v e r y s ig n ific a n t. In the case o f M e th y le n e B lu e and T o lu id in e B lu e the tre n d is d e c re a s in g w ith a w id e b r ig h t range c o n tin u in g so i t a ls o is n o t s ig n ific a n tly a n o m o lo u s . T h is g e n e r a l tre n d is als o r e f le c te d in the cases of the p h e n o ls . E x p lo r a to r y r e s u lts have b ee n r e p o r te d in T a b le s 68, 6 9 , and 70 f o r s u rfa c e tr e a tm e n t o r p re d ip p in g of the cathode fo llo w e d by d e p o s itio n , a p u re W a tts n ic k e l s o lu tio n . the c a th o d e , in the c a s e of T a b le T h is s u rfa c e tr e a tm e n t of 68, c o n s is te d of w ra p p in g the c a th ­ ode w ith W h atm an N o . 2 f i l t e r p a p e r o r d ip p in g th ro u g h a le n s of 1 c in n a m a ld é h y d e flo a tin g on the s u rfa c e of W atts n ic k e l s o lu tio n , and of then p la tin g T a b le s s o lu tio n s 69 of s p e c tiv e ly . in and 0 .5 a 70, g ./l. Tab le 68 p u re the of W a tts n ic k e l cathod es w e re C la y to n Y e llo w d e m o n s tra te s som e s o lu tio n . In d ipped W atts and in M e th y le n e the case n ic k e l B lu e , re ­ s ig n ific a n t m o d ific a tio n of th e d e p o s it, both b y th e f i l t e r p a p e r and the cin n a m a ld e h y d e le n s . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 244 T a b l e 88 M e th y le n e B lu e T o lu id in e B lu e p -A m in o p h e n o l h y d ro c h lo r id e P V M /M A C la y to n Y e llo w o -A m in o p h e n o l h y d ro c h lo r id e o -N itr o p h e n o l P r i m u li n e Y e llo w M o n a s t r a l B lu e 1 ,4 -B u ty n e d io l C h lo r a l 3 ,5 ,3 ' , 5 '- T e t r a n it r o - 4 ,4 '- d ih y d r o x y b ip h e n y l A c r y li c acid b eta - N aphtho 1 p -N itr o p h e n o l R e s o r c in o l C a te c h o l G lu c o s e 4 , 4 ' -D ih y d ro x y b ip h e n y l Phenol Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 245 D ip p in g in p r o v e n b r ig h t e n e r s , h o w e v e r, as sho w n in T a b le s 69 and 70, d id n o t s ig n if ic a n t ly m o d ify th e d e p o s it u n d e r th e c o n d itio n s o f the r e s p e c t iv e e x p e r im e n t s u n t il th e d ip p in g s o lu tio n w as d r ie d on th e cath o d e in th e c a s e o f M e th y le n e B lu e . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. D IS C U S S IO N T h e r e l a t i v e s tre n g th , as b r ig h te n e r s , o f th e o rg a n ic com pounds studied (T a b le 8 8 ) p ro v id e s p r o p e r tie s . some in te r e s tin g c o m p a ris o n s j of t h e i r I t a p p e a rs th a t fu n c tio n a l groups a r e im p o r ta n t in the b rig h te n in g of n ic k e l by p h en o ls. P h e n o l w as the le a s t e f fe c tiv e of the g ro u p w h ile th e am in o p h en o ls w e r e the s tro n g e s t. N itro p h e n o ls w e re in te r m e d ia t e in s tre n g th and p o ly -h y d ro x p h e n o ls w e re n o t m u ch b e tte r than p h e n o l. fu n c tio n a l group. T h e s e data s tre s s the im p o r ta n c e of the p a r t ic u la r The tr e n d o b s e rv e d by c o m p a rin g the r e l a t i v e e ffe c t o f 4 ,4 '-d ih y d ro x y b ip h e n y l w ith phenol and the n itro p h e n o ls tended to su p p o rt th is . T h e fu n c tio n a lity o f the a r o m a tic r in g i t s e lf is a p p a r e n tly also im p o r ta n t. A c o m p a ris o n of phenol, 4 ,4 '-d ih y d ro x y b ip h e n y l and b e ta - nap h th o l shows th a t the n ap h th yl r in g m u s t c o n trib u te som e f a c t o r to the con ditio ns o f m o d ify in g the n ic k e l d e p o s it. 4 ,4 '-d ih y d ro x y b ip h e n y l y ie ld e d v e r y was a p p re c ia b ly W h ile p h e n o l and s im ila r r e s u lts , b e ta -n a p h th o l s tro n g e r as a b rig h te n e r. A s ig n ific a n t p a r a lle lis m at th is p o in t is th e r e la t iv e double bond c h a r a c te r p re s e n t in th e r in g s . P h e n o l and 4 ,4 ' -d ih y d ro x y b ip h e n y l a r e d e riv e d f r o m the b e n ze n e Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 247 n u c le u s , w h ic h is r e p o r te d to h a v e o n e -h a lf d ou ble bond c h a r a c t e r (37) in t h e c a rb o n to c a rb o n lin k a g e , when it s re s o n a n c e f o r m s a r e s id e r e d , w h ile th e c a rb o n c a rb o n bond in the n ap h th a le n e t w o - t h ir d s d o u b le bond c h a r a c t e r . con­ rin g has I f w e e x te n t th is p o in t f u r t h e r and note th e p o s itio n of a c r y li c a c id and 1 ,4 -b u ty n e d io l in T a b le 88, th e r e is a t r e n d to w a rd in c r e a s in g b rig h te n in g r a t io n o f the o rg a n ic s u b s titu e n t. s tre n g th w ith in c r e a s in g un s a tu ­ T h u s , i t w ould s e e m th a t th e d e g re e of u n s a tu r a tio n of an o rg a n ic com pound as a b r ig h t e n e r should b e c o n s id e re d as an im p o r ta n t c o n trib u tio n . I f th is is tr u e , in c r e a s in g the n u m b e r o f h y d ro x y l groups w ould te n d to a tte n u a te th e m o d ify in g e ffe c t o f the o r g a n ic com pound. c a lly p o in t t h is A lth o u g h these d a ta do n o t s p e c if i­ out, i t has b een o b s e rv e d th a t th e h y d r o x y l group added to the a r o m a t ic r in g does a c tu a lly re d u c e th e m o d ify in g e ffe c ts of c e r t a in o r g a n ic a r o m a t ic a c id s (3 8 ). The m o le c u la r s tu r c tu r e s fo r th e th ia z o le dyes (3 9 ), C la y to n Y e llo w Blue (I) a n d P r i m u li n e Y e llo w ( I I I ) and T o lu id in e B lu e (IV ) ^ ( ll) , and th ia z in e dyes (3 9 ), M e th y le n e a re show n. SO,N(L N S .-C H 3 (p re d o m in a n tly ) -s ( / - N N -H I S N= C II S O , N Oy Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 248 — N - — S = — C ,/-fj - N N(cN3)g I w ^ N ' N H ^ a I II N //-A /-,,/ /-/(-H ï /-" -(y The w s tru c tu re (40) of phohalocyanine ( V ) a n d . cornpound of phthalocyanine (V I) a r e a ls o of b rig h ten in g a m etal deposit v e rs u s t h e Is a v a ila b le . T h e s e s tr u c tu r e s o f th e c o m p le x th e o ry a d s o r p tio n c o o d in a tin g This is true of a ll the c o m p o u n d s down to 1,4-butynediol except P V M / M A n ic k e l c o o rd in a tio n show n. ape o f in te r e s t in weighing the a p p l i c a b i l i t y Obvious in a l l of these structures th a t a th e w h ic h n ic k e l s a lt and the nitrophenols w h ic h a r e th e o ry . I t is n itro g e n a to m lis t e d in T a b le 88 c a n a c tu a lly f o r m c o n s i d e r e d la t e r . a T hu s the com pounds with the strongest b r i g h t e n i n g p r o p e r t ie s in v e s tig a te d a p p aren tly can chemically associate w ith o r g a n ic b r ig h te n e r . th e Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 249 The com pound is s itu a tio n f o r th e c a rb o n y l and the u n s a tu ra te d h y d ro x y l s o m e w h a t m o r e in d o u b t. In th e case o f the c a rb o n y l, the c o m p a ris o n w ith o x id a tio n p o te n tia l is d is c u s s e d and th e re a r e in d ic a tio n s o f som e c o r r e la tio n . R e fe r e n c e to the o r ig in a l p a p e r (36) w h e re the o x id a tio n p o te n tia ls a r e r e p o r te d show ed th a t these p o te n ­ t ia ls a r e o b ta in e d f r o m O p p e n a u e r o x id a tio n s o f r e fe r e n c e c a rb o n y l com pounds o f known p o te n tia l, w h ic h w e re o b ta in e d in d e p e n d e n tly . B y p o la ro g ra p h ic a n a ly s is o f s u ita b le e q u ilib r iu m m ix tu r e s of a r e fe r e n c e c a rb o n y l com pound and th e c a rb o n y l com pound of unknown p o te n tia l, th e o x id a tio n p o te n tia l w as N e r n s t e q u a tio n . c a lc u la te d using a f o r m of the W ild s (41) has r e p r e s e n te d the c o u rs e o f the r e a c tio n , in c o n s id e rin g the r e v e r s e R.' H \ case, re d u c tio n , as fo llo w s CH. r' \ H .C H 3 3 A lth o u g h th e e x a c t m e c h a n is m of th e t r a n s fe r of one v a le n c e bond of the a lu m in u m bond and one h y d ro g e n atom is unknown, an in te r m e d ia te a lu m in u m d e r iv a t iv e o f a h e m ia c e ta l (V II) has b een p o s tu la te d in d e p e n d ­ e n tly be V e r le y , M e e r w in , and P o n n d o rf. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 250 C . o c ’ V II W h e th e r such an h e m ia c e ta l sp e cie s is s ta b le in aqueous n ic k e l s a lt so lu tio n and p r e s e n t at the cathode la y e r in a n ic k e l d e p o s itio n is s t il l n o t c e r ta in . H o w e v e r, the a m o u n t of w a t e r w h ic h is p re s e n t in the cathode la y e r , p a r t ic u la r ly w hen an o rg a n ic a d d itio n ag e n t is p re s e n t, is also open to q u e stio n . R e s u lts o b ta in e d by dipping the cathode in a lens o f c in n a m a ld é h y d e and r e p o r t e d in T a b le 68 m ig h t tend to su p p o rt th is . T h e f il m a d s o rb e d on the cathode was v e r y in s o lu b le , the cathode w e tte d w ith d iffu lty , and m a r k e d m o d ific a tio n of the d e p o s it w as r e p o r te d . Thus a p o s s ib le c h e m ic a l a s s o c ia tio n betw een the c a rb o n y l and the n ic k e l sp ecies co u ld be c o n s id e re d . T h e pi e le c tio n s of the u n s a tu ra te d h y d r o x y l com pounds m a y also be c o n s id e re d in the d is c u s s io n of a m o le c u la r c o m p le x th e o ry . A lth o u g h r e la t iv e ly lit t le d e fin ite ev id e n c e e x is ts (4 2 ), p a r t ic u la r ly in a n aqueous s o lu tio n s tate, a pi c o m p le x of n ic k e l and the o rg a n ic h y d ro x y l com pound m ay e x is t. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 251 The c o m p a ris o n of n ic k e l a c r y la te w ith n ic k e l c h lo ra c e ta te and n ic k e l fo r m a te is of in te r e s t in the c o n s id e ra tio n of p i c o m p le x e s . In a llo y d e p o s itio n w ith in c r e a s in g c o n c e n tra tio n s of c h lo r a l, the o rg a n ic a c id au g m e n te d the a c tio n of c h lo r a l e x c e p t in the case of a c r y lic a c id . N ic k e l p ro p io n a te and c h lo r a l als o s o m ew h at au g m e n te d each o th e r in the case of n ic k e l - ir o n d e p o s itio n . H o w e v e r, when c h lo r a l w as added to the n ic k e l s o lu tio n c o n ta in in g n ic k e l a c r y la te , b u rn in g of the d e p o s it in c re a s e d f r o m the h ig h c u r r e n t d e n s ity edge of the p a n e l and a g re e n p o w d e ry su b stance, p ro b a b ly n ic k e l s a lts , d e p o sited r a t h e r th an the n ic k e l w ith a d d itio n s o f c h lo r a l. T h is p h e ­ nom enon is o fte n e x p la in e d b y a s s u m in g a tig h tly bonded m e ta l ion and in s u ffic ie n t e n e rg y — v o lt a g e - - t o cathode s u r fa c e . d is c h a rg e the m e t a l ion a t the A p a r a lle l o b s e rv a tio n has b een n oted f o r the dep­ o s itio n o f n ic k e l f r o m h ig h ly a lk a lin e m e d ia in the p re s e n c e o f s tio c h io m e tr ic am ounts of eth ylen e d ia m in e te tr a a c e tic a c id w hen the p o te n tia l d rop a c ro s s the c e ll w as 12 v o lts (4 3 ). W h e th e r a c o m p le x m o le c u le c o m p le te ly c o n tro ls the m o d ify in g of a n ic k e l d e p o s it, o r w h e th e r these p r o p e r tie s d is cu s sed above a r e s ig n ific a n t f o r d e s ira b le a d s o rp tio n con d itio n s cannot be d e c id e d f r o m the d a ta r e p o r te d . A n ic k e l c o m p le x w ith the o rg a n ic a d d itio n agent does h o w e v e r s ee m to help e x p la in a p o s s ib le m ode o f tr a n s fe r e n c e , in a d d itio n to e le c tr o p h o r e s is , of the o rg a n ic sp ecies into the cathode la y e r . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 252 T he r o le o f the n itr o g ro u p p ro v id e s tio n . som e f u r t h e r c o n s id e r a ­ In the f i r s t p la c e , the o r th o is o m e r o f n itro p h e n o l had a m u c h s tr o n g e r e ffe c t on the n ic k e l d e p o s it th a n the p a r a is o m e r . T h is w as n o t the case f o r the a m in o p h e n o ls , b u t th e re w as le s s d iffe re n c e in the s tre n g th s of the a m in o p h e n o l s t r u c t u r a l is o m e r s . W hen 3 , 5 , 3 ', 5 '- t e tr a n it r o -4 ,4 '- d ih y d r o x y b ip h e n y l w as c o n s id e re d , m o r e than o n e -h a lf as m a n y m o le s w as r e q u ir e d to p ro d u c e the b r ig h t ra n g e c o m p a re d . F i n a l ly , th e fa te o f the n itr o gro u p is in q u e s tio n . p r e p a r a tio n in v e s tig a tio n s E le c t r o c h e m ic a l (44) have n o t r e p o r te d the p ro d u c ts of re d u c tio n o f m o n o n itro p h e n o ls f u ll y in a c id and n e u tr a l m e d ia a t a n ic k e l cathode to d ate. f u lly red u c e n itr o C a lc u la tio n o f the F a r a d a y s group w il l show th a t m in o r am ounts of the c u r r e n t p a s s e d th ro u g h e a c h c e ll cou ld c o n v e rt the n itr o g ro u p . r e q u ir e d to group to an a m in o Thus it seem s d iffic u lt to a ttr ib u te the b rig h te n in g ro le of the n itro p h e n o l f u ll y to the n itr o g ro u p , since it co u ld be re d u c e d to the v e r y e ffe c tiv e a m in o g ro u p . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. SUMM ARY V a r io u s gro u p s o f o rg a n ic sub stances have been added to p u re W a tts n ic k e l s o lu tio n s , s o lu tio n s c o n tain in g 5 g . / l . of 2 ,7 - n a p h th a le n e d is u lfo n ic a c id and n ic k e l- c o b a lt o r n ic k e l- ir o n a llo y d e p o s itin g s o lu tio n s . T h e fo llo w in g co n clu sio n s a r e sug gested, based on the in t e r p r e t a t io n of d ata w ith r e s p e c t to a p p e a ra n c e o f the d ep o sit and its s u r fa c e ro u g h n ess tre n d s . 1. A t 2 5 ° C . and pH 3 .8 , the su g ars in v e s tig a te d b rig h te n e d n ic k e l d e p o s its g r e a te s t, and of the r e p r e s e n ta tiv e g lu c o s e w as the s tro n g e s t b r ig h te n e r . group chosen, S m oothness p a r a lle le d th is g e n e r a l tre n d . 2. T h e re d u c in g p r o p e r tie s of su g ars a r e not r e q u is ite f o r t h e ir b rig h te n in g p r o p e r tie s . 3. T h e gro u p o f n ic k e l b r ig h te n e r s has been extend ed to in c lu d e s y n th e tic p o ly m e r s . 4. T h e m o le c u la r w e ig h t of th e p o ly m e r , w h ic h was r e fle c te d by its v is c o s ity p r o p e r t ie s , is a fu n c tio n of b rig h te n in g s tre n g th . 5. T h e o x id iz a tio n p o te n tia l o f a c e ta ld e h y d e and c h lo r a l c o m p a re s o m e w h a t fa v o r a b ly w ith fo rm a ld e h y d e . n ic k e l d e p o s it o b tain ed f r o m T h e ir e ffe c t on a a W a tts n ic k e l so lu tio n o r a n ic k e l- c o b a lt a llo y -d e p o s itin g s o lu tio n is als o c o m p a ra b le . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 254 6. T h e p h th a lo c y a n in e dye, M o n a s t r a l B lu e has been added to th e c la s s ic a l gro u p of dyes w h ic h b rig h te n n ic k e l d e p o s its . 7. T h e fu n c tio n a lity of an o rg a n ic com pound is im p o r ta n t in d e te rm in in g its b rig h te n in g d a ta th a t is o m e r ic s tre n g th . H o w e v e r, i t a p p e a rs f r o m the s tr u c tu r e tends to in c r e a s e o r d e c re a s e b rig h te n in g s tre n g th o f a fu n c tio n a l g ro u p . 8. A group of o rg a n ic b r ig h te n e r s have b een r e p o r te d in d e c re a s in g o r d e r o f b rig h te n in g s tre n g th . 9. In g e n e r a l, s in g le a d d itio n s of o rg a n ic com pounds to a W a tts n ic k e l s o lu tio n a r e n o t as e ffe c tiv e o r c o n trô la b le as s p e c ific c o m b in a tio n s . 10. T h e n ic k e l- c o b a lt a llo y -d e p o s itin g s o lu tio n has been studied and ad d itio n s of o rg a n ic a c id s h a v e been exten d ed s u c c e s s fu lly to an o rg a n ic a c id of K v a lu e , s im ila r to f o r m ic a c id . A d d itio n s of ald eh y d es also h a v e been extended to c a rb o n y l com pounds o f o x id a tio n p o te n tia l s i m il a r to fo rm a ld e h y d e . 11. T h e b a la n c e o f fr e e o rg a n ic a c id and ald eh y d e c o n c e n tra tio n tends to be im p o r ta n t in d e te r m in in g the b r ig h t c u r r e n t d en sity ra n g e of the n ic k e l- c o b a lt d e p o s it. 1 2. T h e h y d ro x y l group tends to h av e l i t t l e a p p a re n t b r ig h t ­ ening s tre n g th w hen in s u ffic ie n t u n s a tu ra te d c a rb o n -c a rb o n bond c h a r a c te r is p re s e n t. Reproduced with permission o f the copyright owner. Further reproduction prohibited without permission. B IB L IO G R A P H Y 1. M . S c h lo tte r, U . S. 2. W . L . P in n e r , G. S o d e rb e rg , a n d E . M . B a k e r , ''M o d e r n E l e c t r o ­ p la t in g ,'' S p e c ia l V o lu m e , The E le c tr o c h e m ic a l S o c ie ty , In c ., N e w Y o r k , N .Y ., 1 9 4 2 , p. 2 4 2 . 3. E . N . Todd and w'. R . K ing, U . S. 1 ,3 5 2 ,3 2 8 . 4. W . L . P in n e r , U . S. 1 ,8 3 7 ,8 3 5 . 5. P . R . P in e , U . S. 2 ,0 2 9 ,3 8 6 an d U . S. 2 ,0 2 9 ,3 8 7 . 6. E . M . B a k e r , U . S. 2 ,2 8 4 ,6 2 9 . 7. R . L in d , W . J. H a rs h a w , and 8. J. R . S tack, U . S. 2 ,3 1 2 ,0 9 7 . 9. R . L in d , W . J. H a rs h a w , and 10. 1 ,9 7 2 ,6 9 3 . K. E. Long, U. S. 2 ,2 9 0 ,3 4 2 . K. E. Long, U. S. 2 ,3 2 6 ,9 9 9 . W , P . t e r H o r s t, U . S. 2 ,3 6 1 ,7 2 0 . 11. K . M . G a v e r , U . S. 2 ,4 0 1 ,0 7 2 . 12. M . L . F r e e d and O . A . S to c k e r, U. S. 2 ,4 0 9 ,1 2 0 . 13. R . O . H u ll and R. A . H o ffm a n , 14. A . W . L ig e r , 15. W . D . B a n c r o ft, T r a n s . E le c tr o c h e m . S o c ., 16. W . D . B a n c r o ft, T r a n s . E le c tr o c h e m . S o c ., 17. R . T a f t and H . E . M e s s m o r e , J . P h ys. U . S. 2 ,4 1 7 ,2 0 3 . U. S. 2 ,6 1 5 ,8 3 4 . 27 (1 9 0 4 ). 2 6 6 (1 9 1 3 ). C h e m ., 3 5 , 2585 (1 9 3 1 ). Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 256 46, 18. P . K . F r o lic h , T r a n s . E le c tr o c h e in . 19. H o lm e s and C h ild , J. A m . C h em . S o c., 42, 2 0 4 9 (1 9 2 0 ). 20. E . F . K e rn , S o c., 168 ( 1 9 2 4 ).. T r a n s . E le c tr o c h e m . S o c ., 15, 441 (1 9 0 9 ). 21. J. A . H e n d r ic k s , T r a n s . E le c tr o c h e m . Soc., 8 2 , 22. F. C . M a th e r s and J. R , K u e b e r, T r a n s , E le c tr o c h e m . S o c ., 417 (1 9 1 6 ). 23. 113 (1 9 4 2 ). G . F u s e y a and K . M u r a t a , T r a n s . E le c tr o c h e m . Soc., 50, 235 (1 9 2 6 ). ~ G. F u s e y a and M . N a g a n o , T r a n s . E le c tr o c h e m . S o c., 52, 249 (1 9 2 7 ). ~ 24. P a u li, T ra n s . E le c tr o c h e m . Soc., 23, 266 (1 9 1 3 ). 25. J. 26. N . Is g a r is c h e w , K o llo id C h e m . Z e it , 27. L . B . Hunt, J . P h y s . C h e m . 28. W . B lu m and G . B . H o g a b lo o m , " P r in c ip le s of E le c tr o p la tin g and E le c t r o w in n in g , ' ' 3 rd E d itio n , M c G r a w - H i ll B ook C o ., N e w Y o r k , N . Y . , 1949, p. 368. 29. D . T . E w ing and W . D . G o rd o n , P la tin g , 30. D . T . E w in g , R . J. R o m in s k i, and W . M . K in g , P la tin g , 3 6 , 1137 (1 9 4 9 ). 31. R . O . H u ll, U . S. 2 ,1 4 9 ,3 4 4 . 32. R . O. H u ll, ''M e t a l F in is h in g G u id e b o o k - D ir e c t o r y ," 19th E d itio n , F in is h in g P u b lic a tio n s , In c ., N e w Y o rk , N .Y ., 1950, p . 395. 33. R. M a tu la and M . M a ts u m u r a , T r a n s . E le c tr o c h e m . S o c., 36, 213 (1 9 1 9 ). 14, 25 (1 9 2 1 ). 1006, 2259 (1 9 3 2 ). 3^, O . H u ll, P r o c . A m . E le c t r o p la t e r s Soc., 58 (1 9 4 9 ). 5 ^ (1 9 3 9 ). Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 257 34. L . W e is b e rg and W . B. S to d d a rd , U . S. 2 ,0 2 6 ,7 1 8 , 35. E . C . L a n g , ''T h e E ffe c t o f A d d itio n A g en ts on S u rfa c e S m o o th ­ ness o f E le c t r o ly t ic N i c k e l , " M .S . T h e s is , M ic h ig a n State C o lle g e (1 9 4 8 ), p. 7. 36. H . A d k in s , R . M . E lo fs o n , A . G . R o ssow , and C . C . R o bin son, J. A m . C h e m . S o c., 71, 3622 (1 9 4 9 ). 37. L . P a u lin g , " T h e N a tu r e o f the C h e m ic a l B o n d ," 2nd E d ., C o r n e ll U n iv e r s ity P r e s s , Ith a c a , N .Y . (1 9 4 8 ), p. 141. 38. O . K a rd o s , P r i v a t e 39. F . M . 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