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He also fOund that the an de corrosion was increased, and the resis- tance of the solution and efficiency of deposition were lowered. watts also felt that the beneficial effects of hydrofluoric acid additions were due to the formation of a fluoborate. This latter fact is an irportant one since the hydrofluoric acid was rarely add- ed to a solution not containing boric acid, so that the effects re- ported are probably due jointly to boron and fluorine- Woodmansee (146) confirmed Watts observations and also found that more voltage was required in the fluoride solution over the chloride solution, and the resulting deposits were harder in buff. :3 In 1924, hammond (178) nude a study of the effects of the additio of conducting salts, and one of his obserVatioLS'wao that the addition of sodium fluoride reduced the resistivity of the Solution. flaring - 4o - (179) the same year found that replacing amuonium chloride in a.nich— el Ilating solution with sodium fluoride reduced throwinr power. Karina's observation together with hammond‘s, that ammonium chloride additions had the best effect on the eha acter of the resulting nickel plate, helped bring about a change of opinion on the effects of fluo- ride additions. fleanell (140) had earlier found that the tarnish- ing of nickel-plated ware on heatinc was not due to the cepper under- coat, as had been supposed, but due to the codepositi n of iron with nickel. He found that the hydrofluoric acid additions allowed more iron to be deposited Thomas and Blum (189) then found that fluor- ides did not Haterially increase a_ode corrosion, 'md Dorranee and Gardiner (341) found that the fluoride ion does not materially reduce anodic polari‘ation. Hogahoom (255) also found that sodium fluoride additions cause loose particles to form at the anodes, with possible resultant ranch cathode déposits. Macnau~hton and hotherSall (282) in investicating the effect of various additionson the hardness of nickel deposits found that sodium fluoride did increase hardness somewhat, but that potassium.chloride lad the same effect. They also pointed--"A serious drawback to the use of solutions containine fluor- ides is the low arode and cathode efficiency." Fluoride additions enjoyed brief popularity, but occasionally sore good effects were reported. Ollard (219) reported that fluoride addi- tions produced marked brffcring ffects in both the'absence and pre- sence of boric acid. He also found that the fluorides helped keep iron in solution, which reSulted in even, fine—grained deposits, and decreased pittinf. In Centradiction to other investigators, Ollard found that fluorides prodtced a softer deposit. Ollard noted that - 41 - organisms such as Penicilliuniglucinium.have actually been found grow- ing in nickel platine solutions, and that the presence of fluorides seemed to prevent th,ir “rowth. The use of fluorides came into pr ctice more recently when Loose (620) found that magnesium alloys could be successfully nickel plated in a nichel fluoborate solution. The bath contained a sliflht excess of boric acid and 3 to 7 g./l. of fluorine over that reguired to form nickel fluoborate. Except for this Special case, f“uoriCe additions have been generally ignored, althou h nickel fluoborate solutions along with other metal fluoborates have been receivinc some attention. The high cost of the initial bath seems to prohibit their general use, although they are presumably little more xpensive to keep constant than the refular nickel sulfate baths. The hemoval of Fluorine from Licks; Elitll“ Solutions: There are apparently no published Lethods for specifically remov n3 fluorides from a nickel plating solution. It is quite probablg that their removal has not been necessary since they seem to produce no noti- cible effects. -42- GOLD if L.\ Solutions: The probability -— 21.1.93. m 93; Gold in lick“ p of gold occurring as an impurity in nickel plating solutions is very small. The few published articles Jn the subject deal mainly'with gold-nickel alloys. haub and Bihlmaier (458) in 1957 found that when nickel'was added to a gold bath so that the bath contains 1 gram of gold and 1-5 grams of nickel per liter, a fine white gold plate of about 153 nickel composition was produced. Young (591) has also written an article in which Fold-nickel alloys are discussed. Pro- bably the closest approach to determine the effect of gold in nickel plating solutions was made by Puri and.Alvi (571) who found that small additions of a gold 801 had beneficial effects on hardness an” luster of the plate, and the pitting tendency was reduced. Even in tLis case it must be assumed that the results observed were due to the colloidal properties of the gold sol, rather t;an due sold itself, although.the gold may have had a contributing influence. The gemova; Q§_§gld fgzn a nickel Elating_$glutionz Gold could be removed from a nickel platine solution by electrolysis at a low cur— rent density. Rapid solution circulation or a rotating cathode would also facilitate its removal. - 4 3 - HYDROGEN 1139. Effects 9_f_' Exaggen inliic‘gel Elatipr Solutions: It is diffi— cult to consider hydrogen as an inflmrity in nickel plating: solutions because it is probably always present unless some special means is taken to prevent its f0 rxmation. The phenomena of hydrogen embrittle- mént of base metals and deposits is well imown, but such a discussion is beyond the scope of this paper. Hydrogen has been attributed to be the cause of several effects, vhich should be considered. Stock- meir (19) considered hydrogen as a cause of peelinm of nickel deposi- ts, and Forstner (226) has pointed out that heavy hydrogen and heavy watt-r which are known to form in siztze plating: sdlutions might be a cause of some plating difficulties. Although Forstner has no exper- imental results to present, his theory is unique. One of the most common effects attributed to hydrogen is pittirf‘. It is new gmerally considered that pitting is of several different types degcndinf‘ upon the different causes. Hydroeen of itself is not considered to be a cause for pitting, but when hydrogen bubbles collect on grease or other goreign matter on the Surface of the plate, they may be a secon- dary or contribut inn cause of pittinp‘. Kollschutter (181) found that eliminating the film of hydrogen at the cathode produced a coarsely crystalline deposit. He found also that abnormal polarization 7'3" l“"~’r:l;* eliminated and that there was little or no contraction. from Nickel Plat ine- figlutions: In the case IL The figmoval 9_1_’_ li'..rdro ’e of hydrogen in nickel plating? solutions, the "iizapurit;,r" is not removed, but converted to a harmless form. This process probably involves the _44- oxidation of the hydrOgen, the instant it forms at the cathode sur- face, by an oxidizing agent. Hydroenn peroxide, sodium per orate, and boric acid are among the conmounds used for this purpose. In modern, organic-type brirht nickel solutions these OIlClZlng agents are not compatible with the bri hteners, so that setting agents are generally used instead. Wetting agents lower the surface tension of the solution so that it is difficvlt for hydrogen to form and collect at the cathode. Oxidising scents aiduetttinr asents will be further diSCussed as impurities in a later section. Il‘iOI-I The Effectsu I o I1e,cel Elatinm Solutio aims The effects of iron as an impurity in nickel plating solutions are perhags the most widely licrn and studied of all the metallic ixyurities. lhe reM on 0 Q .— for this is quite apgarent since iron and n1c:el,beinj chenaicslly similar, are practically always found to~ethcr. In the earl; part is C-Z‘l’Ltur‘tr vizen CO-E‘I‘j nickel modes were use-C, the residual 8-10} of the anodes was largely iron. This gtVe rise to sludre for- mation and the codeposition of appreciable quantities of iron with the nicxll. At this time there was quite a €iVOrsitr of Opinion as to the actual effects of iron, and there w S some vrgument as to whether it was actually a beneficial or harmfl1l contaminant. One of the more commonly observed effects which was rerorted was that iron in the mic kel pliting solution caused the resultant deposit to be smoother and whiter in color. This View was confirmed in the "Brass World" laboratories (CO), and shared by Proctor (151), Thorp- son (172), Barrows (214}, and Clindinin (295}. Thompson also repor- ted that the ratio of iron to nickel in the de osit was hiiver tilsn that in the solution. The codeposition of iron (2 to 7fl) with nickel at a constant ph was found to give a mere finely crystalline degosit, but the alloy thus formed was also harder, more brittle and under more internal stress. There apeears to be some disagreement on the color of an iron—con- taminated nickel deposit. Thedsh many reported that the deposit was lighter, Setlik (307) reported that, while 0.10 to 0.4053 iron in a nickel bath showed no effect, 0.604fi iron cave a dark de;031t, an 2.025 iron left unplated areas particularly in low Current density resions, aid the deposits were dark and irreerlar. In other cases where dark deposits have been reported as due to iron contamination, the viewpoint has been that iron-containinw nickel deposits tarnish- .ed more easily (CO). Lathers, Stuart, and Sturdevant (81} in trying to overcome sludge formation in nicfiel baths, found that the use of ammonium citrate gave dark deposits containiné 6.28j iron from anodes containing 6.493 iron. The dqgosits from solution containing no ci- trate additions gave deposits containing 2.213 iron. The citrate thus increased the co—deposition of iron with nickel, and the depos- its which resulted were of a bluish, or a dark color. The use of citrates or citric acid for preventing sludge fernation was also dis- cussed by Barrows (46), Later (99 m;d Hathers (257). mothers (257) and Pleadwell (140) also mentioned the use of hydrofluoric acid for the same purpose. In the light of the findings of Mathers, Stuart, and SturdeVant (81). however, it hardly seems that it is advisable to keep the iron in solutisn. One could agrua, however, that the many ill effects due to sludge and suspended iron hydroxide are much worse. Since high-purity anodes are practically exclusively used today, either arrunmnt appearS'weak. It has been widely reported that SHSpOhCOd particles rive rise to Ioufh, hard, cracked de_osits. one of the birrest sources of suspen— ded particles in a nickel bath is iron hydroxide. This precipitate is gelatinous in form and can easily remain suspended in solution, or can migrate through the bath by thermal and electric currents. When these Particles are co-deposited, they can cause rourh deposits, ‘ o . 'J . 0‘,“ " V! ‘___ -v and also ones Which are hero and highly stressed or c_acned. Such obserVations have been reported by Voss (191), Evianiikov and hei- man (506), hattacotti (527), and by :orkhov, and Atchi (566) who also found that the iron to nickel ration was four times greater in the deposit than it was in the solution. They also Considered the permissible liuit of iron to be 0.2 g./1. Echelmann (€47), JOLnson (448), and Shepard (220) reported that, wlen the ferric hydroxide particles settled on the cathode, pits could be formed. Shepard (220) also found that when the iron was in the ferrous state, there was a tendency for snnother deposits to form, and also for pitting to dimitish. Heil (65), Kohlschutter and vuilleumier (106), Schlgtter (142), VUilleumier (142), (158), (222 , (240), Thompson (172), Raub (£91), and Lartin (657), all recornized that iron,con- tamination gives rise to stressed deposits, which also may cause peeling if the stress becomes great enough. vuillenmier (158}, showed that even a small quantity of iron would increase die contrac- tivo effect of nickel deposits by_50 percent. Raub (291) also found that keepinc the pH below 4 prevented peeling when the iron content is high. Martin (657) found hawever, that in low pH Watts-type sol- utions both ferrous and ferric iron increased stress,xwhile at a pH of 5.5, ferrous iron reduced stress. Often ferric hydroxide acts like colloidal particles, and as such may give rise to brighter, smoother plates, but also ones which are hard, brittle, and even "burnt". Romanoff (258) has written that ferric hydroxide is the most Common of the "electro—positive" coll- oids, and any cause pitting. Puri and Bhatia (5:3), and ruri and Jun— eja (570) have added ferric hydroxide sols to nickel platinr solu- tions and reported that luster was increased, as W'S hardness. There appears to be some disagreement in the two cases where the effect of iron on current efficiency was investigated. Bennett, Kenny, and Durliss (59) felt that the iron content of anodes did not materially affect the efficiency, but hathers aid Stugdevant (o2) in an article two years later contended that the iron present in 90— 92} anodes was sufficient to lower efficiency. In either c-se the ffect is not very larse, and in the use of high-purity anodes, as is the practice today, it is doubtful that enouch iron can accumu- late in the solution to materially lower current efficiency. Since the advent of briuht nickel'baths, a new effect has been observed which has been attributed to iron contamination. This effect is that iron causes dulliny, or blushinp of the deposit, and has been reported by Weisbe Q (496), Francis-Carter (508), and Keyer (607). The dulling of a bright deposit is a rather general effect not only from iron contamination but also from COpper, lead, and zinc Contam- ination, as well as from numerous organic materials. Roberts (429) observed that good deposits of nickel Could not be obtained on cadmium or zinc-plated steel in the presence of ferric iron, even when a pre-strike was used. he also found that large add- itions of magnesium sulfate did not remedy the situation. It is obvious that the chemical similarity between iron and nickel, and the ease with which they are deposited, vorld load to t‘e possible electrodeposition of a great variet, of ror-nidtel allo s. The bib- liograpi“ on the deposition of niclel-iron alloys is quite s zeable H in itself. A list of this sort would list articles by'Kuster (l), -49- Br ni and Amadori (47), Suchy and Haas (52), firemann and Haas (60), Benvenuti ('75), EFF-13:11.11 and Lizwg'rlesser (E78), Classtgre (1613), Glass- tone and Svmes (22,7), (542 , Hilts/er (:11), liurrein (2’16), otcut (.120), U '— Stout and Janet (E 28), Leasinhg Ste;ansnov, and Belgakova (253), Paweck, Bauer, and Lienbaucr (556), harshak, Stepanov, and Levius (€87), Eaub and Walter (293 ), (£94), Skalozubov and Goneharova (578), and DuRose and Pine (656). In general the effects due to iron can be summarized as follows: The deposit will tend to be whiter, but more subject to tarnishing and corrosion, and will be harder, More brittle, and under here stress. The perIWis ible limits for iron in modern nickel baths is thoufll b3 Diggin (66171) to be 0.03 to 0.22 oz./§j:11.. - S veral fac- Lie hemovi-‘g 9;; Iron fret“. lic‘tel I 1t: " ’ tors have bren develcked from tife to tire w‘ic? have materiall' adCed the reHoVal of iron from nickel platiné s_lutions. One of the first of tb ese factors was 01-e 1oted b" Calm1 1e aid Gamma'e (9) in 1907. These men found that agitation of a 1ic e1 solution contam- nated with iron caused the deposition of iron to be S to 5 times ...]. greater than in a staf‘nant solution under the same current conditions. Guess (115) described a n thod of. electrolvtic1”ly refi: _in' nickel in the presence of iron and copper b7 usinv a sus iension of c alciam carbonate to which a little glue had been added. It is only recent- ly that much has been done on the electrolytic method of removine iror-~ from a nickel bath. ‘..'eisb..rr# (468), (1'41) . and Li"{_ji;; (6611) h ave found th.at electrolvsis at a eitéode current densitf of 5 angs./ sq.ft. 1"ould successfully remote iron and zinc. - 50 - The most practical and successful method of removiyp iron has been by the precipitation methof. It can not be definitely stated when this method originated. Since the early nickel bathn were Operated at a pH above that at which ferric hydroxide precipitates, the rero- ' val of iron by this method was actuallf aarries on auto atiCally. A large amount of the “sludge" Which received so much attention in the early days was ferric hydroxide, and this precipitate settled to the bottom of the tank and was removed periodically. The first precipitation methods employed the use of nickel carbonate {111), or nickel carbonate and barium peroxide (157), or magnesium carbon- ate and armonium persulfate (172). Then Fink and Rohrman (271} in preparing pure electrolytic nickel found that, after removinr most of the iron by electrolysis, the remainder could be removed by add— ing ammonium h droxide until the iron precipitated and then aerating the solution for twenty-four hours, followed by filtration. Although Lisconm's (530) method was primarily used for removing other metallic impurities by carrying them along with the ferric hydroxide precipi- tate, the method ovbiously also renoved iron. Gutman and Kayantz (349) modified the precipitation method a little by first oxidizing any ferrous iron to ferric iron by usinc manganese dioxide and then treating the solution with magnesium or calcium carbonates to preci- pitate both iron and aluminum Zalharova, I-;iS‘...arovz-1, Baunmn, and Galendeev (268) found they could remove iron froxznickel sulfate sol- utions by afding sodium carbonate and then aerating the solution to oxidize aiy ferrous iron to the ferric state. Costello (370) has re- commended nickel carbonate treatment of the solution to raise the pH -51.. to a value to precipitate the iron. This method of raising the pH of the solution has gained consid rable favor since no ext? reefs cations are ad ed t4 the solution, vLicC DTLVeLtS the ill effects sometimes attributed to the alkali metal ions. However, as recently as 1929, Gindlin (511) has suQPested remOVal of iron by treating the solution with hydrogen peroxide and sodium hydroxide, and filter- ing to remove the precipitate. Jeveli (519) and Smith (558) have also recommended the precipitation method as has Stacker who sugges- ted raisina the pH of the solution to 6.0 with line and nickel car- bonate, then addinc hydrosen peroxide, and finally filterin . The most recent reconmendation has been made by Dirgin (654} who has given the following instructions: "Raise ph of the bath to above 4.7 (electrometric), afd one pint, per 100 gallons of solution, of 100 volume hydrogen peroxide to the hot solution and filter." These two general methods are the most common methods which have been, and are being practiced for removing iron from nickel plating solutions. Howev r, several suggestions have appeared in the liter- ature, which are interestinc. Berthelot and Gaudechon (25), for in- stance, fround that iron was precipitated as ferric hydroxide when subjected to the action of ultra-violet rays in the presence of nickel or cobalt. .A patent by Grgnningsaeter (317) indicates that iron can be removed by the action of powdered activated nickel. 'Wille and V31- kel (438) have a German patent for removing iron from solutions of nickel and cobalt by the use of alkali perphosphate. Samuel (575) has a British patent for removing iron by adding c llulose pulp, nickel or cobalt peroxide, higher oxide or hydroxide, to the bath, and filtering. Shepard and Knierim (658} have recently obtained a -52- patent for removing iron which stipulates adjusting ti.e pH of the sol- ution to 3-4, heating: to 80-1800F, oxidizing wi th hydrogen peroxide, and then maintaining the pH by the addition of calcium hydroxide- The calcium hydroxide and hydroe n peroxide are adi ed to the solution as a Slurry- LElD In 1924 Shepard- ghe Effects 9i Leg; _i_;j_ iiiekel I- (186) (209) recommended that a brinhtener for nickel plating solutions could be made by adding acetic acid to a 20]; lead acetate solution until it was clear, and addine Z oz./?al. of this solution toyether with-%—oz./galo of glycerine. Excellent results were claimed for this brightener. Hhen the plate began to dull after some time of Operation,loz./lOO gal. of the 83% lead acetate solution was’added to brighten the deposit. Raub and Wittum (459), and Uittum (469), (5:8), fbundthat lead caused fine-grained lustrous deposins, which were bright and brittle with a tendency to peel. They also noted that when lead sulfate was precipitated, the deposits were dull, and rough spots were likely to occur. Cosrrove (408)also reported that lead contamination caused non-adherence of the deposit, and also noted that this did not appear until chfone plating was practiced. Ballay (344), Mattacotti (527), Meyer (529),(607), and Stocker (540) found that lead gave rise to dark, streaked deposits, and the effects were Ebst noticeable in low current density regions. Martin (657) found that in a low pH Watt's type bath, lead in low concentrations had little effect on the stress of nickel deposits, but at a pH of 5.5 lead reduced stress. In brioht nickel solutions Eckelmrnn (£47), Jehnson (448), and Francis-Garter (508) have reported that lead con- tamination caused dark strcaks to appear. In nickel-cobalt bright nickel solutions Weisberp (496) has found that under avera e condi- tions 5 mgo/l- of lead revealed dirk portions at the bend of bent -cathodes. Diggin (664) has also reported that while lead was only - 54 - slightly soluble ’n nickel solutions, the presence of citrates, ace- tates, and formates held lead in solution, and he considered the top permissible lihit of lead to be about 0.002 oz./btlo. Since the permissible lizit of lead is very low, lead is one of the worst contahinants of nickel solutions. Lead plumbinp and lead tank linings have been a freqzent source of lead contamination. The ttlp deposits H. effects due to lead can be summarized as causing br with a tendency to peel under chromium deposits. The deposits also tend to be dark in low current density r rions, and dark streaks may appear in normal current density regions. Under certain conCi- tions, very szooth and brieht regions an: appear in the deposit. Tie Eenonal of Lewd frag Iickcl llfti p S utions: The renoval of lead fronlnickel baths does not produce any difficulties. Nittum (469) proposed that lead could be rezoved by strongly acidifyine the solution with sulfuric said, and heatin: it in order to form insolu- ble lead sulfate. The solution was then cooled, filtered, and the pH restored. The trouble'with this method would be the difficulty in restoring the pH, which would require quite some quantity of nickel carbonate. The most practical method has been preposed by Stockir (540),Mattacotti (484). Heisberg 541), and Ligsin (664), who pro- posed low current density electrolysis at 2 to E amps./sd.ft., to- gether with a pH of abou. 2, and a fairly hifil texpvrature. -55- in * alumni; nii§_LlQ3§l Plotipp §93ution : A great many effects have been attributed to the presence of ma'nesium in nickel p atinf salutions. Durinp the period of 1910 to 1920 map— nesium sulfate additions were quite popular, and as a result, its effects vere well investigated. One of the first effects noted was that the plate which resulted from a solution containing mannesium sulfate ”ad a yellorish tince to it. This was reported sirultan- eously by Sizelove (GS) and Taylor (69). Proctor (66) had earlier reported the use of newnesium s lfate as a grain-refining'or bri'ht- ening agent. More recently Lakar'eva (482) reported that deposits resultin? from the addition of marnesium sulfate were more lustrous, harder, and more uniform in texture. Evlanrikov and heiman (506) in an effort to produce nickel plate free from pinholes found that may- nesium sulfate in quantities from 1 to 100 g./l. produced matte, white deposits. Another report by Walters (102) pointed out that a small amount of magnesium sulfate added to a nickel bath produced a more ductile plate, but if it was added in excess, the deposit might be arkened. Richards and Henniges (208) aCCed magnesium sulfate in amounts from 4 oz-/éal. to 16 oz./ gal. to nickel solutions contain- ing 1 lb./bal. of nickel sulfate aid 3 oz./§al. of boric acid. They noted that the deposits were good and white at all concentrations, and in a ranxe of current densities from 6 to 15 amp./sq.ft. there was slight gassinr at aconcentration of 16 eso/eal, but no pittina was no— ted in any case. Diygin (664), (596) Has reported that the presence 0f magnesium Sulfate in the solution made the resultins deposit muci -56- softer and easier to buff. In a nickel-cobalt bright nickel he found the Uicker's hardness to be reduced from 5'98 to 2'98 by the addition of 2, oz. gal. of Ingresiur; sulfate. Diffg‘li; (597) also studied the effect of substitrtingz'j magnesium chloride for nickel chloride in standard baths and reported favorable results up to a concentration of E oz-/§_:'al. Above this concentration the deposit developed hair-line cracks. Two separate invrstig-‘ations have been made to determine if any magnesiuniis co-deposited with nickel, if the solution contains Iraniesium sulfate. In one of the first ar- 1' ticles on the use of this salt, 'flaser and Schulz (45) found that 1.5,: magnesium was co-deposited with the nickel. In 1938, howeVer, Bul- alsh (475) investigated this probiem and reported no madnesium in the plate. In the light of what has been learned since 1912, the observation of Bulakh, is undoubtedly correct. Many effects have also been reported on the effects of magnesium s lfate additions 0:1 the Opt‘r‘ii.t10n of nickel platine baths. hammond (1’78), Underwood (2321), and Dig-gin (664-) have reported that it in- creased bath conductivity. Magnesium sulfate also increases the throwing power of nickel plating solutions, accordine- to Marina: (179), and Diggin (596). liatixers, Stuart, and Sturdevant (81) reported the use of magnesium chloride to prevent anode sludge formation, and a similar report was made by Robinson (87) , usinrr mayrncs ium Sulfate. Robinson also noted that the anode surfaces remained quite clean, and any trouble due to pittng was removed. Magnesium sulfate additions have received much favor in.plating non-ferrous materials. Proctor (51) advocated the use of magnesium sulfate additions to nickel plating so lutions when die-castings were +0 La. Plated. - 57 - D‘ (‘3 Herrick (148). Thompson (312), and Gordon (27¢) ve since confirmed the value of this adfiition. Proctor (118) also piOLccred in the use of magnesium sulfate in nickel solutions used to plate aluminum. Holland (165) found that Harnesium.chloride could also be used, but Foss (258), Werner (291), l*rause (828), and Balkiy (242) have pre— fereed the use of mamesium sulfate. Underwood (26:) has also re- conmended the use of a solution containing hashesium Sulfate, a non- ium chloride, and codtnium.ehloride for brihht plating small lead parts- Tie Removal of figfihesium fron nickel Platino golutions: L0 in- formation hzs been fbund on the removal of magnesium from nickel platin" solutions. magnesiuniis not a very probable accidental contaminant, and its Lresaace is g morally attributed to intertion- SD ...: $3 A! (... cu,- [—0. O m 3 4, ‘or special ;urposc platinjw The effects of magne inn: are, as a rule, not objectionable; however, if a mctled of removal is desirable, such investirztion will be ndertahen 'n connection with this research. MANGANESE \II The Effects 33 Manganese in Nickel Plating Solutions: Very little has been.pub1ished on. the effect of manganese in nickel plating solu- tions. Barrows (214) andlfleyer (4540 have pointed out, however, that. manganese is sometimes added to deoxidize molten nickel before it is cast into anodes. ihey pointed out that if manganese gets into the sol- ution rough deposits may resuit. Botassium.permanganate has been fre- quently suggested as an axidizing agent to overcome organic contamina- tion of nickel plating baths. Shepard (188), (220) and Romanoff (267) have overcome the ill effects of organic contamination in this manner. Shepard also found that the potassium.permanganate additions counteracted the hardening effect of cadmium.as a brightener. ihe argument for the use of potassium.permanganate over other oxidizing agents in overcoming organic contamination was that the permanganate acted as its own indica- tor, denoting when enough had been added. if an excess of permanganate is added to the solution a precipitate of manganese dioxide is formed, Which will eventually dissolve in the badth. Thomas and Blum (210) found that permanganatue additions did not markedly decrease porosity. Since 1930 it does not appear that the use of potassium.permanganate as an ox- idizing agent in nickel solutions has enjoyed much popularity. Since the reduction product of hydrogen peroxide is simply water, it would obviously be preferable. Campbell ‘174) showed that it was possible to form.alloys of manganese and nickel by electrodeposition. In certain concentrations, it'would appear that manganese is not harmful in nickel solutions, but a real source of information on the effects of manganese in.various concen- trations is not available, nor has work been done on its removal from nickel plating solutions. -59.. 1.231101%}: 2L6- £125.19. 9.; .azm an akin—1. La tirw Solqtj Ops: There are two publh‘l-od accounts of the presence of mercury it: nickel pl-xtigr" 0, (“Of ..7 solution The first account was. mvde b;r1.‘;tts ( 9:3) 1;; y“, tried lw": . ‘ ‘r" ‘0 ’, "“l‘ 1. ‘ .. r: . *1 ‘.~ ‘ r . ’fi, . - - ‘ 'p- the 11x». itloa on :-o.-=.011/: c lozice l}! -- c-.f‘o:‘t to pro-“n-1, 131.0 for- 1.10.th11 0'2" ILL’CT'DL'CL .‘U the 0 It" 060. The :‘1 sult of the :“fi ition vrzrt . tint the. dOjcl’il‘lr'ilif‘ "Lotion vat: so "to t7; it no nickr‘l would Fio- posit. In the ot‘rugr account 3013,1321 and i511‘:;°‘.- (51;) added trace amounts of 1::er0uric chloride to a nickel Llatizzrf solution, an ob- . served that the depos its which resulted- were louse 316-. powdery- From the results of these two cases, it is obvious that Mercury contamination of a nickel platinu solutloz': would either totally in- ‘i‘r‘it (”Clinositioa or L‘l‘OdLCQ entirely ‘.‘1L‘17.lt'"‘.b1€ depo sits. J -60- ‘r - ~r~y~~~a -' wrvv ...ULalJlJlan chi The Effects f KolflC ‘1‘ in LicLel Elntinv Solutions: In 193 , Barrovm (121) ad ed 31711101111131-101;.7-‘15'1170 to a nickel mlfzzte solution - containinc MifiEJSl m sulfate and buric “air, 3rd r ported that a black éeuosit was obtained. Since blac? Ceposits forw Tron agin- thFlS containinf' mol;-"u€.:1ter3, it it: rzzztilr‘r Certain that rziolgrbdewm in nickfil plating solutions unuld lead to black or dark colored de- posits. In the only oth r account on the effect of molybdenum in nickel solutions, Iuri and Seth (612} found that a molybdenum sol added to a. n1 1:621 801 tior. irparted luster to the deposit. here again is a case vhere the colloidal properties of the 301 may be the con- tributing fan tor to the obSerVed results. ~61- LIDEATES The Effects 0. ilitrates Lniiicliel 2153:1312!" Solutions: The effects of nitrates in nickal plating solutions have been known for some tire. In 1915 Su an (52} found that nitrates or nitric acid could cause dark deposits. Kathers and SturCeVint (82) also found that nitrates, which.nmg oocur as an iu;urity in nickel salts, depressed the current very stronmly. Hudson (128}, and Watts (192} found thzt nitrates were a. such stronu depolarizers thzt tney could ensilg cause deposition of nickel to cease co;plctely. highol and Jatts (204) have reported that the amount of nitrates necessary to cause no deposit to for: was the neiélborh:o6 of 40 §./l. According to Eldridge (212), however, at H 3-4 1,-) E. Bailey of Er nce reoo.mended the use of small amounts 0: nic cl nitrate as an oxidi'ing afient. An encess of the nitrate wns reported to cause fragile and burnt deposits, as well as a ratio dr0p in the current efficiency. hothorsall ant Harmmnd (351), (560} than under- took a study of the effect of nickel nitrate on nickel deposition and found that it increased hardness and streSS, and brightened the deposit. Since the deposit was stressed, t (re so: also a tendency for the deposit to become cracked and exfoli ted. As electrolyscs continued the nitr to was reduced to a: oni1,uhich in turn preVented the precipitation o :' nic‘t.‘~ 1011': 21.5%" “oxide. .iitii incrse' si “ conson- trition of nitrate the Cathode potential was gradually noted to fill, and the arount of hydroccn rcleasef at the catiode decreased. At a concentration of 2.6 fi./l. the formation of hydrogen ceased entirely. ‘As nitrate mas added to the solution an 'nitial increase in pitting was also notic-c, but then it gradually decreased witL further nitr te -62- add i t 1 0:13 , and fir. ‘31 1,”; c 8.35 ed when. 1-5;6 r0 (“€21 fo r111 t i o ..: 8.1 s 0 nitrates he ve not found Very extem ve use as oxidiziiiy priharily sir ce hycr0“en peroxide produces better resalts, eLSier to cor trol. Ecgardt (C45), (:72) has recommended depositin ‘ lion-11020113 81.6 hyC‘rOf‘mn-i‘ree Ce )OSitS , union sodium.nitrate, Fadeeva that control w0u1d be very difficult. tly investira ated that tEe additio: did sot cecre se porositv. has also been shared by Di win (596), (664) who not only incre sed pittin creased throwing power. In also found to restrain the deposition of nickel. ___e_B€I:1OV§L___ ”:11 tzates __m__1 iota”... Pleat in golutions: val of nitrates from.nickel platinw baths becomes evident observation of Hothersall and ia1zond (E 51 that nitrates duced to a Ponia durin" the operation of the'bath. tingfconditions have been surgested b; Diggin Wit}; that the bath he finds acifi 2 cc./bol. of S If ric operated us inc dum.sy cepler eat odes. laths acid ceased. a'ents, and i S for contained but the conwosition of the baths is so Complex 551} has more recen- ted the use of nickel nitrate in solutions being oper- This viewpoint found that nitrates but lowered cathode efficienCY. and de- cobalt nickel baths, the nitrates were The remo- Trom tLe are re- The best opera- (664) vho proposed 1 “‘1 1‘ (.1: -LA then - 63 - 'f.‘ '. ..f‘».-. .- ; qr a - r» V ‘ a l~x.»-'J~'~()\A....¢L. IJJJLUASIL L The Lfectzt- oi PFC.“ .. 1* Eerogf "e mIILQ‘ggl Elgtjnr‘ “o utions: hy- O drogen peroxide is added to nickel ylatinv solutions ibr tre purposes. The primary purpose is as an ingredient of nickel baths for :rcvcn- tine the deposition of hyCropel at the cathode. Stdgcr (125} was the first to studr this addition when he adled hydroren peroxide as a depolarizin" spent to the solution and noted that the normal stress on the degosit ans r duced. Hadsen (182) was the first to recontuend this adfition in retllar pr: ctice. Ie recoxrmendede do 11y addition of 4c.c./l. of Ca peroxide, or a concer 'tration of 0.12r./l. of nic} :61 solution. Haring (loo) fbund that peroxide in t is concentration re- duced the throwing power of the solutions, and Blum ard Thomas (210} found that peroxide also promoted anode passivity. In 1921, Hother- sell and Eammond (£51), (zoo), undertook a investigation of the effects of i gdrogc: ;eroxide on niciel Ceoositior, ind their regort has brvn Hos: V11? 11 . AdditiOILS of 1croxi€e mere found to increase hardness, stress, ano the briyht a;wle~rance of the (:e :osit. The de- posits thus tended to become crzcfied and expoliateC, and this was attriJuf ed to the precipitation of larg jer amounts of be s'c colloidal m1ttcr with the ris in. rate of hydrogen ion discharge. Wit; increas- ing acditio no of peroxide, the amount of hydroflen released at the cathode become Cradually reduced to zero, but on further additions the gas discharge recomme1ced. They attributed this observation to the rcdu ction of the nickel ion concezitration at t: 1e cathode b as as a result of the IT ecipitation of a considerable guwnt‘tv of b,s ie matter. The cathode efficiency'was also oose rved to be linearly de- creased vitn increasirj additions of yeroxide until a minimun Value - 64 - was reached uhich corresgondod to zero hydrorencs01 r~e at t -e c:1th— ‘fio ode. As the additions were increased beyond this critical con extra- tion, the catLode potential showed a mar;ed L were Thise authors also felt that any effect w 101 hy'r “:n p “15 had on reducirc git- . ~.~. nm ‘as cue 011" to tie innisition of hydrOflCn Cisclarre- If the ‘4. t solution is imy a e, However, the action of err ride in oxicizing and pr cipitatinw iron, w‘thc oi112i Cert aiso~;ti0a of other i:;uri- ties hr the nrecipitate, =,7ust be t.ken into account. 'he second use of hydroqeu sore”iCe 1n nickel glstil‘r' solutiors is for reroving contznixation b; iron and orp111ic como01nds. A Cis- cuSSiono the effects of hyCrOFen :eroxiee in tgis seiner is found under the sectim on renoval of these ingurities. T19;EIDV3L,OfIfmr Pr; Pcroxidg_figu;‘. Ififihorwm_:eroxide is very easily removed from nie?nl Vlfitilr solu- tions- Raisin? he tangeratur , or the 32 of the Solution, or a c m- bination of these, will ra;idly Cecompose hydrogen peroxide. Green (512) showed that a e ph of 5.62, hydro~en onroiniC 1:13 ahout 97 q cecovyosed in 2 hours. At a 3h of 2.7 and a temnaratur. o; 60 o. the hydroCcn geroxide V38 92; Cece 1108 ;C in an heir and a half. A combination of these cor 1ditions would prohablr fr ctlf 3C39107"t0 the deCORJOSitiono The eds e O removal of LyCr0§vr prroxiCe 13 well as its chemical constitution accounts for its greater aydlication as an O:~:iC.i'/ting:' 23!) nt. - 65 - 1.“? ‘ :"n' r; \ .-_ 1.4qu 4-U1LLQ The «' cts Elstiir Solutions: The effects (1 .L w H due to phosphorus », . l -rc practically uufimown. Blum and Kasper (E66), and Cotton (499) have investigated the effect of p osghoric acid as a fiuffer arc;t in nid‘el rioting solutions 31C found ‘ a (1 1.7 ‘0‘; 1.3. cf ’3 sol- ha it ine?fcctive. IioVal has Ree: Cegositcd frow a grvo~ U) ition {‘1 ution Ry Koygngi (ICC), ’ut tiis is the Solitar” 0339 of ego of nickel from any lhosphatc solution. ilosghats contaminatiox is possible from C19: in? Solltions, but if axy ill effects result, they are as yet unknctm, or unrcgorted. -66- '9'v :JLL . :1 .' Lzlvi The Effects of Selenium in Kick; H: The effects due to 601611111171 are Verff little 1;;_O'-."1;g It is not a probable contam- ‘ (- inant, althOuph accordin to Youn~'(“§a), selenium ma; ie 36691 in {‘1 swell traces to Certain yroprietery bright nicke s luti'ns. Burt and Juneje (570} have also found thit sols of selenium adtec to nickel solutions 1r;roved the luster and harfiness of the de;osito With the exception of several 3‘ onts, only these two cases have hes; p Elish- ed on this impurity, and the effect of other than trwce aaounts of seleniunzhave not Icon reve led. - -‘ ya 1‘ ‘.~ \ - s- - l \ - ' v. . , . L. - x 3. w The i novel cl be ,- .s i in, ~t1nr ¢ dblOLS‘ accorcin' .- to Stooger (617) selenium can be remoVeC fnam nickel platiny solu- tions in tw0'wa:u- The first met 0c is by raising the pH of the sol- ution to 6.2—6.4, (electromctric) abdinr nickel hyfivoxide or nickel carbonate, and an oxidizinf ercnt such as hydrofiun pe“oxide, or po- tassium german~snate. Selenium will thus be grecipitstcf along with iron, zinc, aluminum, trivalent chronfiunn an: csfmium. Stocker also found that seleni m could be removed from nickel platin“ b1th° by cementetion on iron or nickel. SILICOJ 2113 Effects 9}; i con Lwrlqtjnr figgutigns: Kern and Feb- ism (18) and Ken: (23) have contributed the sole references on the effect of silicon in nickel pletinrfsolutions. In tiis cese es in the 0138 of some othir irgurities, it is not the vleuen wLich is in— volved but fluosilicnte. Bless authors h:ve reported successful degosits of nickel from a nickel fluosilicete solution. What tLe effects of silicon or of silicates are, have not been rcgorted- It would agesr from t. is lack of inforzxition that silicates have no real detrimental effect in nickel ylating aalutions, at least in small arinunts. This is evident since there is certainly the possi- bility of silicate contaminatio of nickel pletinr solutions from cleaning solutions. - 68 - C ’ V ' J .-L 55;: Eh§_flfifects n§,§ilzer_in,fiichel Elating Solutions: Silver is not a very probably contaminant of nickel solutions, and if it were to occur, it would probably nor remain in 331ution in other than very smell concentrations. Th re thy be sons possibility that silver might be 31 igltljf solubl, in certain niche-l ylatirfj' solutions, but in those containing chloride, it would probably'be larrely precipitated as sil- ver chloride. Kickel~xi1ver alloys have been electrodeposited by Behnke (905), and flathers and thnson (48:) but in neither case was the solution of comparable composition to en? nickel plating solution. Puri and lhatia (5:2), and Euri ant". Alvi (5371) have added silver sols to nickel platinfi solutions and found that a beneficial result was produced on hardness and luster. It must be remembered that the sil- ver was present as the element, and not in solution, and that the effects observed may be due solely to the colloidal groperties of the $010 -59.. SULi‘Uh figlutions: Sulfur has been reported as a. contaminant in nickel plating-*7 solutions in 3. var- iety of different forms. Since nickel deposition is done in sulfate solutions, sulfates can not be considered as imfl.‘;urities. In 1908 Turrentine (20) proposed that persulfates could be formed in sulfate later Couteulx U) solutions by the anodic effect of nickel. A few year (26) found th-it bright nickel deposits could be ob mined from 3. dan- ble-ni kel sulfate solution to uhicT ammonium persulfate had been adfed as a brightener. Sgerry (44) also reported a solution of nickel Slilf".te and armonium chloride to which had been added sodii-m 1361‘8111- fate. Another solution Sperry r8130 rted contained, besic‘ es nickel s 1- IA. fate, Hugueshum sulfate, boric as d, and sodium persulfate. Since no ill effects due to )3ch lf-‘tes have been re‘prted, zinc. sevtral ("1.2- erent baths have been founi’ to yield successful it'osits 1.1. t‘ c- ;..re- sence of Lersulfates, it is reisonablc to believe t: at they have no 111 effect, other tha the effects generallyjat‘ ributed to all oxidi- zing: agent, i.e. hard, brittle, stressed deposits when present in excess. Thiccysnates have been COIIB;..)Il ingredients in black nickel solutions. Solutions have been sue: sted by Watts (54), Deflars (76), Blum (105), Proctor (109), Ilegaboom, Slattery, and 3:3.“ (117) _. (155), Leah‘s. (171), ilamzell (18;), Barrows (22L ), LLoline (648), and others, which contained sodium or potassium thiocyanate. The t‘.~.ioc;rrn:ates have an 1:71;“)ortont part in producing tie blaci ("egos it, and Iior'abcom, Sl atte 'y, and ham (117), (12.5) Lave regorted as much as 10 to 1d; sulfur in blac‘” nicl‘el deposits from solutions containinrt thiocyarates. Some recent we Ii: has been done or. sulfmlate baths of nickel, with varyine claims of success. Cambi and Piontelli (502), zmd Piontelli “1nd Guilotto (5223) claim nickel can be both electrorefined and elec- trode}; osited from nickel s -‘111 Hiate s lutions. C ofuill (501) also deposited nickel from Sulfamate solutions, bu; reported that the de- posit this not briyftt. Sulfifies hive long been knovr to be Fri} t“L11f a ants h;!n:;r 1 types of beth. Lenin 133 (627) gointed out tLat so< .4. m sulfide 0,416 be used as a brivltuner in nic cl pl ting solutions, but tLe be is m1sastifrzctor Clue to the evolution of hydrogen s‘lfide $11 the pr cipitation of 1M;c1 su1: ‘ide. Argl self ngifefi, and aryl sulfbni: Mile .3 as well as golrs-1£onic acids h‘v- been i mieC by :in:- s\.-lutio:.s. They also jointei out the altlpouj-h other aryl sulfonic aciés gave reduced grain size, but 110 brightness, they also permitted the use of higher concentrations of 011 "1teness sue} as cadmium and .1 zines-1.113, sodium ferrite, aldehydes, Itetones, and 2121:1313 po1~zryl 3 o metLanea, and enhance tneir action. £111 excess of these additions ~pro-- Ve ts depositi n at low current densities and ca ses brittleness 311 poor aChesions. Br “'1'1-t nickel dqosi ts have been 1’ ound to contain 4 . 1. q . . 0.02 to o.»6,1 sulfur wnen (..egesitee from a solu 10:: containinr‘ one of the. se organic sulfur co:r;;ounc1so q Kern and 13111311; (18) trier. Celwosition of 1:10 1 el from a ('it1‘1io‘11rizte - L but found it iuistat-ible (”110 to sngm‘ ' tier. of? 311111...- . bod-111.: suli‘ite ws 21616-61 to a 1110‘ el. s11utio1‘1 by Luring; (171') 1.110 r ported ‘ '1 I g 'f" _ _ " res lter at 1.1:) , es,r‘ '(fllt densi t1 1S, 1-.rrgzcu1 to O 0 U) H. c f- U) and Gurewicz (4111'?) have degositefi. '~ 1: 9 eoyacr- 115:31-7e1 allot from a Hits entiiLing a 00;;2r CLlOTiCo-tlinnrea ce;LleK, Lie? 1 S lfutc and thiourea and acetic acid. Rolland (1&5 L;s also 3e90rted the use of sodium thioszlfa e in producinv heavy iickel cogosits. lounp 9rd Kerstcn (471), (449) hwve also formei Eeyore nicficl~o"lfyr Com- poxnés 3* electrodeposition fret a C;u”le nickel sulfate solwtion- Congo.“ .613 containing i‘TQL" 27,: sulfur :26 72,3 nickel , to 8,3 sulfur and 87$ nickel W:re formed- Beutel and Kutzclniwv (7&1) fornd that nickel sulfide was (egosi- ‘4. t... -L ‘ .i 1‘! 1-1- 1 ) v (N - -\f1 '71 but; .J..l(, QT .JCJLUO drunel ted from nickel sglfitiOLs wlaj Lqu"1f (J '1 r‘) (5 ’1 C? (D r): d l ('f' .A ") ‘.I 5. O I 1 f.) U) FJ H: _ J C+ O (.0 O h’ (‘7' . t—JO (.2 H V-J 0) <1 \- (‘3' 1' O 'i Ch 1 d (400} blSLlffitO migit form along with 3-1 ) H I“ ..‘J l (‘1 (D C O) t-J. d H 9 ,_s d (J .—J O J I_JO C’- H. (D m Fl y— ‘4. ’3 3 o I _J LiCKJI ye oxide. Puri and Juneja (57“) ad ed a sulfur sol to a nickel plating solu- tion and the deposit which res ltee was bis-k and Sgon'y. One of the most coixpn sources of sulfur contamination is from rubl‘er 1534.1}: linings. Azcordiwc to True (619) the contamination tray be caused by a L130? sulfur covyo nd caused by the unreactod clem- ental sulfur in the r bber compound. - 72 - TIN The Effects of Ti; in KLCKQJ Elqtine Solutions: Although tin is OLe of the more co non elements, the yossibflity of its presence as an imLurity in nickel plating solutions in lrobably slight. Thtre may be tin contamination from.br012es which are nickel—glstefl, 33r- tivularly if they fall to the t’LK bottom, or become tezgorarily ano- 1 ' flic, but nothin: of this sort has been reyortcd. In such cases, tLe effects due to zinc and coyyer whicn are usually present 1” hif er conclntration than tin ii bronzes, would orobahly obsolre any effects due to tin. Solanki and Singh (615) added trace amounts of stannous chloride ot nickel yleting solutions and reported that the éeposits were loose and powdery- ERIC. 6 TZJ ff cts Q1 ML mm a Iggtig‘pfi: Tung'st—r. has been adieu to nickel sulfate solution; so that a nicxcl-tun"sten alloy couli be electrode;ositedo Althourh tunhsten alone is fieposi— ted from alueous solutions, when nickel is also yresent in the solu- tion, the two c'n be co—degosited. Articles on the de:osition of nickel-tunwste- alloys have Feen written by Gol'tz uni hhurlumov (él ), Bclysev 3;.16. Lipovetslczgrs (547) , d‘fly-‘er-nho, Lrgzhizti, J11: Li;s:.l'tz:eva (5:50), CogCi 1:011; our. hislscr'. (628). (65-2 -74.. The E’fgcts f ’inc in Iichnl,ilati;g,Solutions: The effects of zinc on nickel platinr solutions has been well investiflsted. This fund of knowledee has becn accumulated lsroely throush.investioations st nrs. Grahan (165) under- {—1. {J on the nickel platinr of zinc—base die c took a study of the direct electrodeposition of nickel on ninc, and found that the presence of zinc in a nickel both won not Thongson and Thomas (156) upon investigating the purity of nickel Stilts leound that o to 1;: zinc in nickel sulfatc'xa not detrimental, but at 0.2,? zinc the cargo sit '-.'1..ich resulted from the use of these salts tended to be bright on the edges and also tended to pit. At 0.2; zinc in the nickel sulfate, the deposits tended tO‘v’ftl‘d bright edges end splotches of brivht deposits. Setlik (207) also found that 0.113fi zinc in a nickel plating solution retarded the rite of deposition, while 0.226; caused stains to form on the deposit. At 0.45; zinc the bath was useless. Anderson (364) also reported that the effect of more than 0.2 g./lo of zinc in a warm n’cKel solution was to brighten the deposit. Crocking and poor co rosion resistance developed reachinfi serious proportions at about 0.6:./l- of zinc. Anderson also ObServed that spccémens plated from a solution contain- ing 1 gm./l. of iinc in a sulfate-free solution,contained 0.23 zinc. Vbzdvizlunskii and lanolin (42¢) investigated the causes of strong; deposits corld be obtained 1; conocntrations of zinc of 0.é5 karts er 100 tarts of nickel present. At a hi9 er zinc content, J- of zinc I'd between 0.45 and 0.65, strelky deposits of nickel developed, but the streaks could be removed by ralSle the bath temperature. Above 0.65 q zinc the streaky deposits could :ot be aviodet. They also noted that -75- the pH of the salution around the cathode increased with increase of zinc salts, reach ne such a hir' val e (6.07) tint a colloidal precipitate of nickel hydroxide occurred. The positively charped particles of this colloid were then transported to the cathode sur- face and deposited as a dark layer. Heyer (607) has also written, "AS little as 0.006? ozo/bel. of zinc will cause the nickel deposits at low current densities to be bright and somewhat more brittle. Higher concentrations of nine will on se the nickel Ceyosits to be Very brittle and, for erample, a concentration of 0.02 osc/faloof zinc will cause the nickel denosits to be very brittle, particularly at the low current density ranre." Accordinf to Dirgin (664} zinc causes dark plate to result frou bri ht nickel solutions in low cur- rent density regions. It is not accurately hnton LLEI sins was first ended to nickel platinr Solations as a bri itencr, tut lroctor (68) in 1915 mention- ed that zinc was being used for this purpose. Zince this time zinc has been widely used in this manner. One of the most cornnn observations on the effect of zinc in nickel losits. Tor i. platinr allutions is that it leads to dark or streaked de Doest (70), Field (151}, Taylor (89), Thonyson and Thomas (155), Haring (179), VOSS (191), Hirshing (225}, fiothersall (352), Snelling (360), Raub end Bihlmaicr (£92), uni probably others, have all ten- tioned this effect. TWo obserVations have been made on the effect of zinc on the stress of resvltine degosits. vuillenmier (15o) found that the presence of zinc caused an ilcreasc 11 the contraction of niclel degosits. hartin (637} has obserVed were recoltl’. hOTOVGT. tVVt in 10” PK Watts-type ‘1 solutions zinc does not :nterielly effect stress, while at 3 p1 of 5.5, zinc reduces stress. TLis later observntion is i; contradic- tion to Vuille‘nicr's obserVation which won also wide on a hirl p1 solution. Karina (1“9}. (1 0; rcgorted that the frcsencv of zinc in- creased the throwinv rower of a nichcl plating solution. Zinc has also been a corhon in“r:(icnt in black nickel solutions, and in both one 3 its wresence is Canned necessery. nnnr srtiw-es have been written on blust nichel Sol ti n: wlic cantzinc? sine. Some of tiese "re bV: Hans (1(2), ( CI), Lebolt (161), Watts (5a), Blum (105), HongOJm, Slattery, and Ran (117), (125), Larwcll (182}, .5 and Barrows (25:). nctorCinr so Toyeboom, clattery ;;U 1;: goo: .-D. O a t Q! r,- I . I I i? Pr; (J F) black—nickel Cegxxiits usually contain 20 t3 (0132 fall into the class of alloys. Other nickel-zinc alloys have been degosited, probably the first bein” done by Schoch and Kirsch (10}. Investifgtions on the Ce;osition of nick l-zinc 3110"s hifle a so bee; carried on by Glasstonc (226), Le Lora (5&9), and Lustnan (646). Izgeryshev and RetikiOVicL (518} have also reported on the electro- deposition of a cogjnr—zinc-nickel alloy. To summarise the effects due to zinc in nic”el 31stirc solutions, the following effects can He considered a: fairly acceptable facts. In the neighborhood of 0.007 oz./bal. of zinc is permissible es s brifiltener in dull-nickel plotinq solutions. ii Lvr concentrztisns ' o fl ‘7. will yielf brittle deposits, x;;c; say be eit‘cr dgri or stro ted. bright nickel solutions the effect of zinc in lower concentrltions than 0.007 oz./gal. mey beco c evident by darkeninr in the recesses, or at low current densities. - 77 - 1‘11 9 Ego-r: ovg__ f§_____ : 'ro:‘ __i___e1:o';_1. :1 ti domitiogs: ills-re ere taro gonernl procedures for re DViLf site centuriistion from a niche] xlst— inn solution. lrobibly the first mentioned nus th proc‘gitution hotl— 0d, or the LiscOMb matted (2:0). This metlof consists in first preci- pitatinb large ousntities of ferric hyfroxide in the nickel bath. If the iron content of the solution is not very higliza ginti ty of an iron salt is usually added. The iron is also grnerslly oxidized first eitL b aeration, or by the‘use of hyCrogen peroxide. ns tie ferric “"droxide preciwitst e settlim it adsorbs 0th r metallic i *urities and carries them out of Solution. me Solution is th;n filtered 0.6 the In adjusted. The pH is o'di mily -~i¢od by affine nicitl cer- \. ( bonute to the solution, and the use of heat aids in 4recipit3tinfi tie iron. This trestm nt has been found by Anderson (564} to reduce he zinc concentration from 1 gm./l. to 0.0 253./l. biesner (6;5} found that zinc was not a_3 recioblv removed from nickel sulfite solutions until a pH of 6.4 nus reached, usinr arnonium or sodium hfdroxide to raise the pH. At a yfi of 6.8 and by heating the Solution at 10000 for 3 hours, the zinc was conyletely removef. st this pk, however, considerable nickel was also precipitated. When the solution was buffer ed the rcatment at a pH of 6.0 left about 500 mg./l. of zinc. Vicsner's investigations were made in the absence of iron as an im- purity, so it is nit certain what effect iron.precipitsting at the sane tine would hive under these conditions. In most cases the drastic Lis— comb method is not neces rr to remOVe zinc. A tygicel procedure in precipitatins zinc has been outlined by Stocker (617}. This consists of heating the bath to léOOF., agitating the bath, and then rlising the ;n to 5.8 b addinh freshly prec H3 aiteted nickel Oarsonatt as a slurry, slowly’with much stirrine, to the solution. About 2 to 4 - 7g - pounds of nickel earhonate per 100 gallons of solution is normally required. .A slurrfi of lime is then added slowly'with vi orous stir- ring until the 1H ap;roaches 6.0 to 6.2, requiring about i 1b./100g31. of solution. About a half pint of 100 volume hydrogen peroxide is then added per 100 gals. f salution to oxidize the iron to the fer- ric state. The solution is then stirred throoughly, allowed to sett— le aand final v filtered. This treatment is not enlv effective in 9 u u remeviny zinc, but aluminum, iron, trivalent chromium, selenium, and ‘— cadmium. Costello (270}. fiov 1i (51$), omit” (5L7), geisherg (496), (_ and Heslet and hoehl (6&0) have also rrco mended this procedure, or one essentiall, the same. Zinc can also be removed from nickel platine solutions by electro- lysis at a low current density. Hattacotti (484) has given a typi- cal procedure of this t"pe of purific tion. H1. lie-it b-th to 1250-14005‘. 2. Agitate continuously. 2. Fill tank:with as large a Cathode surface as possible. 4. Operate at a current density of 2 arperes/Sqoft, for cepger and lead. 5. Other inpurities operate at 5 amp./sq.ft. 6. Pass 2 ahpere hours/ballon in case of cepper and lead. ass 5 arpere hours/hallon in the case of zinc, etc." Weisberg (496), (582), Anderson (264), and Diggin (664) have also recommended low current density electrolysis as a good method for re- nwving zinc. This latter method s heconfing more popvlar because it adagts itself better to contivuous filtration methods. SUSPHDE MATTER mmnmmnmmmm' 8“- posdod latter is nickel baths has long been a source of trouble. By «spudod latter is Icant particles of all sorts which arc small ‘- ouch. or light nough so that thoy are hold in tho solution for a por- iod of tins. Ion-is hydroxido is probably the greatest single con- stituent of uspondod matter. his procipitato is light and golsti- loss and is ossily uspondod in tho solution, oidsd by oloctrical and thorlcl carrots. no torn, "suspended utter“. is gosorslly consi- dorcd to oxcludo colloidal partiolos, which sro particles of such small siso that thou can not to rolovod by on: normal filtration locus. no cflocts of oolloidsl psrticlos cro similar to those cusod by ssopondod utter. but then arc slso msny offocts so dittorost that tho: till to discussed soparatoly. Bancroft (d) was ass of tho first to rocogsiu thst oxides, hydroxidos. sud other‘ossis sclts could have s protoud oftoct on nickel doposits. Blsssott (33) slso recog- nisod thot rough deposits could to found shot: sediment sottlod on (tho work. Ensclcsn (87) nods s similar obsorutios. ad sisoo torrio hydroxido was tho principsl kind of suspsndod matter. ho proposod mak- ing tho solution moro soid. Box-rows (46). on tho other hood, sugges- tod adding citric scid to provost tho function or torric hydroxido. sod Doric ocid to provost ‘sosio nickel colts from forming. Watts (57), hompsos (71), and Wsttors (78) slso pointed out that slilos and sus- pndod lotto: woro s some for rough and oxfolistod deposits. ‘11 1927 sunbeam (no). (855) nose-ted thst high purity nickel nodes 1.. used to provut tho formation of slsdgo and floating partiolos. Hotshoon -30.. also found that in some cases finely divided particles of metal were mechanically carried over from me anodes and deposited, causing rough deposits. Upthegrove and Baker (“7) wadertook a photomicro- graphic study of rough or nodulised nickel deposits, ad found them to be due to suspended particles which had settled on the work and had been bridged by the deposit. Watts (348). Thomas and Blu- (210), (Ill). Voss (191). Laban (401). Geogrove- (869). Oynboliste (410), (441). and nethersall and Hammond (480) , came forward with en. I11:- gestion that suspended particles were also a primary source of pitted and porous deposits. Ballay (341) showed that baths of a pH of 7 to 9 were unsatisfactory die to the formation of hydroxides and basic salts. he also found that boric acid caused a premature precipita- tion of hydroxides, and advocated the addition of citric. lactic or clycollic acid as a preventative of precipitation. Hothorsall (352) felt that the basic latter in the cathode solution layer was the con- trolling factor in the properties of nickel deposits. Bomanoff (858) also showed that the inclusion of basic particles in the deposit cou- sod hard deposits, ad Lonarchands and chiesco (384) shoved that ni- ckel hydroxide also deposits with nickel. Liobrich (385.) and Man-- chton (8“) also pointed out that the cathode solution layer becomes alkaline during electrolysis, and that the basic salts which form these cause hardness, and may alter the normal crystal growth and or- ientation. lisro recently articles have been written by Ooscrove (we) , . Yosdviahmskii and Hakolin (4.34). mun-t. and Balauze («2), Pin- ncr and Borchert (489), Cohlschuttor md members” (‘21), Wood (545). and Wornick (584) inch repeat the observations already made, that responded particles give rise to rough, porous, pitted. and even lus- ~81- trous deposits. names (638) has also pointed out that another source of aspadcd latter is fatty material vhich my set into the bath from contaminated work. Porter and award (205) have also pointed out that carbon particles from nickel anodes may be another type of suspended particle, and may lead to rough deposits. Planer and Borohert (489) have also found that as such as 0.04% of loose nickel from anodes ea case rough deposits. . 2h. W at. W hits: from mm mm W3 1h. sin of the particles of suspended tutorial generally found in o ai- ckel plating solution is large enough to allow their removal by fil- tration. I the first type of filtration was simply carried out by fil- tering through cloth, but as time went on, better methods and mater- ials were developed to improve the effectiveness of filtrat ion ad to speed up the process. The use of filter aids and activated car- bon has advanced filtration techniques many-fold. The filters used for purifying electroplating solutions are generally constructed of stainless steel, bronze, or are rubberlined. Earlier filters were often of iron construction, but iron contamination sometimes resulted. lbst filters consist essentially of a series of herisontal or verti- cal plates which contain filter cloth, which may also be coated with filter aid, activated carbon, and even nickel carbonate. The solu- tion is forced through these plates, and thence into another tank, or into the same tank if continuous filtration is desired. Amber: (478) has given an excellat discussion of the use of filter-aids ad has pointed out that they are used for four definite reasons: First, that they allow a higher filtration rate: second, longereycles -32- are obtained betwoen filter cleaning: third, a variable degree of clarity can be obtained by using different grades of filter aid: fourth, through its use, the life of the filter cloth is attended. I. filter-aid is used to present the filter-cloth, it is mixed with water and passed through the successive cloths, until each is coated with a layer of the filter aid. llast filter-aids are diatomsceous earths. Meyer (485) has written an artidle on the cathode of mixing filter-aids with plating solutions which is very instructive. For a discussion of filter pimps, articles by Weisberg and Green- wald (:62), Pass (390), (425). and Belhe (501) are very instructive. Other articles on the-general subject of filtration and purification which are very good are: Hobbs (48), Shepard (187), Watts (248), La- ban (270), Jeveli (519). Meyer (529), Smith (538), (5:59), Green (556), (599). Werniok and Silman (585), Wynne-Williams (589), (590), some (coo). Stocker (e18). Rankin (can, and Case (553). Green (599) has also issued a note of cation in pointing out that rough nickel deposits ca result from filter-aid and activated car- ben passing into the solution. Weinberg (582) has also pointed out that once activated carbon gets into a solution, it is difficult to ”7.0 -83- ORGAN I 0 SUBSTANCE mmnmwnmmmw 9.1.- 3331 have been one of the most semen of organic substances in ni- ckel plating solutions. boy were first used for keeping iron in sol- ution by fearing a soluble complexit. Barrows “6) was probably the first to make this recommendation. Hathers (81) found, however, that. the addition of citrates increased the amount of iron codepesited with the nickel. Since the «deposition of iron was not considered to be as bad as the effects of sludge in the tank, the addition still re- solved some popularity. Articles were successively written by lose (94), Later (99), Werner (145), Mathers (857), Ballay (34.1), (34.3), Raub (391), Baub and Walter (393). lathers (420). and Krause (552) recommending citrates as an addition for keeping iron in solution. Another popular use of citrates and citric acid was in the electro- plating of zinc and aluminum materials. Weber (74), Nelson (108), rrooter (134). 11.11 (in). Lodin (151). mmpan (212). r... (25:), Werner (.91), (083) ad frat-Ian (899) have found-citrates of value in plating tn... materials. Haring (175) .19. observed that sodium citrate additions greatly increased the throwing power of a nickel solution. Martin (657) found that citrates also decreased the stress usually found in nickel deposits when used in solutions at both low gnd high pH. Another cosmos use of citrates is their buffer action. out» (409), and lloyer (454), have found them to be excellent buff- ers, and Pollack (651) has made a similar observation in regard to citric acid. citrates have also boon noted by Werner (145) to make depos its tougher. ~84:- m are also used in nickel plating solutions. Kersten ad Young (on) used nickel ferIate in depositing nickel—iron alloys. he most common use of formates today is as a constituend ot bright nickel baths. 'oisberg (542),(588), (583) has investigated the use of both nickel and sodium formats in nickel baths. The action of both cospounds is similar, they tend to lake the deposit harder, act as buffers, and make a contribution to the brightness of the bath. to for-ate is usually used along with formaldehydr in the Weisborg baths. Martin (05?) investigated causes of stress in nickel plating solutions ad found that the addition of formats decreased stress in both low and hid: pl! solutions. m have been used as buffers in nickel plating solutions. O'lullivan (cos), Watt. (:10) and sun and Soshkarev (505) have found acetates to be satisfactory buffers. Acetic acid has also been add- ed as a hffer by Cotton (409) and Irause (562) ad Haas (94). Mar- tin fend that as in the ease of formates, acetates decreased the stress in nickel deposits. m have been cannon addition agents to nickel plating solu- tions. lass (153), (133), found Rochelle salts to be a valuable con- stitubnt in black mom solutions, and Hathsrs, Webb, and 3.1m: (854.) have used Rochelle salts with ethanolamine in alkaline plating baths for nickeland cobalt. Along with citrates, tartrates have boa used to keep iron soluble in solution. Baub (391) found that this addition prevented the accumulation of free iron. m are similar in action 0 the compeads already mentioned, although their use has been more reoat. Nichols (354) has found -35- that lactates retard the d9 ocition of nickel on sine by inmersion, ad 'that they do not produce the yellow colored deposits which cit- rates tad to form. WALL”. particularly the acids of the salts already mention- ed have frequmtly been added to nickel plating solutions. Haas (94) added basoie, tartaric, acetic, and succinic acids to nickel plating solutions and found that they gave large polarisation values, so were therefore unsuitable addition agents. Citric acid was found to give satisfactory deposits. Ballay (3a), (“3), investigated glycolio, lactic, and citric acids for prevating the precipitation of iron and found all to be effective, particularly citric aid. llalic and tar- taric acid were hand to be without action. Banb (391), however, found that citric and tartaric acid additions yielded good deposits, but lactic acid caused poor deposits. Xrause (562) has found that acetic, citric, and tartaric acids were all effective in preventing the precipitation of iron, manganese, and chromium hydroxides. Oct- ton (409) investigated acetic, citric, lactic, succinio, formic, and tartaricvacids as buffers, and 1’01th “51) found tartaric, glyex- alic, and glycolie acids to be excellent buffers, and that baths con- taining these three acids could be used to plate light metals. Poll- ask found the deposits frn ouch baths to be superior, in appearance ad adherence, to these from baths containing citric acid. hrmio acid has been used primarily as a brightener, and as such has been in- vestigated by Ioicberg (see) and mm and Wittum (572). one latter authors found that formic acid caused a weak increase in brightness, but had no effect on the mechanical properties of the deposit. In nickel-cobalt ulntions fornic acid was found to increase the reflec- tivity of the deposit markedly. Bulb and Wittum (572 ) also inves- tigated pyroaeemic and lcvulinic acids, but found them to have little effect on either the brightness or physical preperties of the deposit. nasunov and Bohl'c'ttcr (“5) have pointed out an important fact ro- gardinz the use of these compounds which form soluble complexes in solution. and that is that undeconposed complexes enter into the dc- pesit lattices, and may therefore affect the prsical properties of the deposit. tum: (cos) investigated organic aiditions agents, and found an: the addition of bmsaylacetie, diphenylaeetic, phenylaceturic, hel- scneoulforrie, toluie, and tropic acids produced unsatisfactory re- sults as brightaing agate. 'hm Rant and Wittum (‘78) investigated aromatic acids they found that bmsoic ad salicylic acids had no effect on the brightness of nickel. Leetylsalicylic acid, however, produced milky shite to brilliant deposits in concentrations from 0.1 to 0.2 g./l., while other acids vhich they investigated, even in tinfold concentration produced no effects. no mechanical proper- tiol of deposits obtained from solutions containing acetylsalicylic acid were coed. Phthalie acid and phenolphthalein produced no no- ticeable effect. Ihn tannin was added to a nickel bath, it was only slightly soluble and no distinct effects were observed for the small quantities which were soluble. W have been added to nickel baths, but even in large amounts they have 11m. effect on 11.1.1 deposition. mm and Wittum (In) -87- havo made this observation in regard to methyl and ethyl alcohols. M a bath was saturated with iso-amyl alcohol, the deposits were milky in color, but the physical properties were altered only slight- ly. Of the alcohols, the tri-hydroxy alcohol, glycerin has been the lost frequent addition to nickel plating solutions. In 1921 Watts (144) added a mixture of fluoborate and glycerin to a nickel bath and noted that the resulting deposit was remarkably smooth. Shepard (186), (809) used a lead ad glycerin combination as a brightaer, and found that hoth the lead acetate and the glycerin contributed to the bright- ness of the deposit. Schneh (860), ad Werner (291) have found gly- cerin to be a valuable addition to nickel baths‘used for plating alanine. lathers and Guest (555) have found test glycerin reduced to throwing power of a nickel plating solution wha operated at ghih current densities. Bab ad Wittum (578) added 50 ec./1. of glycerin to nickel plating alutions ad found that a nah brigitcr but milky deposit was formed. Deposits with a thickness of shout 0.00024 in. had a reflectivity almost as great as buffed nickel. the deposits had, however, a golden coloration, and as the thickness increased, the coatings beoallo are matte, and less reflective. When the glycerin was added in amount exceeding 50 cc./1. the deposits became non-uni- formly cloudy, and matte. Bab ad Witte- also noted that hydroga has a greater tendacy to dhcre to the cathodes in solntions contain- ing glycerin. In small concentrations glycerin did not produce any effects on the aspssit. Stout (432) has pointed out that polyhydrie alcohols, particularly the glycols, are being increasingly used as nickel brightcaers. W “I, m have been added to nickel baths, and of these hrnldehde has been the most investigated. Weisberg (548) has fead for-aldehyde to contribute very definitely to the bright- ness of nickel-cobalt plating solutions. Nickel deposits can be pro- duced with this addition which produce reflectivities closely approa- ching buffed nickel deposit». Banb ad Wittum (572) have found that wha for-aldehyde is used as a brightener, the brightness is depau dent only on the surface condition of the base plate. In thick dc- posits, even a matte base plate will result in brilliant deposits. The deposits from solutions containing formaldehyde show very defini- te layering. Photonierogrmhs illustrating this layering phenomenon in fomaldehyde-oontaining baths and other bright nickel baths are to be found in papers by Rab and Wittun (I72) and by Young (592). nanb ad 'ittum (578) also observed tint the brilliant deposits from solutions containing formaldehydr tended to be brittle, and that crap cks night form on bading, but only in spots subjected to the great- est defcrsntion, ad exfoliation parallel to layering is not found. Irittlslcssowas found b increase with increase in thickness of die deposit, but no noticeable decrease in adhesion was found. Appar- atly cos-tin organic natcrials are codepesited with nickel in solut- ions containing formaldehyde, sinec an unpleasat odor is noticed wha the dQesit is heated. Rab and Wittum attribute this pehnonaon to the polymerisation of formaldehyde by which colloidal latter fonns. 'i'hey also noted that formaldelwde increased the polarisation decided- ly hr nickel deposition. In still baths at low currat dasities, the prcsace of formaldehyde was found to lead to brittle and streaked deposits. \Wha the solution was gitated, hcwaver, the polarisation at hidisr current dastties was has than in still solutions. Baub -89- and Iitm (57s) felt that the solution they inastigated had its best properties with a formaldehyde content of from 1 to 14 os./gal. fhose authors also investigated acetaldehyde and propylaldehyde additions. With acetaldehyde the effect was similar to formaldehyde, only strong- er. !he lochanicsl properties of the deposit were impaired however, d it was under high tasion, and covered with hair-like cracks. prepyladehvde in amounts up to 50 cc. per liter had no effect on the brightness of the do osit, and an increase in hardness and a decrease in ductility occurred. The addition of acetone at 10cc. /1. resulted in milky brigit to bright deposits, but the deposits tended to ex- foliate in scales, even in the bath. heavier coatings from acetone containing solutions were gray to black gray. Liniok (605) added bensylasctone to a ndckol bath, but an unsatisfactory deposit resulted. W have been added to nickel plating baths, primarily to find out if they have brightening properties. deletin has been one of the bra cannon of these additions. It is probably true that the dfcsts of felatin glue, etc. Are due primarily to their colloi- dal properties. and as such they have been widely studied addition agents to nickel baths. In 1911. Proctor (as) rescue-idea the addition of a small amount ofgelatine or transpaer white glue to produce bright nickel deposits. providing the deposit was not to be very thick. vniiieunier (148) then investigated the effect gelatin had on the con- traction of nickel depps its. and found the effect to decrease the con- traction. lrglich (176). and lrglich aid Clark (200) also investiga- ted gelatin dditions and proposed that the effect of gelatin at the cathode surface was to acumlate and prevent circulation of the elec- trolyte. or actually to dilute the electrolyte at the cathode surface. In high 1! nickel solutions Prolich found carbon in the dqaosits, dish is in disagreemt with the expected nigrat ion of gelatin par- ticles to the anode at a pH greater than 4.7. Ballay (344) found bright deposits to result after the addition of gelatin, and reason- ed that solutions which contained colloids which pro-exist in the bath give more uniform results over a wider plating range than those which form in the cathode sono- Acoording to an anonymous German author (“5) gelatine is an effective brightaier in concentrations as low as 2.5 .../1. Lewis (203) found that the addition of gelatin to a sin- gle nickel salt bath which exhibited normal throwing power of 32% was reduced to 17%, and the cathode efficiency was also reduced to 88.5%. Oahour (407) found that gelatine increased the hardness of nickel d1: esits up to a certain concatraticn, and then began to de- crease it. nethersall and Garden (479), and llattacetti (527) have also found .clatin to yield brittle and hard deposits. Fischer (362) found. that organic oompomds like gelatin first showed signs of con- centration polarization and high resistaico at the cathode at a con- sutration of lOg./l. or above. A core reeut theory of the action of gelatin has been proposed by Glasunov aid Dreschor (414) who be- lieve that to addition of gelatin and other colloidal tutorials causes a reduction in the numerical value of the crystallisation vel- ocity. which is not dependent on a decrease in viscosity. Xoohanov- skii (450) has proposed that nickel ions become inactivated by Inla- ones. of 1y0philic colloids like gelatin, and that the instigation is greater the more lyophilic the colloid is. BS has not tried to adapt this theory to the effect of gelatin in nickel plating solutions, but it my be a plausible theory. Glue exhibits effects similar to gelatin when presut in nickel plating solutions. Osnndng (294), Liscoai (380 )0 lothersall and Garden! (447), Shcherbakov, Loshkarev, and rectum (535), and Matte. cotti (527) have pointed out that glue, vanish, resin, and sap from wood can severely contaminate a nickel bath. According to Liscoub (350), if glue is present the bath will fnth, ad the dqcsits are bright, streaked, and brittle. Gelatin M glue are really proteins, and other proteins such as albumin, casein, and peptene act quite similarly. Baub and Wittun (572) have pointed out that all protein substances do not eat alike. Casein, inch is only soluble in small quantities was found to be very detri- mtal to nickel solutions. Ihoy observed that scum was formed on cur-foo of the cathode, ad as a result the base metal was only in- completely covered. and the adherence was very poor. They also found that the cathode potutial fluctuated quite strongly after casein was ddcd, and found that a usable cathode potmtial-current dens ity curve was impossible to mks. hub and Wittun also recorded similar effects for albumin, peptone and glue. Additions as small as 0.01- 0.05 g./l. were formed however, to allow the dqcsition of plates of high spectral reflectivity, which approached that of buffed nickel. he ductility was found to be very poor in these doosits, and on bonding the spedinns cracked in spots of greatest tm ion. The brillinoo of the deposit was found to increase with the protein con- ccntraticn .d with the thicknessof the deposit. At higher protein content they observed the deposits to be discolored. lab and Vittun also observed that with small additions of protein to an agitated bath, a strong increase in cathode potutial was observed, but in a still -92.. bath, only a small increase was observed. They exppained this phon- omenon as being the to the fact that with a small protein concentra- tion in a still bath, the protein at thecathode is quickly depleted, but whu the bath is agitated, the protein at the cathode layer is being continuously replenished. When the temperature was increased to 5500. in a bath containing peptone, the brittleness was only sli- ghtly reduced. landi (304) has investigated the effect of albumin on the deposition potentials of mettle, and Dolley (500), (344) has discussed the brightening action of gelatin, starch, dextrin, gum ' orabic, agar agar, egg albumin and casein. Robinson (8'?) reported in 1916 that l ore/gal- of yellow dextrin made an end lent brigh- toncr solution. This solution was ad ed to the bath as one gluid os./300 gallons of solution. Gun arabic and gum tragacsnth have be. added as brightmers to nickel plating solutions by Hills (100), Underwood (265), and Bisolove (462). Biscleve found that an excess of gun arabic caused dark streaky deposits, aid where the streaks occurred, little or no nickel was found. fire other carbohvdrates which have been investigated as bri- flltuing seats in nickel plating solutions. The use of glucose has been mentioned by Blum (112). and mnitel and sucrose by sols-hi and Singh (615). Stout (432) has also listed sucrose, corn sugar, and melt syrup as brightaors. He also found that glucose added in con- centrations of 1% to z os./ga1. yielded improved nickel deposits over those from ordinary gray-nickel baths. Baub ad Iittum (572) inves- tigated dextrose, lactose, and maltose additions and in the case of dextrose found that the deposits were only milky briglt at boot. Lac- tose in concci trations of d os./gal. had little influence on the reflec- -95.. tivity of the coatings, and above 4 sin/gal. of lactose the coatings again became matte. Neither dextrose nor lactose were found to mat- crially affect the mechanical properties of the deposit in concen- trations between 2.5 and 5.4 oz./gal. Maltese additions resulted in streahd deposits at a concentration of 0.67 os./gale which tended ' to be brilliant at times. The mohanical properties of the deposit were poorer thatn those from solutions containing dextrose. Methyl cellulose, mother carbohydrate, was also investigated by Baub and Within aid at a concentration of 0.02 os./gal. the dqmsits were not affected. !ho potntial for nickel deposition was displaced, however, about 20 to 30 nill ivolts toward the non-noble potential. m m min, have been systanatically investigated by flab ad Iittum (872) to determine their effects in nickel plating soluticns- ternanido was found to increase the brightness of deposits, hit thcir nochenieal properties were seriously impaired. it c concen- tration of 0.067 os./gal. of formamidc the deposits were non-uniform, matte bright to brilliant deposits, ilich showed good adhesion and ductility on b-ding, aha the coatings were not very thick. in a solution containing 0.13 oz. /gal. of formamide, the deposits became exfoliated in the solution as soon as their thickness exceeded 0.00016 inches. Urea additions aoeutuatod pitting in a nickel solution, due to increased adhesion of hydrogal bubbles to the cathode. filo bright- ness of the deposit was not increased by urea additions, aid the pol- arisation of nickel deposition was increased. “ethyl urea additions yielded matte, hard, and brittle deposits. Uric acid alditions in con- cntrations of 0.005 cs./gal. cased marked increase in the brightness -94- cf the deposit. no adhesion of the deposit was good, but due to in- ternal stress, the ductility was poor. Ehiuor coatings were fond to be fall of fine cracks. When the eonoutration of uric acid was inn-cased to 0.13 os./gel. the deposits were brilliant, but exfolia- ted in the solution. As the uric acid concentration increased, the count of hydrogen evolution increased, oven at low curmt densities. Caffeine which is a conlpcund derived from uric acid was found to mark- edly disturb nickel deposition even in oonoutrations of 0.001 os./ga1. semi-carbusido, another urea derivative, produced less mrked ef- fects than urea at a concentration of 0.005 os./gal. as regards spec- tral reflectivity. !he mechanical properties were but little influ- clccd. As more semi-carbuidc was added, the deposit gain became ntte. lthyl carbonate, or urethone, had a powerful brightening of- foot and with additions of 0.025 ou/gsl. brilliant deposits were ob- tained after N minutes of plating. Polarisation and hardness were also increased by urethane additions. Oxamide additions were found to cause a strong evolution of hydrogen, and this evolution increa- sod with amide coneentratiu and curmt dmsity- than only low currat densities were permissible with this addition, and the dope- sit produced showed only a weak increase in reflectivity but no mar- ked change in mechanical prOpertios. At high current daisities the deposit was dark and spongy. Glyoocall was tested as an ample of an amino acid and at a concentration of 0.3 g./l. there was no notice- able effect on the deposit. Guanidine sulfate was also found to pro- duce spongy and pulverant deposits, aid was harmful in all concentra- tions. hexamcthylenetetrauine was apparently similar in its effects to formaldehyde. Since it is formed by the combination of formalde- hyde with amonia, Daub and Wittum reasoned that the hexamathylenc- tetranine broke don into these compounds in the bath. Another amino acid, phcylalanine, was found by Linick (605) to produce m excell- ent brightening effect when added to nickel solutions. In 1920 Ali- vcrti (119) added strychnine to a nickel bath and found that it de- creased the contraction of the deposit. can and sum (57:) also investigated certain aromatic nitrogen coqounds. boy found no apprecialbe effect on increasing bright- ness of nickel dqosits by aromatic amines, but a marked increase in polarisation of nickel deposition was noted. lethyl red, a sulfate- frcc aso dye did not increase brightness, but methylene blue, which contains sulfur, did increase the brightness of the onsits. 0on- catraticns of 0.02 to 0.1 g./1. of methylene blue produced brilliant deposits which closely approached buffed nickel in reflectivity. The deposits were found to be highly stressed however, and brittle, and usually were observed to exfoliate in the fclution. Bacoharin was also found to be a stolen; brightener, and the best results were ob- tained using 0.1 to 0.2 911.. with higher concentrations the bri- llimce began to diminish, with coincident ippairmsnt of mochmical properties. W mm “mm“. were also fund by Raub nd 'ittum (878) to have marked effects on nickel deposition. Ithyl mer- eaptsn and allyl custard oil were dded, but their obnoxious odors lilitcd their use. In concentrations up to 6.5 coc./1. of ethyl mor- ceptn, and up to 10 c-c./l. of allyl mistard oil, the dchit was distinctly brightened, and no loss in mechanical properties was no- -95.. ticed. hieurea was found to be a strong brightening agent, ad the deposits produced exceeded oval those from formaldehyde-containing “linens. An addition of only 0.15 9/1. was sufficient to produce deposits as reflective as buffed nickel. 'i‘he deposits became increas- ingly brilliant with thickness, but the cohesion of thick deposits was weak. Whm the deposits were bent, the nickel not only cracked at the bonds, but exfoliated in thin sheets. When deposits from thiourea-oontaining bzths were heated small bubbles of gas qpeared all over the surface which reacted distinctly alkaline, therefore, indicating an amine. When the deposit was dissolved in hydrochloric acid, the lac c‘lved contained hydrogen sulfide and traces of a gas with ml odor like methyl sulfide which was not absorbed by alkaline er iodide solutions. Oxidation and polymerisation products of thie- ava were also noted to form sl imy and partly fibrous mtcrial on the anodes. rho cathode potential-current dusity curve was strongly displaced to the negative side by thiourea additions. At high cur- rut dusities, the potential measurements were uncertain and strong fluctuations occurred wish led gradually to lower potential values. Oystine, a sulfur bearing amino acid had no distinct effect on nickel deposition at a concentration of 0.15 g./1. Procter (dd) mentioned in 1915 that ethyl sulfate was a good bri- ghtencr, and model (as) recommended the use of sodium ethyl sulfate. mu, m constitute a great moi-ity of the brighteners added to smdern bright nickel baths. Decides being added as bright- uers, certain of these acids and their salts have been used as wet- ting agents. mardt (37:) in 19:55 recomended sodium phenolsulfonate as a wetting agent. Blcunt (474” found that an alkyl aromatic sulfcn- ate cased a whiter, brighter plate to firm, which was also softer, fineigrained, and easier to buff. i‘he sulfonate also prevented the adherence of hydrogen bubbles to the cathode. 9.00 high a concentra- tion of this wetting was formed, however, to case pitting and bare spots, Stocker (540) has also pointed out that wetting agents as a isle main the plate more susceptible to grease contamination. since 1938 some excellent articles have been written on the use of wetting agate in nickel plating solutions in particular, and all plating sol- utions in general. some of these are by: he Newark Branch of the American llcctroplater’c Bocity (487) Young (546), l{artshorn (558), senartsw (57d),0rowe (594), Davis, Wolfe, and Irene. (595), Planner (535), nerarlane (560), and Silman (tel). ‘ ’ lteut (432) mentioned in 1935 that aromatic sulfonic acid deri- vatives were finding increasing use as brighteners in nickel solu- tions. dpringer (464) made the same observation a year later and Ecthersall and Gardem (516) in 1939 investigated the structure and properties of nickel deposited from baths containing 5 g./1. of ni- ckel naphthalene trisulfonate. Another bath these authors investi- gated nas one containing 30 g. /l. of so“ ice-propyl naphthalme sulfonat'e. Young (592) in his study of bright nickel processes men- tioned the use of naphthalene tri-sulfonic acids, culfonated clco resin, ad bensene or o-toluene sulfonamide. nearer (606) also found that sulfonated bensene or naphthaline derivatives made deposits mre ductile. Hmdrioks (627) and. a similar observation, pointing out that when brightncrs-such as sinc, cadmium or the poly aryl me- thmle dyes are used alone, a hard brittle nickel deposit is obtained. -98- if an aryl sulfonic is used in conjunction with these brighteners a bright and ductile deposit is obtained. Pinner, Bederborg, ad Baker (609) listed polysulfonic acids, aryl sulfonamides, and aryl sulfoni- mides ac brightmers in nickel baths, and listed other aryl sulfonic acids as grain-refiners, but not brighteners. These latter sulfonic acids permit, however, larger amounts of brighteners such as the salts of cadmium and sine, formates, aldehydes, ketones, md amino polyaryl methanol to be used and even enhance their action. stepanov and Ly- ashchako (616) also found sulfonated naphthalenes to be valuable brightaers, and Pollack (636) made the same Judgement consuming sod. ium phenolsulfaonat. Linick (605) found no brightening action from the additions of potassium phenyl sulfonate, ‘=ens.esulforic acid, and sodium baseue culfonate. Bach and Wittum (5'?!) have made the most cosplote and estasive investigation of aromtic and heterecyclic sulfonic acids, and their findings have yielded valuable information. Although they found few gueralities regarding these cospounds, they did find that deposits from solutions containing sulfonic acids always evolved hydrogen sul- fide gas when dissolved in hydrochloric acid. they also found that the amount of sulfur codepesited was dependenton the current density and the type of sulfonic acid. he sulfide form of sulfur which was detected in the deposits was found to be from the decomposition of the sulfonic acids, and the brightnessof the deposit was independent of the sulfur concentration. The nickel being deposited was also found to catalyse the break-down of these compounds and when the bath was operated for some time the odor of sulfonic acid-free coupounds could be detected in the aromtic sulfonic acids were all found to displace potatial-currcnt density curves in a negative direction. Potassium phenolsulfonate was investigated and found to be ineffec- tive in concentrations up to 8.6 g./l., as a brightener, and the de- posits were brittle and covered with fine cracks. Alpha and beta naphthalene sulfonic acids were found to be powerful brighteners. The alpha acid as the more offective of the two, but both produced deposits approaching buffed nickel in reflectivity. Mechanical pro- perties of deposit were not impaired as long as the concentration of the naphthalene sulfonic acids was kept low. Concentrations of 0.8 to 0.6 g. /1. were satisfactcry,'while higher concentrations led to exfoliated deposits. Naohthaleneflfifi, sodium trisulfonate was in- vestigated as a typical tri-sulfonate, but the deposits were millq bright at best. filo adhesion and ductility of the deposit were only slightly diminished. Anthracene-l sulfonic acid in the small concu- tration which was soluble in the bath and menanthrene 3-su1fonio acid at a concentration of d g./1. were uneffective. no l- and 2.- monosulfonic acids of dibutylnaphthalene produced excessive trubidity in the bath at a concentration of 3 g. /1. Bright deposits were, however, obtained, which were poorly dherat, and poorly ductile. lhm the concentration wasreduced to 2 go/l. the de- gree of brightness remained, nd the moohnical properties of the de- posit were generally better. Luother slightly solutlb compound, ben- syl napthslene sulfonate, was also tried, but yielded only milky bri- ght deposits. 0f several unknown poly-substituted napthalene sulfon- ic acids tried, only one was satisfactory as a brightener. his com- -100- pound was a strong brightaier even in concentrations of 0.1 g./1., but it greatly inereased the polarization of nickel deposition. fhe addit ion of 0.1 to 0.5 g./l. of 2 naphthol-é-sodium sulfohate, S-nsphthcl sodium di sulfonate, 3-naphtho1-3,6,8-sodium trisulfonate, and z-naphthcl 3,6,8-sodium trisulfonate produced deposits which were very nearly as bright as buffed nickel. The deposits however, were internally stressed, were covered with hair-like cracks, and were poorly adheer to the base metal. Bad cases of pitting were also observed through the use of these compounds. lhe sdum salts of anthraquinone and dioxyanthraquinone sulfonic acid were found by Bach and Wittum to be strong depolarisers, and therefore led to dark and poorly adherent deposits. The 84,2-6, 8-7, and 1-4, naphtholamine sulfonic acids were added in com entra- ticns up to 2 ¢./1., but the increase in brightness inch they pro- dused was slight in comparison with that produced by the naphthalene and naphthol sulfonic acids. The hardness was mrkedly increased, but the ductility was only slightly decreased. 2-amine-l naphthal- 7 sulfonic acid, lothyl orange, and congo red were found to be un- satisfactory brighteners. Quinoline-B-sulfonie acid in eonsentrs- tiond of from 1 to 6 g. /1. gave matly bright to brilliant coatings with fairly good mechanical prOperties. men the concentration em- ceeded C lg/l. the deposits became dull and discolored. and the me- shmical properties are also impaired. lieterocyclic Mwere also investigated by Baub and Wittum (572), particularly fuffurol, pyridine, crthohydrosyquinoline, and cuisine. mural was found to increase the brilliance of deposits -101 - quite strongly. In concentrations between 0.2 and 0.6 g./1. the reflectiveties of deposits were only about 10% lower than buffed nickel, ad the brightness was independmt of thickness. A few drops of pyridine per liter resulted in dose of adhesion of the de- posit te the base metal, and the coating was not noticeably bright- ened. Orthohydrosyquinoline was even more effective as a bright- ener than furfurel, and as long as the concatration was not very high, the properties of the deposit were not appreciably lessened. the optimin concntration of saturated crthohydrczyperinoline solu- tion was about 30 cc./liter of nickel solution. innine acted as a depolarisor, and at higier concentrations prevented nickel deposition. Des ides the organic materials mentioned there are several other organics which have beai discussed. One of these is living organic matter. Ollard (335) recorded that three types of micro-organisms have been found in nickel baths, but their effects are not Brown. Ollard (219) also found that WW, a micro-organism, has been found growing in nickel plating solutions. Barley (371) has also pointed out that a bath my develop surface sold by fermentation of organic latter from water or brightuers in the bath. Stopping- cff materials have been another source of organic contamination in nickel baths, as pointed out by Macnanghton and Hothorsall (281) and Iaite (666). Other sources of organic contamination mentioned by Iaite are filter clotters, mode bags, and tank linings. Orgmic materials, regardless of their iwpe have long been known to cause ill effects in electroplating solutions. The effects attri- buted to organic contamination were: brittleness, hardness, pitting, pooling, and dark or streaked deposits. Besides the articles mentioned -102 - previously. articles by the following authors also mentioned these effects: nether- (139), Madam (182), Porter and Sward (s05), Ollard (sis). ampere (220). Darlay (346), Snelling (360), Shcherbakcv, Loch- karev, and Loshkarev (576), Stacker (618), Meyer (529). Mattacotti (627), case (665), Diggin (665), Waite (666), and others. IMMKWWMMWW3 more have been several methods suggested for remOVing organic con- tamination from nickel plating solutions, and all of them are more or less effective. Probably the first method suggested was the ch- lorination method of laden (182). In this method chlorine gas is bubbled through the solution to destroy the organic matter. lbre recently Bother-sell (352) reconmaded the chlorine treatment again followed by the addition of Kieselgahr and filtration. This type of treatment is obviously a difficult one to perform since chlorine is a poisonous gas. A second method which has received more popularity is the hydrcgai peroxide oxidation method. Hydrogen peroxide is a effective oxidising agent and will destroy most organic matter. this method was suggested in 1925 and 1926 by Porter and award (205) and Dobbs (215), although the method was evidmtly in use before this tine. 'A typical procedure hr hydrogen peroxide treatment for relev- al of organic contamination has been given by Mattaeetti (dad). his consists of (1) Heating the bath to iso°r. (2) Adding while stirring f gal. to 2 gal. of lOO wlume hydrogen peroxide. The variation in amount allows for the oxtmt of organic contamination. (I) Allowing the solution to stand warm overnight with agitation. If the throwing power of ihe bath is decreased, Iattaeotti reccmends that the tem- peraturo be raised to expel any excess peroxide. -103 - Another oxidation method which has been used to some extent is the potassium permanganate treatment. this treatmtne was suggested by Shepard (220) in 1925. Shepard preferred potassium permanganate to hydrogen peroxide since the peroxide taided to flocculate colloi- (”a1 ferric hydroxide. Hothersall and Gardam (4.47), and Thomas (638) have also found potassium permanganate to be very effective. more is one factor in favor of the use of permanganate, namely as long as orgmiic nutter remains in the bath, the permanganate will be decol- erised. As soon as the organic matter is destroyed, the purple per- Imganato will turn to brown nunganeso dioxide, thereby indicating when the reaction is complete. The effects of manganese are not well he. in nickel plating slutions, but one argumt against the use of permanganate is that it adds manganese as a metallic conta- minant to the bath. A method of treating contami ated bath with po- tassium permanganate has been given by We isberg (541) who swgestcd that the pH of the olution be brought to a value of 2, heated and than 3 lbs. of potassium permanganate per 1000 liters of solution be added. The solution is then allowed to stand to allow the per- manganate to roast, and then allowed to cool. The pl is the raised by the addition of nickel carbonate until the excess pernmnganato precipitates out as manganese dioxide. The precipitate is than fil- tered off, and the pH adjusted. Another method was enacted by Darlay (571) inch appears to be unique. lo smested that organic nutter be removed by filtering the bath and then treating it with salicylic acid or mercuric chloride. Probably the smst widely used effective method for the removal of -104 orgsnic matter is by file use activated carbon. Articles by Helbig (m), (605) have fully descrubed the use of activated carbon. This material is highly porous, and possesses extr-nely large surface area. the particles of this material exhibit tremendous adsorptive powers hr most organic materials found in nickel plating baths. Hol- big recommended that the carbon be presented onto the filter by the slurry technique, using sulficient carbon to fill about three-quart- ers of the available filter cake space. He also found filter-aids as effective partners to activated carbon in aiding filtration both in speed and effieimcy. The circulation of solution through the filter was recomended to not exceed 25 gals./hour for each square foot of effective filter area. Activated carbon Ins also been added directly to the contaminated solution and thoroughly agitated. Bah a procedure has been recomended by nettaoetti (484), smith (538), Stocker (617), (618) as being more effective, providing stops are taken to effect cocmletc removal of carbon from this solution. 130 do this Stacker (017) recomonded that a separate treating tank be used, so that these would be no chance of carbon remaining in the sol- ution. thn a solution is treated in this sanner it is usually no- cessary to precast the filter with filter aid to make certain that the carbon does not pass through the filter. Apparmtly pro-coating the filter with carbon is the preferable method. It may reguire a longer purification period than the direct sulution addition method, but it eliminates danger from carbon contamination. An article by nelbig (608) very completely covers the use of this material in pur- ifying plating solutions, and is recommded to anyone for removing organic contamination in nickel baths. -105- Other cmsellent articles on the activated carbon method of puri- fication are by: Joveli (519), llattacotti (527). Here:- (529), Smith (528), 'oisberg (541), thherbakov, Loshkarev, and Loshkarev (576), Weisberg (582), gtocker (617), (618), Case (663), and Diggin (664). A. method of removing organic matter has been proposed by Weinberg (468) which is based on high ourer das ity electrolysis. Not all organic matter can be removed in this manner, but it is effective on some types of contamination. The organic material which are destroy- ed have not been well-classified. Mattasotti (484) pointed out that the less of metal by high-current density electrolysis could be less- ened by lowering the pl to 2. ‘i'he electrolysis is carried out between 2 and 150 amps./sq.ft. depending on the type and degree of outamina- tion. Due to the uncertainty as to whether the contamination will be removed, ad the cost due to less of nickel, this method has not been Ctnsively adopted. In general the carbon treatment is probably the best method where the quipment is available. Continuous purification is coming into Dre extensive use, and activated carbon also has the advantage of luding itself to such a practice. Diggin (664) has pointed out that in cases where activated carbon does not effectively remove organic ccntmination, treatment with activated clay is often effective. The peroxide method does have an advutage in that the procedure also re- moves iron and small amounts of other metallic impurities along with it. In this connection, the purification method of Liscofl (330) should also be mentioned since the large amount of ferric hydroxide which is formed by this method also removes some organic contamination. -106- mummmmmms colloi- dal latter of specific compositions have already been discussed. How- ever, a discussion of the general effects of colloids should be made since they have great bearing on the electrodeposition of metals. the theory of colloid action on electrodeposition has gone through a: interesting develooment, and it is difficult to make a decision on my particular theory since the cathode layer where the fundamental reactions of electrodeposition take place is extremely thin. One of the earlier concepts was that of Betts (5) who felt that any action a colloidal material had on electrodeposition was due solely to some chemical reaction. It is true that most colloidal subetmces have in- dividual properties, but there-are a goat number of effects which ap- pear to be common. this sort of a phenomon would be difficult to sqlain from the concept of Betts. One of the general effects attri- buted to colloids is that they refine grain structures of electrodepo- sits. Dial (112) and Blum and Man (160) recognized this latter fact and attributed the effect of colloids such as glue and gelatin to the increase in vixcosity of the solution, thereby hindering convertion and diffusion, and thus reducing the effective metal ion concentration at the cathode. They also felt that if the colloid migrated to the cathode ad accumulated, it would probably be adsorbed by the deposit, mid thus alter the arrangement of the crystals of the deposit, and their growth. Blum mid Rawdon attributed the specific effects of different colloids to differences in the degree of their adsorption by the de- posited metal. Another early observation was made by Whitcomb (126) who pointed out that colloids could carry electrical charges, mid might therefore mi- -107 - grate to the electrode of Opposite charge from their om. He also felt that colloids tended to preveit the formation of tank sediment. Kohlschutter (150) also made the observation that colloidal absorp- tion film might cause overvoltage. One of the most complete inves- tigations of the role of colloids in electrodeposition was made by and (141), (164) who investigated the following: their colloidal nature and inclusion in the deposited metal: their gold-number and absorption relative to their effectiveness: their action after ad- sorption: microstructure of deposits; equilibrium potential; trans- fer resistance and polarization: over-voltage effects: mechanism producing the final structure of electrolytic metal deposits; the im- portance of colloidal substances accidmtally present or incidentally produced; colloids at the anode: and colloids in applied metal depo- sitiono Solution composition has an effect on the form of electrolytic de- posits, and Hughes (166) has found that the presence of colloids ef- fect the influence of solution composition. Hastinghton and Esther- sall (245) in a discussion on the senses of pitting proposed that cap- illary forces at the cathode caused by colloidal matter be considered as a cause of pittine- Romanoff (287) also studied pitting causes md found that emlsoid colloids caused the mat difficulty in plating, but that electropositive colloids such as colloidal ferric hydroxide were probably those which cause pitting. Imagiton, Gsrdam end Hammand (332) investigated hard, unall- grained deposits and found that they contained basic colloidal matter of a positive charge. Ballay (344), in investigating bright nickel produced by colloidal action, found that the brightness of the deposit was connected with me existence of mineral or organic colloids in the cathode film. In ordinary baths it is possible to produce a bri- ght deposit in a current density range Just prior to the formation of burnt deposits. Ballay attributed this to colloidal hydroxide in the cathode film which is formed at the h1g1 pH of the cathode film cared by high current density. He also found that nickel plating solutions which contained colloids wish pro-existed in the bath as organic colloids, gave more uniform results over a wide plating ran- ge, than those baths in which colloids were formed in the cathode sone. Iohlschutter (382) has also pointed out that the probably cause of "somatoid" elements of strucuire in electrodeposits is of colloidal origin. llacnaughton (386) followed up his earlier paper with his coworkers with one in which he stated that the hardness of nickel deposits was due to the difference in crystal structure cau- sed by interference to normal growth caused by inclusion of basic ni- ckel coupeunds, in colloidal state, which are produced at the cathode face as a. result of local reduction of acidity. The quantity of col- loidal utter thus formed, determined the properties of the deposit. Another effect attributed to colloids was pointed out by Meyer (388) (‘22) mo found that hydrophilio colloids were a cause of peeling. A theory by Glamov and Drescher (414) attributed the effect of cell- oids to the reduction of the numerical value of the crystallization velocity, and pointed out that it was not dependent on an increase in viscosity. fhey felt that the effect of colloids is best explained by the assumption that complex cations are formed. Kochanoskii (460) found that nickel ions in solution were inactivated by the presence of ~109 - lyophilic colloids, and that the degree of activation was dependent directly on the degree with which the colloid was ly0philic. In 1939 flasher (525) proposed a theory on the influence of colloids on the structure of electrodepos its which was quite unique. lie pro- posed that colloids were adsorbed on the cathode during electrodeposi- tion, and thereby formed a porous diaphragm with a"pin-cushion" struc- ture. the discharge of the cations and the deposition of the metal he believed to occur in the intermiccllar spaces in the diaphragm. The pores of the diaphragm were small and the menber of crystal nuclei was large, and since the growth of the nuclei was hindered by the diffusion of the ions in the colloidal diaphragm, the deposit would be fine-grained. nmdricks (627) has written an excellent article on the mechanism of brigit electroplating. He believed that the deposition of bright nickel was a Liesegang phenomenon brought about by a periodic adsorp- tion of a colloid, or a colloid mixture, thereby producing striated deposits of high reflectivity. He also ascribed the increase in cathode polarisation due to nickel brightneers to "a resistance thr- ough the colloid film caused by a porous colloid membrane. Even when the colloids are inorganic, the membrane will offer resistance since nickel ions from a complex with such colloids regardless of their charge, which travel by cataphoresia to the cathode.“ his idea of colloid. migrating catapheretically to the cathode ... earlier brought out by hunt (314) who felt that if the proportion of metal ions to in- ert particles was low, due to the presume of colloids which had li- grated catapheretically into the film or were codepesited there, the crystal growth would be altered. Glazunov (555) also proposed that -110- colloids which uveloped the cations and traveled to cathode by cata- phoresis prevented the growth of crystals and increased the number of nuclei of crystallization on the cathode surface. He also proposed that the discharge of 00110 idal substances which combined chemically with mtal resembled the discharge of compls ions, and since the de- position of the metal was a secondary process the deposit could not be lads finer-grained by the presence of colloids. Besides the artifles mentioned, a number of other pod articles are listed in the literature on the effects of colloids in electro- plating solutions. These are by: Riedel (85), Killian (18d). Fro'lich and Clark (200), ahikata and Hosski (288), Glasstone (375), Oymboliste (410), Johnson (£17), Meyer (483), (455), Stout (432), Yosdvizhenskii and raisulin «ashram and Bhatia (ass). Hamster and Vervey (557), Puri and 5’.er (5'70). hri and Beth (612), Snelling and Thews (613), Haller (631). Planner (635). and Discher (‘62). m. m 2:. mm mm mm mm nails: solutions: The raval of colloids from any solution is a problem since the particles are so small that they can not be removed by ordinary filtration. acme colloids can be precipitated by electrolytes, but it is assumed that colloids existing in nickel plating (solutions would not be of this type since the solution is a strong electolytc. An article by Bonneff (28'?) appears to be the only one available on this subject. Bomoff sugges- ted that ”emulsoid" colloids could be removed by operating the bath at high current densities. He also recommended infusorial earths ad simi- 1.} material? as being valuable for filtering out colloids, of which colloidal iron hydroxide is a type. could sometimes be precipitated by -111 - the action of strong oxidising agents. Obviously, the colloids which are apt to cause the greatest’difficultics in electrOplating solutions are those which become positively charged and migrate to the cathod. lug: currut density electrolysis is then one means of removing this type, although it is not apparently kndwn to what degree of complete- ness the elimination may be carried out. It is possible that this pro- cess is too expensive in terms of the nickel also deposited out. to be practical- .d large percentage of the colloidal material found in electroplating baths is of organic composition. A.good many-colloids of this type can be successfully removed from nickel plating solutions by filtra- tion through activated carbon. The elimination of metallic colloids, however, remains a difficult problem. there are, of course,.mothods for removing colloids from solutions such as dialysis or electrodia- lysis, but thesc.methods would be impractical for application to elec- troplating solutions. Here again it is hoped that the experimental portion.of this researohwwill supply the answers to some of the unan- swered questions on electroplating. -112 - EEEEEBEEAEEI 1. 2. 3. 4. 5. 6. - 113 - 1901 H Hunter, F.W. "The CoaDeposition of Iron and.Nicke1 from a Solu- tion of their Sulfatcs." N Z. fur Elcktrochem. z, 688 (1901). 190 2 01km, T. "Electrolytic Refining of Composite Metals.” Trans. Am. Enoctrochem. Soc._1, 95-104 (1902). 1904 Bancroft, W.D. ”Electrolytic Purification of Cobalt and Nickel." Trans. Am. Electrochem. See. p, I, 39-40 (1904). Bancroft, W.D. "The Chemistry of Electr0p1ating." Trans. Am. Electrochem. Soc. é, Pt.II, 27-43 (1904). 1905 Betts, A.G. WPhcnomena of Metal Depositing." Trans. Am. Electrochemical Soc. g 63-99 (1905). Hybinctte "Electrolytic Separation of Metals." Fr. #360,101 Dec. 5, 1905. 7. 8. 9. 10. 11. 120 ~114- 1906 N Muller, E. and Spitzer, F. "0n the Anodic Formation of Oxides and Passivity." Z. Anorg. Chem. égn 521-354 (1906)e Richter, C. "On Some Experiments for Recovery of Cepper and Nickel from Waste Products in Nickel Plating. " Elektrochem. Z. 3, 185 (1906). 1907 Calhane, D.F. and Gammage, A.L. "A Study of the Cause of Impure Nickel-plate, with Special Reference to Iron." Jo Am. Chem. SOCo 29, 1268-75 (1907). 80110011, 13.13. and Kirsch, A. "Electrolytic Deposition of Lickcl- Zinc Alloys." Jo Ame Chem. SOCO 22., 314-21 (1EO7)o 1908 Anon. "Preventing of Tamishing of Nickel Plated Objects." Brass World 2, 264 (1908). Bancroft, 1H.121. "Relation of Electr0p1ating to Electrolytic Analysis. " J. Phys. Chem. _1_.3._, 36-46 (1908). 13. 14. 16. 17. 18. - 115 - Brochet, M.A. ”0n the heactions of t5e hickel Plating Bath." Corpt. rend. 145, 627-8 (1908). Brochet, H.A. "Iho deactions of Nickel Plating." 211110 SOC. 0:;1..":io (‘3) 1-2, 11KJS-1; (190(0)o Foerster, F. "The Electrochemical Behavior of Motels." 2- Electrochem. ng l5L-65 (1908). Fredenhagcn, 0. "Review of Lifferent Tassivity Theories and flew Observations of the Passivity of Iron, Lickel, and Chromium." Z. physik. chem. cg, 1-47 (1908). Harmer, G. "The Absorption of Nitric Oxide by Solutions of Ferrous, Nickelous, Cobaltous, and Manganous Salts." z. physik. chem. 52, 416-25 (1908). Kern. E.F. and Fabian, F.G. "Electrodeposition of Nickel." Electrochem. Met. Ind. p, 265-5 (1908). 19. 21. 22. 24. - 116 - H a L Stockmeir, H. rdvances in the Chemistry of Metal WOrking." Chem. Zty. 32, 743-4 (1908). o -v' n o e - 2. Turrentine, J.u. The Action of Ammonium rersulfate on metals." Jo 1;)‘lzf510e ChC‘ILc ll, 62L-C1 (1908)c 1909 Anon. "Lepositinp an Alloy of hickel and Cobalt." Brass World 5, 208 (1909). Kern, E.F. "The Function of Acdition Arents in Electrolytes." Trans. Am. Electrochen. Soc. 5, 458-465 (1909). Sohooh, EgP. "The Electromotive Force of Lickel and the Effect of Occluded Hydropen." Ame Chemo Jo fl, 208-8- (1909)c u‘ Slater, h.i. a Black Nickel Solution." Metal. Ind. Z, 12 (1909). 25. 26. 27. 28. 29. 30. -117- Berthelot, D. and Gaudechon, H. ';Comparative Action of Ultra- violetrays on Organic Compounds of Straight Chain and Cyclic Structure." "A Study of Mineral Salts in Agueous Solution." Compt. rend. 152, 376-8 (1910). Lambris, G. "The Deposition of Carbon in the Electrolysis of Nickel from Solutions." Ze Electrochem. 15, 973-81 (1910)c Schoch, 15.13. and Randolph, C.P. "Behavior of Iron and Nickel Anodes in Various Electrolytes." J. Physic. Chem. lg, 719-37 (1910). 1911 Anon. ”The Effect of Capper on Nickel-Plating Solutions." Brass world 1, 45-45 (1911). Anon. "Effect of Ammonia on Nickel Plating Solutions." Brass World 1, 137-8 (1911). anon. "Iron in Nickel Solutions." Brass World _7_, 154 (1911). 519 52. 53. 54. 35. 36. ~118- Anon. "The Advantage of a Large Amount of Boric Acid in a Nickel- Plating Solution." Brass World 7 234 (1911). Anon. "The Fitting of Nickel Deposits and their Prevention." Brass World 1, 316-7 (1911). Blassett, E. Jr. "The Cause and Prevention of Pitted and Rough Nickel Deposits." Hetal Ind. g, 462 (1911). Brown, P .S. "Nickel-Plating. "' Metal. Ind. 9 17-8, 84-5 (1911). Buchanan, C.H. ”A. Review of the Nickel-Plating Industry." Brass World 7 20-2 (1911). Coutculn, Le. "rho Role of Ammonium Persulfatc in Nickel Baths." Assoc. ing. inst. nord Nos.10,11, and 12, 49-50 (1911). s7. 58. 41. 420 -119 - Engomann, K. ”Peeling Off of Nickel Deposits." Z. Elektro Chem. 11, 910—7 (1911). Proctor, C.H. "'Plater's Wrinkles." Metal Ind. 2, 590 (1911)e Russo, G. "Anodic Behavior of Nickel in Presence of Chromous Salts.” auflo shim. 1531c fl, II, 101-9 (1911)e White, 0.3. "The Electrolytic Corrosion of Some Metals." Jo Physic. Chem. .15.! 725-92 (1911). 1912 Bollard, A. "ElectrOplating Nickel at High Pressure. Tin and Zinc Plating." Bull. Soc. Encour. Ind. Nat. July (1912). Hybinetto, N.V. "Electrolytic Isolation of Cepper, Zinc, and N1QkCIc” Brit. 5,806 March 6, 1912. 44. 45. 45. 470 -120-- Paterson, Joli. "Chemical Reactions Taking Place at the Cathode end Anode during the Electrolysis of Simple Salt Solutions." Pros. Univ. Durham. Phil. Soc. g, 187-220 (1912). Jo 8000 chem. Ind. El, 1040 (1912’s Sperry, 3.8. ”Obtaining Thick Nickel Deposits." Brass World 8 391 (1912). " Waser, 7.3. and Schulz, E.H. "Photo-and Photo-Micrographic .Re- production of Electrolytic Metal Deposits." Electrochemz. 12, 504-7 ' (1912). 19 13 Barrows, 9.8. "Solutions in General." (Quart, 3". Am. Electroplatcrs Soc. 1, No.1, 23-26 (1913). Bruni, G. and Amodori, M. "Formation of Metallic Alloys by Bloc tro lysi s. " Atti. acad. sci. lett. ed. arti, Padova pg, 349 (1913). Hobbs, 35W. "Filtering, Agitating and Heating of Nickel Plating Solutions." Metal Ind. 1;, 344 (1913). 49o 51o 52. 53. 54. - 121 - Holland, A. “Nickel, Tin and Zinc Baths." Metal Inde 21, 522 (1913)e Lieeomb, F.J. "What are Conducting Salts?" Wart. ROVe Am. mCQtI‘OplatOT'B 3080 1, No.2, 10-14 (1913)e Prootor, G.H. "Practical Nickel Solution for Plating Die-Castings." mean Ind. .11. 11-2 (1912). Suchy, G.T. and Maae,.R. "The Electrolytic Deposition o£.Alloys and the Metallographical and Mechanical Investigation of their Properties. I Niekel-Iron.Alloys Deposited at Ordinary Tempera- tures." Monatah. $5.11. 1757-1809 (1913). Suman, n. "Nickel Solutions." Quart. Rev. Am. Electroplater's Soc. I No.2 43-45 (1913). Watts, o.1>. "Black Nickel Solutions." Quart. Bev..Am. Electroplater'o Soc. 1, No.2, 18-26 (1913). 55. 56. 5'7. 58. 59. 60. -122 - Watts, O.P. "The Eleotrodeposition of Nickel.” Metal Ind. Ll. 293-4, 53-4-6, 380-1 (1913). Watts, O.P. "Electrodeposition of Cobalt and Nickel." Trans. Am. Electrochem. Soc. 23:, 99-151 (1915). Watts, O.P. "Factors Influencing the Nature of Electrolytic Deposits." Metal Ind. .11. 32-3, 85—4 (1912.). 1914 Baum, H. "Slime in Nickel Solutions." Monthly Rev. Am. Electroplater's Soc. 1, No.5 16-17 (1914}. Bennett, 031., Kenny, 11.0. and 'Dugliss, B.P. "Eleetrodeposition Of NiOKQIO" Trans. Am. Eleetrochem. Soc. gfi, 3:5 —345 (1914). Jo Pher Chem. _L8, 373-84 (1914)e Iremann, R. and Haas, R. "The Electrolytic Deposition of Alloys, etc. V. The Nickel-Iron Alloys Deposited from Sulfate Baths at High Temperatures." Monatsh. £53, 731-5.: (1914)e 61. 620 63. 64. 65. 66. -123- Nat. Lead Co. "Eleotroplating Zinc-Alloy Die Castings." Indmtrial Eng. 13, 107-8 (1914). Sehooh, P. "Mechanism of Anodic Reactions and the Behavior of Iron and Nickel Anodes." Trans. Farad. Soc. g, 274-80 (1914). Met. Chem. Mg. 1;, 682 (1918). Watts, O.P. "Black Nickel Solutions." Metal Ind. 33, 24-5 (1914). 1915 Bennett, 0.19., Rose, 0.0. and Tinkler, L.G. 'Eleotrodeposition of Nickel." J. Phys. Chem. 9, 564-8 (1915). Heil, aw. "Single Niekel Salt Solutions and hesults I Get." Monthly Rev. Am. Eleetroplater's Soc. ,3, No.3, 13-16 (1915). Eybiaette, NJ. "Separating 00pper and Nickel from High-Grade Copper-Nickel Mat er ial ." U.8,1,128,313-4-5-6 Feb. 16, 1915. 57s - 68. 69. 70. 71. 72. -124- Intseheller, A. "The Action of Certain Colloids on Ions During Electrolysis." Met. Chem. Eng. 1g, 355, 42.9 (1915). Proctor. C.H. "Some Methods Used by Platers to Produce Bright Nickel Deposits." Metal Ind. 13;, 57 (1915). Riedel, R. "Electrolytic Separation of Nickel from its Chloride Solutions . " Electrochem. Z. 31, 5-19 (1915). Tor Doest, HoJ. "Observat ions on Nickel Plating." Monthly Rev. Am. Electroplaters Soc. 1, No.8, 12-16 (1915). Thompson, E.3. "Reactions of a Nickel Solution." Monthly Rev. Am. Electroplater's Soc. 1, No.11, 8-10 (1915). Walters, J. "Slime in Nickel Solutions." Monthly Rev. Am. Eleetroplater's Soc. .2_, No.4, 18-15 (1915). 74. 75. 76. 77. 78. -125- 'Watts, O.P. "Cleaning and Plating in the Same Solution." Hammond, L.D. ”The Electrodeposition of Nickel." Trans. Am. Elecirochem. Soc. gg, 201—29 (1916). Monthly hev..Am. Electroplater's Soc. 3,2N0.7, 4-10 (1915). Weber, W.H. "Nickel riatinp on Zinc." I‘iet'il Inde £9 8:6 (1915)e 1916 Benvenuti, P. "Alloys of Irln and Nickel Deposited Electri- .oally." Atti r. inst. Veneto 16, 455-77 (1916). De Mars, J. "Black Nickel Finish." Monthly hev. Am. Electroplater's Soc. g, No.12, 10 (1916). Hell, E.W. "Reactions of Conductin? Salts in Nickel Solution." Monthly Nev. Am. Electroplater's Soc. g, No.8, 4-9 (1916). 79. 80. 81. 82. 830 8‘- -126- Lissomb, F.J. ”Nickel Anodes." Metal Ind. a, 284 (1915)e Liscomb, F.J. "More About Fitting." Monthly Rev. Am. Electroplater's Soc. 31, No.12, 8-10 (1916). Mathers, F.C., Stuart, E-H., and Sturdevant, E.G. "Nickel Plating." Trm'e Am. Electrochem. SOOe _2_S_3_, ”183-92 (1916)e Mathers, F.C. and Sturdevant, E.G. "Current Efficiencies in Nickel-Plating Baths with Rotating Cathodes." Trans. Am. Eleetrochem. Soe. g9, 135-144 (1916). Miller, B.E. "Calcium Chloride in Nickel Solutions." Monthly Rev. Am. Electroplater's Soc. g, No.3, 5-6 (1916). Newberry, E. "Overvoltage Tables. I Cathodic Overvoltages." J. Chem. Soc. 103, 1051-66 (1916). -127- 85. Riedel, R. "Electrodeposition of Nickel from Chloride Solu- tions.” 20 Elektrochem. 22‘: 281-6 (1916). Jo 80's Chem. Ind. fl, 957-8 (1915)e 86. Robins, G.S. "Caleium Chloride in Nickel Solutions." Monthly Rev. Am. Eleotroplater's Soc. §_, No.4, 11-12 (1916). 87. Robinson, DAV. "lziaglesium Sulfate in Nickelplating Solutions." Metal Ind. 11;, 287 (1916). 88. Sizelove, 0.J. "Nickel." Monthly Rev. Am. Electroplater's Soc. 51, No.3, 11-14 (1916). 89. Taylor, S.R. "Nickel Solutions." lionthly Rev. Am. Eleotroplater's Soc. _._'3_, No.8, 7-8 (1916). 90. Van Derau, C. "Electra Plating Die Castings." Monthly Rev. Am. Electroplater's Soc. §_ No.12, 15-16 (1916). -128 - 91. Wadsworth, F.J. "The Plating of Die Casting." MonthlyRev. Am. Electroplater's Soc. ,1, No.2, 8-9 (1916). 1917 92. Anon. "Hy'binette Electrolytic Nickel-Refining Method." lining Sci. Press 114, 666 (1917). 93. Brown, '13. "Some Rapid Nickel Aquntures." Metal Ind. 1;, 8-9 (1917). 94. Haas, J.Jr. "Some Hperiments on Nickel Solut ions." Monthly Rev. Am. Electroplater's Soc. A, No.12, 4-8 (1917). 95. Hazueha, R.J. "Nickel and Brass Plating of Die Castings." Monthly Rev. Am. Eleotmplater's Soc. 3,, No.10, 11-12 (1917). 96. Hell, E.W. "Resistance and Conductivity of Nickel Solutions." Monthly Rev. Am. Electroplater's Soc. 5;, No.11, 5-12 (1917). 97. Rybinette, NJ. "Separating Nickel From 00pper." Sled. 42,495 May 9, 1917. 98. 99. 100. 101. 102. 103. -129 - Itemnn, R. and Breymesser, R. "Electrodeposition of Alloys and their Metallographie thmination. VIII Cathodic Deposits of Iron and Iron-Nickel Alloys Obtained at Ordinary Temperature under High Hydrogen Pressure.” Monatsh. pg, 91-111 (1917). J. Chem. Soc. 112, II 574 (1918). Later, E.P. "Intelligent Use of Nickel Plating Solutions." Foundry g, 333-5 (1917). Mills, H. "Casket Hardware ElectrOplating and Finishing." Monthly Rev. Am. Electroplater's Soc. A, No.10, 15-16 (1917). Robinson, D.W. "Mechanical Plating." Metal Ind. 5, 61-4 (1917). Walters, J. "Nickel and the Use of Sulfuric Acid and Magnesium Sulfate. ” Monthly Rev. Am. Electroplater's Soc. 4, No.5, 10-12 (1917). Walters, J. "Nickel Plating Store Castings Commercially." Monthly Rev. Am. Electroplater's Soc. 4 No.8, 16—19 (1917). 1049 105. 106 . 107. 108. 109. -130- 1918 Allen, W. "Government Black Nickel." Monthly Rev. Am. Electroplater's Soc. 5 No.12, 13-14 (1918). Blum, W. "Military Applications of Electmplating." Metal Ind. 19;, 498-9. (1918). Kohlsehuetter, V. and Vuilleimier, E. "Physical Phenomena Accom- panying Cathodic Deposition of Metals (Nickel)." Z. nektrochem. 32, 300-21 (1918). Later, E.P. "Nickel Solutions." Foundry 46, 213-5 (1918). Nelson, J. "Plating and Polishing of Tin and Zinc Sheets." Monthly Rev. Am. Electroplater's Soc. 5 No.3, 16-17 (1918). Proctor, 0.11. "The Use of Sodium Thiocyanate in Black Nickel Solutions." Met. Ind. lg, 26 (1918). 110. 111. 112. 1130 114. 115. - 131 - Saul, LE. and Crawford, D. "Separation of Traces of Copper from Solution." Analyst 3;, s (1918). The Yokohama Gyoyu Kabushikikiwaisha "Purifying Nickel Solu- tions." Jap. #32, 476 Apr. 2, 1918. 1919 Blum, W. "factors Governing the Structure of Electro-Deposited MOtfilie" Tranle AU]. mOCtI‘OCthe 3000 :31, 213-241 (1919)e Carlson, 0.11. "The Use of Cadmium in Nickel Solutions." Monthly Rev. Am. ElectrOplater's Soc. 6, No.12, 10 (1919). Chicago Branch of the AoE.S. "Why Does a Nickel Solution Plate?" mnthly ReV. Am. Electroplater's Soc. _6_, No.12, 11-13 (1919). Guess, G.A. "A Process for Electrolytically Ref ining Nickel." Trans. Am. Electrochez:1. Soc. $1.51. 259-62 (1919). 1160 117e 1180 1190 120. 121. -,132 - 11.11, aw. éiiuriatic Acid in Nickel Solutions." Monthly Rev. Am. Electrolllater's Soc. 6, No.1, 7-9 (1919). Hogaboom, G.B. Slattery, T.F. and Ham, L.B, "Notes on Black Nickel Solutions." Monthly Rev. Am. ElectrOplater's Soc. 6, No.7, 14-18 (1919). C.H.P. (Proctor. C.H.) "Nickel Plating Cast or Sheet Aluminum." Metal Ind. 11, Eb (1919)e 1920 Aliverti, G. "Contracted Condition of Electrolytic Metallic Deposits." Atti aoad. Lincei 2;, I, deg--7 (1920). Anon. "Nickel Plating Rolled Zinc." Metal Ind. _1,_e_, 308 (1920). Barrows, \‘hS. "Black Deposits." Monthly Rev. Am. Electroplater's Soc. 1, No.13, 11 (1920). 122. 125. 124. 125. 126. 127. ~133- Knickerbocker, R.G. Electrolytic Separation of Copper from Cepper- Cobalt-Nickel Mat." Mining Sci. Press 121, 45-50 (1920'). Lovering“, E.G. "Lovering’i‘hagic Fluid." Monthly Rev. Am. Electroplater's Soc. 1, 1.0.2, 4-5 (1920). Proctor, C.H. 'Tltiting: of Sheet Zinc." Metal Ind. lg, 495-7 (1929). - H - . Stager, Hans “Electrode neactions. Effect of Temperature and Depolarization 0:: the Type of Nickel Deposit Obtained." Helvetica 01111.2. Acta. _z_, 564-613 (1920). Whitcomb, H.H. "The Application of Science to the Electro- Deposition of Metals." Monthly Rev. Am. Electroplater's Soc. _7_, No.10, 4-6 (1920). 1921 Anon. "The Hybinette Process for Separating COpper and Nickel." Z. Elektroehem. 31, 61-63 (1921). -134- 128. Blum, Wm. "The Use of Fluorides in Solutions for Nickel Deposi- tion." Trans. Am. Electrochem. Soc. _32, 459—79 (1921). Brass World 11, 121 (1921). 129. Elm, We and Slattery, T.F. "The Electrolytic ~Reprodliction of Engraved. Printing Plates." Chem. ilet. Eng. 25, 1320-1 (1921). 130. Buchanan, Coll. "Nickel anodes." Monthly Rev. Am. Electroplater's Soc. _8_, No.6, 12-14 (1921). 131. Field, 0.0. "Nickeling Die Castings." Monthly Rev. Am. ElectrOplater's Soc. _8_, No.9, 17-18 (1921). 132. Haas, J. Jr. "Black Nickel Solutions I." Metal Ind. _1_9_, 23-5 (1921). 133. Haas, J. Jr. "Black Nickel Solutions II." Metal Ind. _1_9_, 73-4 (1921). 134. 135. 136. 137. 138 . 139. -135 - Haas, J. Jr. "Survey of Nickel Solutions (1).” Metal Ind. _L9, 364-6 (1921). Hogaboom, 0.13., Slattery, TJ‘. and Ham, L13. "Black Nickel Plating Solutions." Bur. Standards Tech. Piper 130.190 (1921). Hughes, W.E. "Progress in the Commercial Application of Elec- trolysis (Electroplating)." Electrician 81, 640-2 (1921). " N Kohlschutter, V. and Nageli, A. "Tepochemical i‘teactions. The Formation of Carbon on Contact Surfaces." Helv. chim. Acta 4, 45—76 (1921). Madsen, C.P. "Ductile Electrolytic Nickel." Trans. Am. Electrochem. Soc. 559, 482-90 (1921). Chem. 111913e Enge a, 923-4 (1921)e Mathers, F.G. "Organic Substances in ElectroPlating Solutions." Monthly Rev. Am. Electroplater's Soc. _8, No.10, 4-10 (1921). 140. 141. 142. 1430 144. 145. - 136 - Pleadwell, 17.8. "Observat ions on the Use of Hydrofluoric Acid in Nickel Solutions." NOeG, 8-9 (1921)e Monthly Rev. Am. Electroplater's Soc. 8 Sand, H.J. "The Role of Colloidsl'n Electrolytic Metal Deposi- tions. (Addition Agents.)" Brit. Assoc. Advancement of Sci. 4th Report, 1921, 346-51 (1921). Schlotter, M. "Nickel and Cobalt Plating." Stahl u. Eisen, .4_1_, 293-7 (1921). Vuilleumeir, E.A. "The Peeling -of Nickel Deposits.” M0583. Ind. (NeYe) E, 419 (1921)e Watts, O.P. "Polarization, Cleaners and Hydrofluoric Acid in Nickel Solutions . " Monthly Rev. Am. Electmplater's Soc.§_, No.8, 4-10 (1921). Werner. Eugene "The Care of Nickel Plating Baths." Elektrochem. Z. 31, 35-7 (1921). 146. 147. 148. 149. 150. 151- - 137 - Woodmansee, E. 'Hydrofluoric Acid in Nickel Solutions." Monthly Rev. Am. Electroplater's Soc. 9, No.11, 5-7 (1921). 1922 Carl, R. "Electroplat ing. " Oesterr. chem.-Ztg. 25, 9-11, 15-8 (1922). Herrick, S. "Plating of Die Castings." Metal 1nd. _2_0_, 554 (1922). Hughes, W.E. "Building Up Worn Parts by Electrodeposit ion." Chem. Met. Eng. 25, 267-9 (1922). II Kohlschutter, V. "Colloidal Chemistry and Electrochemistry." Kolloid-Z.‘§l, 263-6 (1922). Ledin, T. "Nickel Plating on Aluminum." Metal Ind. 251, 351-2 (1922). 152. 153. 154. 155. 1569 157. - 138 - Newark Branch of A.E.S. "Distribut ion of Current Upon a Flat Cathode in a Nickel Plating Solution." Monthly Rev. Am. Electroplater's Soc. 9, No.10, 4-15 (1922). Proctor, CoH. "MHd.in Nickel Tank." Metal Ind. (NeYe) fig, 7 (1922)e Sand, H.J. "The Role of Colloids in Electm lytic Metal Deposi- tions (Addition Agents)." Fourth Report on Colloid Chemistry, Dept. of Science and Indus- trial Research 19 g, 353. Thompson, 11.11. and ThomaS, cm. "The Effect of Impurities in Nickel Salts Used for Eleetmdeposition." Trans. Am. Electrochem. 3000 L2, 79-94 (1922)e Thompson, Moli. and Thomas, 0.53. "The Purity of Nickel Salts." Monthly Rev. Am. Electroplater's Soc. 2, 4-11 (1922). Vuilleumier, LA. "The Peeling of Nickel Deposits." 158. 159 . 160 . 1510 162. 163. -139 - Mlleumier, E.A. "The Application of Contractometer to the Study of Nickel Deposit ion." Trms. Am. Electrochem. Soc. _4_2_, 99-112 (1922'). Watts, O.P. "Relation of Anode and Cathode Efficiencies." Monthly Rev. Am. Electroplater's Soc. 9, No.7, 4-14 (1922). 1923 Blum, W. and Rawdon, H.S. "The Crystalline Form of Electrodepo- sited Metals." Trans. Am. Electrochem. Soc. 44, 597-425 (1925). Debolt, W.E. "Black Nickel Solutions." Monthly Rev. Am. Electr0p1ater's Soc. 10, No.4, 14-15 (1923). Glasstone, S. "Cathodic Behavior of Alloys. I.Iron-Nicke1 Alloys. ” Trans. Faraday Soc. 9, 574-83 (1923). Graham. A.K. "The Electrodeposition of Nickel on Zinc." Trans. Am. Electrochem. Soc. 44, 347-358 (1923). 164. 165. 166. 167. 168. 169. - 140 - Heil, E.W. "Resistance of Nickel Solutions." Monthly Rev. Am. ElectrOplater's Soc. 19, No.12, 8-12 (1923). Holland, A. "The Production of Heavy Nickel Deposits." .Aluminium-, Messing- and Kupfer Waren é, No.18, 8 (1923). Hughes, W.E. "Electrodqposition of Metals. XI. Structure of Electrodeposited Metal." Beama 12, 215-25 (1925). Martel, C.C. "Agitation of Hot Nickel Solutions." Monthly Rev. Am. Electroplater's Soc. 1Q, No.1, 5-10 (1928). Mere, A. "Defects.Appearing in the Nickel-Plating of Castings." “ Giesseri-Z. 0, 559 (1923). Philadelphia Branch of the A.E.S. "Hydrofluoric Acid in Nickel Solution." Monthly Rev. Am. Electroplater's Soc. 1Q, No.4, 12-14 (1923). 170. 171. 172. 173. 174. 175. - 141 - Proctor. (MI. "The Production of Bright Nickel Deposits.(By the Aid of Cadmium as the Colloidal Factor.)" Monthly Rev. Am. Electroplater's Soe. _1_0_, No.6, 9-13 (1923). Rea-ma, H.H. "Black Nickel Plating." Monthly Rev. Am. Electroplater's Soc. 19, No.4, 16-17 (1923). 3. Thompson, M.R. "The Effect of Iron on the Electrodeposition Of Nickel." Trans. Am. Electrochem. Soc. 44;, 359-93 (1923). 1924 Audubert, R. "The Structure of Electrodeposits." Rev. metal. _21, 567-84 (1924). Campbell, A.N. "Electrolytic Formation of Alloys 8: Amalgams of Manganese." J. Chem. Soc. 25, 1713-9 (1924). Detroit Branch of the A.E.S. "Special Report No.17-Research Committee. The Nickel Plating of Zinc Base Die Castings." Monthly Rev. Am. Electroplater's Soc. 11, No.10, 14-17 (1924). - 142 - N 176. Frolich, P.K. "The Amphoteric Character of Gelatin and its Bearing on Certain Electrochemical Phenomena." Trans. Am. Electrochem. Soc. _4_§_, 67-83 (1924). Monthly Rev. Am. Electroplater's Soc. 12, No.4, 12-15 (1925). N 177. Frolich, P.K. "The Introduction of Carbonaceous Matter in Electrodeposited Iron and Nickel." Trans. Am. Electrochem. Soc. 46, 87-103 (1924). 178. Hammond, L.D. "Conductivity of Nickel Solutions." Trans. Am. Electrochem. Soc. 45;, 219-227 (1924). Monthly Rev. Am. Electroplater's Soc. _11, No.6, 4-9 (1924). 179. Haring, H.E. "Throwing Powers of Nickel Solutions." Monthly Rev. Am. Electroplater's Soc. Q, No.9, 4-13 (1924). 180. Haring, HeEe "Throwing Power, cathode Potentials and Effi- ciencies in Nickel Deposition." Trans. Am. Electrochem. Soc. ‘6, 107-129 (1924). 181. 182. 183. 184. 185. 186. - 143 - fl Kohlschutter, V. "The Relation Between Polarization and Struc- ture in the Electrodeposition of Metals (Nickel)." Trans. Am. Electrochem. Soc. _45, 229-240 (1924). Madsen, C.P. "Mechanically Perfect Electrolytic Nickel." 'Trans. An. Electrochem. Soc. 42, 249-56 (1924). Maxwell, H.B. "Black Nickel Plating." Metal Ind. (NeYe) 22, 449-50 (1924)e Millian, E. "Action of Colloids on Electrolytic Metals." Bull soc. shim. Belg. _3_3_, 542 (1924). Rothmand, V. "The Influence'af the Anions on the Passivity of Metals.” z. physik. Chem. 110, 384-93 (1924). Shepard, R.I.. "Use of Lead and Glycerin for Bright Nickel." Brass World 39, 416 (1924). 187. 188. 189. 190. 191. -144- Shepard, R.I.. "Filterat ion System for Nickel Platiz'g Plant." Monthly Rev. Am. Electroplater's Soc. 1 , 50.3, 12—14 (1924). Shepard, 1.L. "Report of the Joint Conference of the Bureau of Stmdards and Research Committee of the A.E.S." Monthly Rev. Am. Electroplater's Soc. _ll, No.11, 1-14 (1924). Thoma, CoT. and Blum, "u’. "Nickel Anodes for Electroplating." Trans. Am. Electrochem. Soc. _4_5_, 193-214 (1924). in Thomas, 0.33. and Blunt. W- "Behavior of Nickel Anodes." Monthly Rev. Ana. Electroplater's Soc. 11, No.3, 5—11 (1924). 7083, W. "Diseases of lfickel Deposits." Metal Ind. 22, 66-7, 154-4 (19.94). Watts, O.P. "Pitting of Nickel Plating." Monthly Rev. Am. Electroplater's Soc. _11, No.2, 8-12 (1924). - 145 - 1925 193. Anon. "The Microstructure of Electrodqposits." Metallwaren-Ind. u. Galvano-Tech. 2;, 442-4, 467-8, 491-2 (1925). 194- Anon. "Defective Phenomena in the Nickel Plating of Castinrs." Metallwarcn—Ind. u. Galvano-Tech. £3, 470—1 (1925). 195. Anon. "Rust-RCSESLant Lickel Plstiu~." hctullvarQfl-Ihde u. Galvano-Tech. 3%. 505-6 (1935 ‘ IE6. Berger, M. "Defective Nickel Plating." Apparatebxu 37, 64-5 (1925). 197. Bernard, H.C. "Overcoming Plating Troubles." Abrasive Ind. 6” 380-1 (1925). 198. Eichstadt, T.C. "Nickel-Plating Automobile Bumpers." Metal Ind. (London) 26, 603 (1925). 199. Ellis, W.C. "A Study of Factors Affectinr the Electrode Poten- tials in the Deposition of Nickel." Thesis: Rensselaer Polytechn. Inst. June 1925. 200. 201. 202. 203. 204. 205. -146- Frolich, P.K. and Clark, G.L. "The Electrodeposition of Metals. II. X—Ray Investigation of Electrolytic Nickel." Also-"I. Theory of the Mechanism. " z. Elektrochem. 351, 649-55, 655-58 (1925. _-\ Hineline, 11.13. and Cooley, 37.15. '"Electrodeposition of Copper- Nickel Alloys." Trans. Am. Electrochei... Soc. 48;, 61-66 (1.25). Lang-fie, H. "The Iz'aportance of Anodes in the Galvailoteclniics." Z. 505. Giessel‘ei Prazzis: Das Iletall 46, 197-8 (1925); Lewis, B.£“. "Use of the Distribution Box for Better Plating." Monthly Rev. Am. Electroplater's Soc. 12, No.1, 16-19 (1925). Nichol, P.A. and Watts, O.P. "Effect of Nitrates on Current Effi- ciency of Plating Solutions." Trans. Am. Electrochem. Soc. 48, 31-33 (1925). Porter, 9.11. and Sward, E.F. "Insoluble Matter in the Nickel Bath and its Effect Upon the Protective Value of the Plate Applied." Monthly Rev. Am. Electroplater's Soc. 12, No. 12, 12—15 (1925). 206. 207. 208. 209. 210. 211. - 147 - Proctor, C.H. "Hydrogen Pitting in Nickel Plated Deposits. Its Cause and Cure." Monthly liev. Am. Electroplater's Soc. 12, No.12, 5-12 (1925). Proctor, 0.11. and Sizelove, O.J. "The Electrodeposition of Nickel." Metal Ind. (1;.Y.) 2;, 415-6 (19 £5). Richards, H.J. aid Menniges, F.P. "Magnesium Sulfate in Nickel Solutions." Monthly liev. Am. Electroplater's Soc. 2, No.7, 23- (1925). Shepherd, R.L. "Use of Lead and Glycerin for Bright Nickel." Monthly Rev. Am. Electroplater's Soc. 12, No.1, 7-8 (1925). Thomas, C.T. and Blum, 1"]. "The Protective Value of Nickel Plating. " Trans. Am. Electrochem. Soc. fl, 69-87 (1925). Thomas, C.T. and Blum, W. "The Protective Value of Nickel Plating on Iron and Steel." Monthly Rev. Am. Electmplater's Soc. 12, No.9, 4-9 (1925). 212. 215. 214. 215. 216. 217. - 148 - Thompson, m.h. "The Nickel Plating of Zinc and Zinc-Base Die Castings." Ibntnly Rev. Am. ElectrOplater's SOC. lg, 13004, 6-11 (1 25 0 Trans. Am. Electrochem. Soc. 47, 16L-135 (1925), B.A.H. "A Comparison of immoriuw Chlorife an? Sodium Sulfate Nickel Baths for Barrel Platinr." month y Rev. Am. Electroplater's Soc. 1;, Ko.1, 11-18 (1926). Barrows, H.S. "Lickel Anodes and Their Use." Can. Fou dry 11, 14—5 (1926). Ibbbs, E.J. "Cornercial Electrodeposition of Nickel." Electr0plater's And DePOSitor's Tech. Soc. Nov. 1-7 (1926). Faint, B.U.To "Plat1233 Autorobile Parts for SerViceo" Ionthly Lev. Am. Eleotroylétor's Soc. 1:, Ico8, 8—9 (1926). harris, U.E. ”Bleetroylatiry on Iron and Steel-" Electriciar. 21, 610-1 (1926). 218 o 219 . 28)- 221. 222. . 223. -149- Matuachek, J. "Rapid Nickel Plating: in Still Baths." Metallwaren-Ind. Galvano-Tech. £34., 249-50 (1926). Ollard, E.A. 'Nickel-Plating Solutions: Their Composition and Properties." Metal Ind. (London) .722. 551-5 (1926). Shepard, 11.1.. "Use of Permanganate in Nickel Solut ions." Monthly Rev. Am. Electroplater's Soc. 1:), No.9, 14-16 (1926). Underwood, J. "Nickel Plating in a Combination Manufacturing let and Jobbing Slop." Monthly Rov. Am. Electroplater's Soc. 3, No.9, 14-15 (1926). 1927 Anon. ”Theory and Practice in Electroplating." Metallwaren-Ind. Galvano-Tech. fl, 27-8, 47-8 (1927). Barrows, W.S. "Depositing Black Nickel and Gun Metal." Oan/Foundryman 6nd Electroplater 1g, 13-4 (1927). Brass World fig, 221-2 (1927). 224- 225. 226. 227. 228. 229. -150- Bohnek, Hans "Galvanic Coatirgs On Aluminum." I. Foereter, F. and Kruger, F. "The Behavior of Nickel Anodes in NickeléPlating Baths." 2. Elektrochem. angew. physik. Chem. gig, 406-25 (1927). Glautone, S. "Studies of Electrolytic Polarization. VLBleetro- deposition Potentials of Alloys of Zinc with Iron, Cobalt, and NlIkele" Je Chem. 8000 1937, 541-7e Gleeetone, 1.8. and Symon, LE. "The Eleetrodeposition of Iron-Nickel ‘ Alloys. ,. Trans. Faraday See. _2_;_, 2122-26, (1927). Graham, Adi. "Spotting Out." “.1581 Ind. (NeYe) _2_5_, 290-2 (1927)e Hogaboom, G.B. "Nickel Anodes." Monthly Rev. Am. Electroplater's Soc. .13, No.12, 10-12: (1927). 230., 231. 232. 233. 234. - 151 - Hughes, W.E. "Studies on Electroplatino. (Second Series) Electrodeposition on Aluminum. III.The Non-Adhesion of Elec- trodeposits." Metal Ind. (London) 33, 293-6 (1928). I. Kohlschutter, 10V' and Jakober, F0 "Electrolytic Crystallizat- ion.Prooeeses. III.The Formation and Properties of Adherent Met- allic Layers." Z. Electrochem. angew. physik. Chem..§§, 290-308 (1927). Nchaughton, D.J., Hothersall, A.W. "The Hardness of Electro- deposited Nickel." Trans. Faraday Soc..§fi, 387-400 (1927). Metallges. A.G. .."RemovingiHalogen Ions from Salt Solutions for Use in Eneetrodeposition." Car. 484, 198 Dec. 2, 1927. Naville, PoH. "Electrolytic Deposition of Metals on an Indus- trial Scale." Chimie et industrie Special NQ., 405-7 (May 1927). 235. 236. 237. 238. 239. - 152 - Nieol, A.E. "The Conductivity of (Nickel and Silver) Plating Solutions.” Metal Ind. (London) 39, 90-1 (1927). Watts, O.P. "Throwing Power." Honthly Rev. Am. Electmplater's Soc. 15, No.4, 5-11 (1927). mun, 11.0. and Proctor, K. "Effect of Cadmium Salts in Nickel Platinge" Chem. and Met. Bag. 353;, 472 (1927). Zwolfmeyer, M. "Metallic Preeipitates Under the Nieroscope." Blatter Unters. Forseh. Instr. 1, 53-6 (1927). 1928 Blum, W. and Winkler, J.H. "Niekel Electrotyping Solutions." Trans. Am. Electrochem. "Soc. 53;, 419-54 (1928). Coeks, 11.6. "The Effect of Superposed Alternating Current on the Deposition of Zinc-Nickel Alloys." Trans, Faraday Soc. fl, 348-358 (1928). 241 . 242. 243 . 244. 245 . 246.. -153- 'Dorrance, R.L. and Gardiner, 11.0. "Polarization and Resis- tiVity in liickel Plating Solutions. Trans. Am. Electrochem. Soc. i2- 303-312 (1928). Glasstme, 3. and Symes, T.E. "Electrodeposit ion of Iron-Nickel Alloys e" Trans. Faraday Soc. _23, 370-8 (1928). Hansen, J. "The Mechanism of the Action in Galvanic Baths." Metallborse L8, 257-8, 314—5, 483—4 (1928). Hughes, 17.19.. "Studies in Electroplating. Electrodeposit ion on Aluminum. III. The Non-Adhesion of Electrodeposits.“ Metal Ind. (London) gg, 173-5 (1928). MaeNaughton, D. J. and Hothersall, A.W. "The Causes and Pre- vention of Pitting in Electrodeposited Nickel.” Trans. Faraday Soc. _23, 497-509 (1926). Morel, B. "Good and Bad Nickel Plating." Plating 1, No.4, 4-7 (1928). 247. 248. 249. 250. 251. 252. - 154 - Upthegnove, C. and Baker, E.M. "Photomicrogrsphie Study of Rough or Nodulized Eleetrodepos ited Nickel." Trans. Am. Electrochem. 308- no 389-412 (1928). Watts, O.P. "More Perfect Metal Deposits." Monthly Rev. Am. Eleetroplater's Soc. 1;, No.4, 12-16 (1928). 1929 Anderson, E.A. and Reinhard, 0.13. "The Plating of Rolled Zinc and Zine-Base Die-Castings." Research Bull. N.J. Zinc Co. Nov. (1222). Metal Ind. (London) 312, 85-6, 88, 110 (1930). Barrows, W.S. "Magnesium Sulfate in Nickel Plating Baths." Can. Machinery Q, No.19, 71-3 (1929). Bogitch, B. "An Electrolytic Refininanrocess for Nickel." Gompt. rend. 188, 328-9 (1929). Ewing, D.T., Archer, JoE. and Shadduck, H. "Bibliography of Electrodeposition of Nickel." Mich. State 00110 3119:. Expt. Sta. B11110 NOe 226.9 (nggle 253. 254. 255. 256. 257. 258. - 155 - Foss, B. "Nickel Plating: of Aluminum." Monthly Rev. Am. Eleetroplater's Soc. l6_, No.11, 7-8 (1929). Fuseya, Giichiro, Liurata, Kwanji and Yumoto, R. "Addition Agents in Electrodeposition. III, Application of the Complex Cation Theory to Baser Metals." Tech. Repts. Tohuku Imp. Univ. 9, No.1, 32-56 (1929). Hogaboom, G.B. "Nickel Solutions." Metal Ind. (11.14421, 172-5 (1929). BaeNanghton, D.J. and Hammond, B.A.F. "The Progress of Niekel Deposition in Recent Years." Metal Ind. (London) E, 79-92 (1929). Mathers, F.C. "Conditions that Cause Changes in the Composi- tion of Plating Baths and Possible Remedies." Monthly Rev. Am. Electmplater's Soc. 6, No.12, 9-24 (1929). Oesterle. K.M. "The Conditions of Formation and Properties of Very Thin Electrolytic Nickel Deposits." 20 Elektrochem. gig 505-19 (1929)e 259. 260. 261. 262. 263. 264. - 156 - Schlotter, M. "Electrolytic Deposits and Coatings Obtained by Hot Dipping." Metallwaren-Ind. u. Galvano-Tech. 21, 269-72 (1929). Schuch, Karl "Surface Treatment and Galvanizing of Aluminum. " Metallwaren-Ind. u. Galvano-Tech. 31, 88-90 (1929). Skowronski, S.— "Refinery Production of Nickel Salts Used in Elec troplat ing . " Eng. Mining J. 28, 544 (1929). Uhderwood, J. "Bright Plating on Small Lead.Parts." Monthly Rev. Am. Electroplater's Soc. 16, No.5, 44-6 (1929). Underwood, J.E. ”Production of Bright Nickel Deposits." Metal Cleaning and Finishing 1, 435-6 (1929). Von, Wm. and Snelling, R.J. "Failures in Nickel Plating- Their Causes and Their Cures." Metallbgrse 12, 1967-8, 2023-4 (1929). 255. 266. 267. 268. 269. 270 . -157- Wernick, S. "The Prevention of Corrosion by Electrodeposition. VI. Nickel Plating as a Corrosion Preventative." Ind. Chemist _5_, 106-10 (1929). 1950 Adams, B.A. "Removal of Lead, Zinc, Copper and Tin from Drink- ing Water by Means of Base-Exchange Materials." Water and Water Eng. §_2_, 415—9 (1930). Ballay, M. "The Scientific Control of Electrodeposits, Espec- ially Deposits of Nickel and Chromium." Rev. Metal _21, 1516-25 (19.30). Chimie 8: industrie Special 110., 252-62 (March 1930). Pink, C.G. and Lah, K.H. "The Deposition of Nickel-Cobalt Alloys." Trans. Am. Electrochem. Soc. _5_8_, 373-381 (1930). Fink, C.G. and Lah, K.H. " A Silver-White Alloy Plate." Proc. Am. Electroplater's Soc. 8, 22—24 (1930). Fink, C.G. and Rohrman, P.A. "The Preparation of Pure Elec- trolytic Nickel. I. The Elimination of COpper from Nickel-Copper Electrolytes." Trans. Am. Electrochem. Soc. 52. 525-338 (1930). 271. 272. 274. 275. -158 - Fink, CoG. and Rohrman, FoA. "The Preparation of Pure Electro- lytic Nickel. II. The Final Elimination of Copper and the Re- moval of Cobalt and Iron." Trans. Am. Electrochoz.;. Soc. 56 AOL-423 (19.20). _, GlaSStone, 1.8. and Spea‘acrran, J.G. "The Electrodeposition of Cobalt -N ickel Alloys . " Trans. Faraday Soc. _2_§, 565-74 (1930). Gordon, S. "Electrodeposition of Nickel for Chromium Plating." Metal Cleaning & Finishing 2 (:10 (19:0). —’ Metals and Alloys _2, Abstracts 67 (1931). Gordon, S. "The Electrodeposition of 1418101 and Chromium on Zinc Die Cast ingrs." Metal Cleaning and Finishing? _2_, 765-6 (191-0). HogabOOE, G.b. "Anode Mods.” Proc. are. Eloctroplatm"s Soc. LS, 89-91 (1920). 276. 277. 278. 279. 280. - 159 - Laban, N.R. "MasséProduction Methods in Depositing Nickel at High Current Densities.” J. Electroplater's and Depositor's Tech. Soc. SJ 129-54 (1930). Lange, H. "Defects in Nickel Plating and their Prevention." Z. ges. Giessorci praxis 51, 17-6, 22-2 (1980). Liscorh, 5.3. ”The Contamination of Solutions (in Cleaninj and L1 ectropiating-J ." Metal Inde (l:eYe) iii, 4:7-9 (19:0)e M chaughton, LoJ. and Mahmonf, h.A.E. "The Progress of Nickel Deposition in Recent Years." Chenu News 141, 283-6 (1950). Nchaughton, D.J. and Hammond, n.A.E. "The Influence of Small Ammunts of Chronnc Acid and of Chromium Sulfate on the Electro- dejosition of Nickel." Trans. Faraday Soc. 26, Pt. 8, 461-90 (1930). J. Electroplater's and Depositor's Tech. Soc. 5, 151-60 (1950). 281. 28 2. 283. 284. 28 - 160 - MacNaughtcn, D.J. and Hothersall, A.N. "StOpping-Off Materials for Use in the Electrodeposition of Nickel." Trans. Faraday Soc. 26, Pt. 4, 16L-72 (1930). O'Sullivan, J.B. "Studies in the Electrodeposition of Nickel. I. The Effect of it and of Var ous Buffering Agents. The Pre- sence of Oxygen in Deposits." Trans. Faraday Soc. 26, 83—94 (1920). O'Sullivan, J.B. "Studies in the Electrodeposition of Nickel. III. Effect of Snail Quantities of Iron and Aluminum." Trans. Faraday Soc. 26, 555-9, 540-5 (1980). Pitschner, K. "Buffer Action in Nickel Plating Solutions." Proc. Am. Electroplater's Soc. 1g, 64-67 (1950). Mougey, H.C. and Phillips, W.M. "The Deposition of Nickel at 8. LOW 13H 0" Proc. Am. Electroplater's Soc. 1g, 75-79 (1980). ,-.‘ 286. 287. 288. 289. 290. 291. -161- Proctor, G.B. "Hydrogen Pitting and Peeling of Nickel and COpper- Plated Deposits Upon High-Cannon and Other Steels." Monthly Rev. Am. Electroplater's Soc. 11,)No.7, 5—12 (1950). J. Inst. Metals 511, 359 (1931). Romanoff, F.P. "Pitting of Nickel." Monthly Rev. Am. ElectrOplater's Soc. 7, No.6, 28-53, 35-8 (1960). Je Inst. Metals E, 601 (19:1)e Shikata, n. and Hosaki, N. "The Behavior of Colloidal Particles at an Electrode." Chemo News. 140 , 55 (1980). Stout, LE. and Burch, C.G. and Longsdorg, 11.8. "Electrodeposi- tion of Copper-Nickel Alloys." Trans. Am. Electrochem. Soc. _5_7, 113-127 (1930). Werner, E. "When is Nickel Plating Rustproof?” " . Metallborse 39, 1321-2, 1378—9 (1980). Werner , E. "Nickel -P lat 111g Aluminum. " Metallbgrse 2_0, 1434 (1930). 2.92. 29 3. 294. 295. 296. -162- 1931 Altmalmsberger, K. "High-Capacity I‘iickel—Plating Baths." Oberflachentechnik _8_, 185 (1951). 2, 302 (1931). Metals & Alloys Beutel, E. and Kutzelnigg, A. "The Deposition of Sulfide Films on Metals." Monatsch. _5_8_, 295-306 (1931). Canning, E.R. "High Speed Nickel Plating as Practiced in England." Proc. Am. Electroplater's Soc. .12, 78-80 (1981). Monthly Rev. Am. Electroplater's Soc. 1_8_, No.11, 9-12. (1931). Clllldinln, C.E. "Production of Nickel Plating at LOW PH" Monthly Rev. Am. Electroplater's Soc. 1g, No.4, 32-9 (1931). Fink, C.G. and Bohrman, Ft“. "The Preparation of Pure Electro- lyt ie Nickel. Part III. Chemical and Physical PrOperties ." Trans. Electrochem. Soc. _5_9, 359-368 (1951). 297. 298. 2E9. 300 . 5010 302. ~163- Glasstme, 1.5. and Speakman, J.C. "Electrodqmsition of Cobalt- Niekel Alloys.II" Trans. Faraday Soc. _21 29-35 (1931). Glazunoz, A. and Krieglstein, J. "Iron Content of Nickel Deposits." Chem. Obzor. 6, 202-3, 225-32 (232 English) (1931). Hoefer. J- "The Use of Brighteners in Plating Solutions." Monthly Rev. Am. Electroplater's Soc. 1_8_, No.6, 23—9 (1931). Kaneko, S. "Theory of Addition Agents (in Crysallization)." J. Soc. Chem. Ind., Japan 2;, Suppl. binding 103 (1921). Laban, N.R. "Problems in High-Current-Density Nickel and Chrom- ium Deposition." J. Electroplater's and Depositor's Tech. Soc. _6, 159-66 (1931). Liscomb, E.J. "Introduction of Iron into Alkaline Cleaning and Plating Solut ions.” Monthly Rev. Am. Electroplater's soo. 1a, No.1, 17-29 (1931). - 164 - 303. MacNaughton, D.J. and Hammond, R.A,F. "Th. Influence of Acidity of the Electrolyte on the Structure and Hardness of Electrodeposi- ted Nickel." Trans. Faraday Soc. 37, 633-48 (1931). J.E1ectr0p1ater's and Depositor's Tech. Soc. (London) 6, 1-9 (1932). 304. Mandi, 11. "Medical Application of the Polarographic Method. I. The Influence of Albumin Colloids Upon the Deposition Potentials of Metals." A‘ta 5.11010 Med. UIllVe Imp. Kioto My 165-6 (1951). 305. Pan, L.C. "Chemicals-Their Function in Electr0plating." Brass World _21, 79-81 (1931). 306. Pitsehner, K. "Buffer Action in Nickel Plating Solutions." Metal Ind. (11.15) a, 119-20 (1931). 307. Setlik. B. _f'The Influence of Foreign I(letals During Nickel Plat inge 0‘ Chem. Listy 23, 123-4 (1931). 308. 309. 310. 311. 312. 313. 314. ~165 - Stout, L.E. md Faust, C.L. "Electrodeposition of Iron-Cepper and Nickel Alloys from Cyanide solut ions.I." Trans. Electrochem. Soc. 60, 271-296 (1931). Thompson, M. Dek. "Recent Deve10pments in Nickel Plating." Metal Cleaning and Finishing 3, 625-8, 717-9 (1931). Watts, O.P. "Buffering the Nickel Solution." Monthly Rev. Am. Electroplater's Soc. 13;, No.3, 4-11 (1931). Wilmer, M. "New Electrodeposition of Alloys." '9 Oberflachentech. _8, 225-6, 246 (1931). 1932 Eldridge, G.B. "Rapid Nickel Plating. " Monthly Rev. Am. Electroplater's Soc. 19, No.3, 21-29 (1932). Hothersall, A.W. "Recent British fiesearch on Electrodeposits." Compt. rend. congr. intern. elec. 2, 99-111 (1932). Hunt, L.B. "A Study,r of the Structure of Electrodeposited Metals." J. Phys. Chem. pg, 1006-21 (1932). 315 .- 316 . 517e 318 . 319 . 33)- -166 - Hunt, LeBe "The Structure of Electrodeposited Metals IV." Metal Ind. (London) $9, 1:53- (1922). Kurrein, H. "Modern Nickel Plating LII." Chem. Ztg. gag, 93-4, 114-5 (1932). Masaku, K. "Electroplating of (Silver and Copper) Alloys from Cyanide Solut ions." Bull. Chem. Soc. Japan 7 158-68 (1932). Peek, 11.1.. and Knittel, 0.11. "Treating Nickel-Bearing Solutions Contaminated with Copper and Iron.“ U.S. 1, 887, 037 Nov. 8, 1932. Phillips, W.M. "Fitting in Nickel Plating Solutions.” Monthly Rev. Am. Electroplater’s Soc. 9, No.4, 19-21 (1932). Stout, LE. "The Electrodeposition of Alloys." Washington Univ. Studies Sci. Tech. (N.S.) ng, 9-3 (1932). 321. 322. 323. 324. 325.. - 167 - Stout, LE. and Faust, C.E. "Eleotrodeposition of Iron, Capper and Nickel Alloys. II. Discussion of Results Obtained from Cyanide Solutions." 'i‘rans. Electrochem. Soc. 511, 3-41-3152 (1932). Strausser, P.W.C. "Experiences in the Plating of Samples for Reposure Tests." Proc. Am. Electroplater's Soc. _LO, 241-246 (1932)- Vueillenmier, E.A. "Peeling of Electrodeposited Nickel." Proc. Am. Electroplater's Soc. gg,‘eo-a4 (1932). Wilhelm, A. "Throwing Power of Galvanic Copper, Nickel, Zine, and Chromium Baths." Metallwa.ren-Ind. u. Galvano-‘l‘ech. §_Q_, 178.-80, 249-51 (1932). Wirehing, ReJe "Plating of Zinc Base Die Castings." Monthly Rev. Am. Eleotroplater's Soc. 1g, No.8, 9-12 (1932). 326. 327. 328. 329. 330. 331. - 168 - 1933 Forstner, 11.1.1. "Heavy Hydrogen and Heavy Water in Electroplating." N Oberflaehentech. Ll“ 39-40 (1933). Hummer, C. "Faetors Contributing Toward Quality of Plated Zinc Die-Castings." Proo. Am. Electroplater'e Soe. 31, 155—159 (1933). Xrause, H. "Electrolytic Deposits on Aluminum." Mitt. Forsohungs inst. Probieramt Edelmetalle 1, 87-9 (1933). Krause, H. "The Requirements of Good Electroplating and the Peeularities of the Most Important Platings." Oberflachentechnik .19.. 15-20 (1933 . Lisoomb, F.J. "Impurities in Nickel-Plating Solutions with Reference to Pitting of Electrodeposited Nickel." Monthly Rev. Am. Electroplater's Soc. Q, No.4, 6-15 (1933). Proc- Am. ElectrOplater's Soc. 23., 137-140 (1933). Maeehia, 0. "Most Common Defects Shown 1)." (Electro—) Depos- ited Nickel." Industria Chimica 8, 571-4 (1933). 338. 333. 334. 335. 336. 337. -169 - MacNaughton, D.J., Gardam, 8.1%. and Hammond, B.A.F. "The Influence of the Composition and Acidity of the Electrolyte on the Characteristics of Nickel Deposits." Trans. Faraday Soc. 29 729-54 (1933). Manrer, P.A. "Some Problems in Technical Control of Nickel Plating Production." Proc. Am. Electroplater's Soc. 24.9 1622-1658 (1933). Nichols, G.W. "A New Bath for the Direct Nickel ing- 0 f Zinc." Trans. Electrochem. Soc. 64 265-70 (1933). H Ollard, E.A. "Micro Organisms in Plating; Solutions." natal Ind. (London) 9.2... 17-18 (19:53). Pietrafesa, F. "The Effect of Chromium in Nickel-Plating Baths." Atti IV. congr. naz. chim. pura appl. 1933, 776-85 (1933). Pletenev, S.A. and Kuznetzova, V.V. "Electrodeposition of Alloys. I-Nickel-Cobalt Alloys." 2. Elektroohem. _._'5_9_, 301-4 (1933). 338. 339 . 340e 342 . 343. -170- Stout, Le'fl. and Faust, c.L. "Electrodeposition of Iron, 00pper, Nickel Alloys. III. Deposition from Sulfate-Boro-Cit- rate Baths." Trans. Electrochem. Soc. 6_4, 271-282 (1933). Thompson, M. Dex. "Recent Developements in Electroplating." Metal cleaning and Finishing 3, 9—18 (1933). Vuilleumier, LA. "Peeling of Electrodeposited Nickel." Qlart. Rev. Am. Electroplater's Soc. 19, No.9, 10-19 (1933). 1934 Ballay, M. "Importance of pH in Nickel Plating." Usine 4 , No.29, 37 (1934). Ballay, Mo "Nickel Plating of Aluminum." Rev. Aluminium _u, 2355-70 (1934). Ballay, hi. "Electrolytic Deposition of Iiiclrel f1!) m Baths of a pH Greater than 7." COEIpt. rende 198, 1494-6 (1924). 344. 345. 346. 347. 348. -171- Ballay, M. "Electrolytic Deposition of Bright Nickel in Presence of Colloids . " Compt. rend. 199, 60-2 (1934). Darlay, A. 'mfoliation of Nickel-Chromium Plating." Chimie & industrie §_2_, 1352 (1934). Eckardt, W. "Pinhole Elimination in Electrolytic Nickel De- posits." " Oberflachentech. 1.1. 178 (1934). Eckelmann, LoE. "Bright Nickel." Monthly Rev. Am. ElectrOplater's Soc. .219 No.4, 18-35 (1934). Proc. Am. Electroplater's Soc. 32, 129-36 (1934). Faust, C.L., Montillon, G.H. "The Electrodeposition of Cepper- Nickel and Zinc Alloys from Cyanide Solutions 1." Trans. Electrochem. Soc. §_5_, 361-374 (1934). 349. 350. 351. 352. 353. 354. - 172 - Gutmn, 13.1. and Mayantz, A.D. 'Treeing Nickel Sulfate Solu- tions from Iron and Aluminum Impurities." Tzvetnuie Metal 193 , No.6, 63-71 (1934). Hirsch, A. "Barrel Nickel Plating of Fabricated Sheet Zinc Parts." Monthly Rev. Am. Electroplater's Soc. _2_0_, No.5, 31-36 (1934). Hothersall, A.W. and Hammond, 18.11.19. "The Effect of Oxidizing Agents on Nickel Deposition I. Hydrogen Peroxideand Nickel Nitrate." Trans. Faraday Soc. 3Q, 1079-94 (l934). Hothersall, A.W. "Recent Deve10pments in the Electrodeposition 0f Nickel." Metal Ind.h(London) 5_5_, 109.12. 157.9 (1934). Kochler, W.A. "Controlling the Character of Electrodeposits." Metal Cleaning and Finishing _6_, 397-400 (1934). Mathers, F.C., Webb, G.F. and Schaff, C.W. "Alkaline Plating Bathe for Cobalt and Nickel with High Throwing Power." Metal Cleaning and Finishing _6_, 412, 418-9 (1934). '35»- L'v . to (fl 0‘; O 357. 359. 360. - 173 - Marshak, F., Stepanov, L. and Belyakova, C. "Electrodeposition of Ironahickel Alloys." Z. Elektrochem. 39, 341-4 (1954). Paweck, H., Bauer, J. and Dienbauer, J. "Electrodeposition of Copper-iickel-Iron Alloys." 2. Eleflktrochem. 39, 857-62 (19:4). Phillips, 11.12. "Pictorial Study of Plating Conditions." Proc. Am. Electroplater's Soc._g§, 199-209 (1934). V . . I... . . - . . ‘ .x Romanoff, EoP. Ductllitfi and AcheSlon of Elemel Deposits." Trans. Electrochen. Soc. 65, 385-400 (1924). Proc. Am. Electroplater's Soc. 1934, 155-162 Salauze, H.J. "Action of Addition Agents on Metallic Electro- lytic Deposits." Bull. soc. franc. 'elcc. 21; 1-19 (1934). Snelling, h.G. "Vnsatisfactory Results in Nickel Plating and their Elimination." Chem. Ztg..§§, 860-2 (1933). 361. 362. 363. 364. 365. 366. - 174 - Walter, G., Adler, M. and lieimer, G. "Electrochemical Behavior of Complex hetalthiourea Salts." Monatsh. _6_5_, 59-81 (19:4)0 Weisberg, L. and Greenwald, VLF. "Filtration of Plating Solutions." Metal Ind. (NeYe’ g, 15 (1934)e Zakharova, G., Mishurova, 11., Bellman, M. and Golendeev, V. "Pur- ifying'Nickel Sulfate Solutions by Oxidizing Iron with Air." Trudui, VNIIZh 1934, No.3, 30-6. 1935. Anderson, E.A. "Multiple Nickel Plating on Zinc." Monthly Rev. Am. Electroplater's Soc. _2_g, No.6, 24-32 (1935). Anon. "Formation of Bright Nickel Electrodeposits in the Pre- sence of Colloids." Die Metallwaren-Ind. u. Galvano-Technik.,§§, No.5, 97 (1935). Blum, W. and Kasper, C. "Characteristics of Nickel Deposited at High Current Density." Metal Cleaning and Finishing 1, 407-9 (1935). Mbnthly Rev. Am. Electroplater's Soc. gg, No.5, 19-30 (1935). -175 - 367. Brockman, C.J. "Removal of Copper Ions from Water by Sodium Aluminat e. " Ind. Eng. Chem. 21, 217 (1935). 368. Colombier, 1.- "Passive State of Metals. The Passivity of Nickel." Pub. sci. tech. ministere air (France) No.82, (1935). 369. Cosgrove, J.M. "Suspended Matter in Plating Solutions." Monthly Rev. Am. ElectrOplater's Soc. _2_2_, No.3, 27-30 (1935). 370. Costello, G.H. "Electroplating Zinc-Base Die Castings." Monthly Rev. Am. Electroplator's Soc. _LZ, No.10, 14-23 (193"). 3'71. Darlay, A. ”Difficulties in Nickel Plating." Galvano Feb. 1935, 17 an. 1935, 17. 372. DemeS, J.L. "Black Nickel." Proc. Am. Electroplater's Soc. .2_3_, 123-127 (1935). - 176 - 373. Eckardt, if. "Hydrogen-Free Deposits (of Nickel)." N Oberflachentech. .13.. 43 (1935). 374. Faust, C.L. and montillon, G.H. "The Electrodeposition of Copper, Nickel and Zinc Alloys from Cyanide Solutions. II, Dis- cusSion of the Results in Part I." ri‘rans. Electrocheiut. Soc. 131, 231—297 (1955), 375. P‘edot'ev, ;~,'.P. and Kinkul'skii, 11.8. "Electrodeposition of Nickel from Chloride Solutions." 2. rfir anorg. u. allgem. chemie 234, 337-50 (1933). 3’76. Glass'tone, S. "Electrode Potentials and the Form of Electro- Deposited Metals." Trans. Faraday SOGe fl, 1222 (1935)e 377. Gronningsaeter, A. "hemoving Iron from Nickel-Copper Solutions." U.s.1,986,967 Jan. 3, 19:5. 378. Harr, R. “Inorgan ic Acdition Salts in the Ixicknl-‘r latinsf bolt.— pr‘ '1 Trans- nem. Electrochem. Soc. 6;), n..,-444 (193.). L79 e 390. 381. 383. 384. - 177 - Holl, ii. "ixexmval of Lead and Copper from Drinking Water." .Arch. Kyg. Bakt. 113, 296-304 (1935). Hothersall, 1.3. and Hammond, RAJ. "The Effect of Oxidizing Agate on Nickel Deposition. I. Hydrogen Peroxide and Nickel Nitrate." Metal Ind. (London) pg, 201-, 251 (19:3). Iyr1‘1 Hothersall,.A.J. and HJJMDHC, “.A.F. lhe Effect of Oxidizing Agents on nickel Deposition. II. Chromic Acid.” Trans. Faraday Soc. 11, 1574-82 (1925). N {ohlschutter, V. "Somatoid Elements of Structure in Electrolytic Hetal Deposits." Trans. Faraday Soc. 31, 1181-8 (1935). Koyanagi, S. "Electrolytic Deposition of Metals from their Pyro- phOSphate Solutions." 81111. Chem. SOCe Japan E, 355-6 (1985’s Lemarchands, H. and Debiesse, J. "The Electrolysis of Solutions of Salts of Weak Bases." Bull. Soc. chin. (5)_§, 1637-8 (19:5), ”‘8?“ e. as f i (,0 O) o 387. 388. 389. 390. - 178 - Liebrich, E. ”The Effects of film Formalion on thC Structure of Electro—Deposited Metallic Coat'nns." Trrrs. Fl“nCnf Soc. C“ 1188-1194 (1925). ...-3., Macl-i‘augiaton, D.J. "Some Aspects of itescarch in Electrodeposi- tion in Great Britain." Monti-11y l‘ucv. Am. Eloctroplater's Soc. 33, No.7, 49-59 (1935.), Marslmk, F., Stepanov, L. and Levius, L. "Hlectrolytic Separa- tion of Iron-Nickel Alloy .11." Z. Elektrochem. 11, 596-7 (1935). Meyer, 37311. "The Adhesion of Electrode-posits." Proc. Am. Electroplater's Soc. _2_3, 103-109 (1935). Myastsov, A.V. "Removal of Zinc from Nickel Plating Baths." Russ. 45,152 NOVe 20, 1935s Pace, F.D. "Modern Filtration Practice in Electroplating." Monthly Rev. Am. Electroplater's Soc. 1221, No.12, 40—8 (1935). ~179 - 391. Raub, E. "The Influence of Additions to Nickel Baths; the Injurious Effect of Iron." Mitt. Forschunrsinst. fro‘oierargt Etiolmctallc 2, 1-6 (19;: . 5‘32. haul), IS. and Bihlzoaier, K. "The Control of Iiicicol—Platinb; Bat-£150" Mitt. Forschungs-Inst.I>robieramt Edelmetalle _9_, 61-8 (1935). 593. Raub, E. and Walter, E. "Electrodeposits of Nickel-Iron Alloys." 2. Elektrochem. g1, 169-74 (1955). 394. Raub, 13. md Walter, E. "The Codeposition of Nickel and Iron." Mitt. Forschungsinst. Pro‘oieramt Edelmetalle 2, 17-21 (1955). 395. Schlotter, M. "Chemical and Physical Properties of Electroly- tically Deposited Metals in Relation to their Structure." Ii'rzma. Faraday Soc. g1, 1177-1181 (1935). 596. Sohlgtter, m. "Bright Electrolytic Deposits." z. Lietallk'ldo 21, 236-7 (1935). £597. £596. 899. 400. 401. 402. - 180 - Staurenghi, E. "The New Methods of Nickel Plating." Industria, meocanioa lg, 702—4 (1935). Succhi, VoP. ”Adhesion and Causes of i-Ionadhesion of Electro- lytic Deposits." H Oberflachontech.;§J 185—6 (1925). Trmtmann, B. "Nickel Plating"; and Chromium Plating of Sheet Zinc and Zinc Diecastings." Tech-Ind. Schweiz. Chem. Ztg. ;§_, 25-7 (1935). Metallwaren-Ind. u. Galvano tech. gg, 119—20 (1955). Werner, E. "Commercial Nickel Plating." fl Oberflachentech- 33, 219-22 (1935 . 1986 Anderson, E.A. "Some Faetors Governing the Ductility of Nickel Electrodejpos its. " Proc. Am. Electroplater'a Soc. _2__41_, 1853-197 (1936). Beebe, A.H. "Bright Nickel Plating." Metals e Alloys _7_, 273-4 (1956). 403. 404. 405. 406. 407. 408. -181 - Behnke, H. "The Nickel—Silver Process." 3' Oberflashentech. 1;, 1855-4 (1936). Broslimzm, OJ. and Nowlen, J.P. "Deposition of Nickel-Cobalt Alloys from Solutions Contain ing Triethanolamine." Metal Cleaning and Finishingj 247-8, 275 (1936). Brockman, (1..}. and Nowlem, J.P. ”Alkaline Plating Baths Gon- taining Ethanolamines. II A Study of Baths containing Triethanola— mine for the Direct Nickel Plating of Zinc." Trans. Electrochem. Soe. §_9_, 541-551 (1936). Broskman, Gulf. and Nowlen, JoP. "Alkaline Plating Baths Con- taining the Ethanolamines, IV. The Deposition of Nickel-Cobalt Alloys from Solutions containing Triethanolamine." Trans. Electrochem. Soc. fig, 553-555 (1936). Oahour, J. "Hardness of Electrolytic Deposits of Nickel." Oompt. Raid. 202, 659-60 (1935). Gosgrove, J.m. "The Electrodeposition of Nickel on Zinco" Proc. Am. Electroylater's Soc. _2_z}_, 265-275 (1936). 4099 410. 411 . 4120 415. 414. -182 - Cotton, D.J.. "Buffer Chemicals in Nickel Solutions." Proc. Am. Electroplater's Soc. _2_{i_, 276-285 (19313). Cymboliste, M. "The Formation and Growth of Pits in Electro- deposited Metals." Trans. Electrochem. Soc. fl, 879-394 (1986). Darlay, A. "Defects and Errors in Nickel Plating, Their Causes and Prevention." H ‘ Oberflaehentech. lg, 184-5 (1935) e Faust, C.L. "Plating Comer-Niekel-Zino Alloys from Cyanide Baths." Metal Cleaning and Finishing 8 819-24, 334 (1956). Flowers, L.C. "Throwing Power and Current Distribution in Plating Baths. III.“ Metal Cleaning Finishing _8_, 767-8, 770 (1956). Glazunov and Dreseher, E. "Colloidal Addition Agents in Eleo- trolyt is Baths . " Metallwaren Ind. Galvano-Tech. _sg, 131-3 (1956). 415 . 416 . 417 . 413 o 419 . 420. -183- GOI'tX. MN. and Kahrlamv, V.N. "Electrolytic Deposition of Alloys of Tungsten and Nickel and of Tungsten, Nickel and Copper from Water Solutions." Je App110d Chem. (UeSeSeRe) _9_, 640-52 (111 German 652) (1936). Hogaboom, G.B. "Alloy Plating (Cobalt-Nickel Alloyh" Products Finishng 1‘; No.1, 16-18 (1956). Johnson, C. "Films and their Relation to Cleaning Methods BeforeElectroplating." Proe. Am. Elestmplater’s See. 33, 149-161 (1956). Kersten, H. and Young, W.'1‘. "Improved Method for Electro- depositing Alloys." Ind. Eiige Chem. _2_8., 1176-7 (1936)e Lapin, N.P. and Matveeu, C.P. "Influence of Cadmium Salts in Nickel-Plating Baths upon the Properties of Nickel Deposits." Je Applifid Chem. (UeSeSehe) 2, 1260-8 (1936)e Mathers, F.C. "A Review of the Electroplating Research at Indiana University.” Pros. Am. Electroplater's Soc. _ZA, 162.-16$?! (1936). ‘421. 422. 425. 424. 425. 426 . - 184 - McKay, ReJe "Some PrOperties of Nickel Electrodeposits." LIOtals & AlloyS. 7 193—8 (1956)e Meyer, V7.13. "The Adhesion of Electrodeposits." Monthly Rev. Am. Electroplater's Soc. 251, No.2, 5-57 (1936). Meyer, 17.3. "The Orientative Effects of the Geometrical and Crystalline Stmeture of the Basis Cathode on the Crystal Struc- ture of Electrodeposits." Proc. Am. Electroplater's Soc. 24, 123-130 (1936). Meyer, Phil. aid Helmle, 0.0. "The Eleetroplating on Lead- Antimony Alloys." Metal Cleaning Finishing e, 751-6 (1936). Monthly Rev. Am. Electroplater'e Soc. 2_3, No.5, 7-25 (1936). Pace, F.D. "Modern Filtration Practiee in ElectrOplating." Metal Cleaning and Finishing _e, 233-8, 260 (1956). Parks, WC. and LeBarron, I.M. "The Codeposition of Metals of the Same Valenee in Acid Solutions." Trans. Electrochem. Soc. 19 375-7 (1936). 427. 428. 429. 430. 451. '185 - V'- Polyakov, V.D. "Nickel andChromium Plating of Tungsten Fila- mtse" J. Applied Chem. (U.S.S.R.) 2, 1055-? (in English 1057) (1956). Raikes, 11.11. "Ions and the Conduction of Eleetrieity.“ Trans. S. African Inst. Elee. Engrs..§1, 147-58 (1956). Roberts, J.L. Jr. “Nickel Plating on Cadmium and Zinc—Plated Steel." Monthly Rev..Am. Electroplater's Soc. 25, No.5, 24-55 (1956). Sacchi, V.P. "Nickel and Chrome Plating of Zinc and Dieeast Zinc." Industria Meccaniea 18, 554-9 (1956). Spenser,.A.G. "Effects of Composition and Structure Upon Corrosion of Nickel Anodes." Proc. Am. Electroplater's Soc. g1, 285-298 (1956). Stout, L.E. "A Critical Study of Bright Nickel." Ebnthly'Rev. Am. Electroplater's Soc. 5, No.6, 54-9 (1956). 433. 434. 455. 437. -186 - Vozdvizhenskii, G.B. and Faizulin, F.F. "The Influence of Colloids on the Cathode Polarization and Electrodeposition of Nickel in the Presence of Paal Mixtures." J. Phys. Chem. (U.S.S.R.) p, 472-6 (1935). Vozdvizhenskii, G-S. and Makolkin, LA. "Na’mre and Mechanism of Streaky Nickel Deposits." J. Applied Chem. (U.S.S.R.) 2, 1425-26 (1935). Vozdvizhenskii, G.B. and Suleimanova, R.Z. "Bright Nickel De- posits on Unpolished Surfaces." J. Applied Chem. (U.S.S.R.) 2,11415-22 (in German 1422) (1956). Wai te, M. "The Effect of Nickel Chloride in Nickel Plating Solu- tions." Proc. Am. ElectrOplater'e Soc. 3%,, 225—252 (1956). Werner, E. "Nickel Glanee Electrolytes and their Use." Werkstaatstechn. u. Werksleiter 5Q, 1865—? (1956). 438. 439. 441. 44%. ~187- " Wille, 8.. And Volkel, ‘sJ. 'liemoving Iron from Solutions of Nickel and Cobalt." Ger.628,514 Apr.6,1956. Deutsehe Gold-und Silber-Scheideanstult Vormals Roesslero Young, G.B.b‘. and Gould, N.A. "Nickel-Cobalt Alloy Plating from Acid Sulfate Solution." Metal Ind. (London) $.82. 541-4 (1935). Trans. Electrochem. Soc. Q, 585-594 (1956). 1937 Anderson, EOAO, Reinhard, OeEe and Kittleberger, .IVetVe "Thfl Plating of Zinc -Alloy Die Castings and Rolled Zin c." Metal Cleaning Finishing .9, 721-6, 755-6 (1957). Cymboliste, M. "Inclusions in Electrodepos its, Their Orgin and Their Effect on the Structure and Mechanical Properties.” First Intern. Electrodep. Conf. 1257, l4pp. Cymboliste, M. and Salauze, J. "Blister Pits in Electrodeposits." Trans. Electrochem. Soc. 11, 255-46 (1957). 443. 444. 445e 446. 447. 448. - 188 - Egeberg,B. and Promisel, N.E. "Testing and Stri ping of Electrodeposits. III Nickel and Cobalt." metal Cleaning and Finishing g, 575-82, 492-7 (1937). Franssen, H. "Saving of Nickel by Nickel Plating." fl Oberflachentech. 1g, 174 (1957). Glazunov, A» md Schlotter, M. "Comments on the Electrolysis of Solutions of Complex Salts." First Intern. Electrodep. Conf. 125 . Hirsch, A. "Cathode Efficiency of Electroplating Barrels and Its Effect on the Adhesion of Nickel Deposits." Proc. Am. Electroplater's Soc. pg, 97-105 (1957). Hothersall,.A.W. and Gardan, G.E. “Nickel Baths. Organic Contaminants in Nickel Baths. Sources and Methods of Puri- fication." Metal Ind. (London) 50, 609-12 (1957). Johnson, L.W. "Bright Nickel Plating. Resume of Technical Literature." Metal Ind. (London) 6g, 281-6 (1937). 449. 450. 451. 452. 453. 454. - 189 - Kersten, H. and Young, W.T. "Electrical Conductivity of’Nickel- Sulfur Electrodeposits." J. Applied Phys. 8, 153-4 (1957). Kochanovskii, A.M. "Nature of the Inactivation of Ions in Solu- tions of Lyophilic Colloids." Colloid J. (U.S.S.‘i{.) g, 521-6 (1937). Krause, H. ”Defects in Electroplating and Metal Coloring." N Oberflachentech. 14, 75-5 (1957). Krzyanowski, J. and Gurewicz, A. "Electro-deposition of CapperéNickel Alloys." Przemgsl Chem..éln 206—15 (1957). Liger, J. "The Passivity of Metals and its Application to Electroplating." Metal Cleaning Finishing 2, 681-6 (1957). Meyer, W.R. "Bright Deposits. Thickness Control. Feature Plating Progress." Metal Cleaning and Finishing 2, No.2, 105-108 (1957). 455. 456. 457. 458. 459. 450e - 190 - Meyer, 17.1%. "The Orientive Effects of the Geometrical and Crystalline Structure of the Basic Cathode on the Crystal Structure of Electrodeposits." Monthly Rev. Am. Electroplater's Soc. fig, No.2, 95-107 (1957). Meyer, 17.11. "Electroplating “in Europe and the First Inter- national Conference on Electrodeposition." Proc. Am. Electroplater's Soc. 35, 48—69 (1957). Pinner, W. 11.. and Sperry, 1.15. "Experiences in Evaluating Plated Coatings." Proc. Am. Electroplater's Soc. _2_5_, 55-45 (1957). Raa'b, E. and Bihlmaier, K. "Electrodeposits of White Gold." '1 Mitt. Forsch.-Inst. Probieramts Edelmetalle Staat. hoheren ,, . Fachschule Schwab. Gmund 1;, 59-65 (1937). Raub, E. and Wittum, M. "Lead in Nickel Solutions." 0. Korrosion u. metallschutz 1;, 261-6 (1957). Raters, H. "Rust Protection. III." Mitt.Forsch.-Inst. Probieramts Edelmetalle staatl. hgheren Fachschule schwgl) Gmiind. 1_1_, 27-35 (1937). 4510 4530 464. 465. 466. -191 '- Schlotter, ii. "Electrolytically Refined Metals with Different Properties." Research 6: Progress 5, 159-62 (1957). Sizelove, D.J. "Bright Nickel Plating." Monthly Rev. Am. Electroplater's Soc. 34, 193- (1937). Spencer, A.G. ”Corrosion of Nickel Anodes." Metal Ind. (London) 52,, 141-4 (1957). Springer, R. "Bright Nickel Plating." N Oberflachentech. 13, 49-51 (1957). Springer, B. "The Use of Insoluble Anodes in Plating Baths." Z. Metall. u. Schmc‘maren-Fabrikat. Verchrom. 1g, No.10, ll-13; No.11, 11-12 (1937). Tiquet, R. ”Slimes in Electrolytic Baths." Metal Cleaning Finishing 2, 507-10 (1957). 467. 468. 469. 470. 471. - 192 - Underwood, J. and.Philadelphia Branch (A.E.S.) "A Discussion on Barrel Electroplating." Proc. Am. Electroplater's Soc. 36 , 44-47 (1957). Weisberg, L. WPurifying NickeléPlating Solutions by Electro lysis." Metal Inde (I'JeYe) £5, 451-3 (1937). Wittum, M. "Effect of Lead in.Niokel Baths." Forsch. -Inst. Probieramts Edelmetalle staatl. ho'heron H Fachschule schwab. Gmund 1;, 75-7 (1957-58). Young, G.B.F. and Egerman, C. “Nickel-Cobalt Alloy Plating from Low pH Acid Sulfate Solutions." Trans. Electrochem. Soc..1§, 447-458 (1957). Metal Ind. (London)_§;, 605-8 (1957). Young, W.T. and Kersten, H. "A Study of Electrodeposits Con- taining Nickel and Sulfur." Trans. Electrochem. Soc. 1;, 225-229 (1957). 472. 473. 474- 475. 476. - 193 - 1958 Amberg, B.J. "Filter Aids for Filtration of Electroplating Solutions." Metal Ind. (N.Y.) fig, 556-557 (1958). Monthly in. Am. Electroplater's Soc. gag, No.9, 741-747 (1958). (Anderson, E.A. ”Plating Zinc Alloy Die Castings Commercially." Metal Cleaning Finishing 12” 482-90, 514, 548-52, 610-12, 614- 16, 642, 679-80, 682, 684, 704 (1938). Blount, E.A. "The Use of a Wetting Agent to lrevent Pitting in Not Iickel Solutions." Products Finishing 2, No.8, 57-9, 42 (1958). Bulakh, A.A. "The Presence of Metallic Magnesium in Nickel Deposited by Electrolysis." Korroziyai Bor'ba.s Nei 4, No.2, 164-6 (1958). Faust, C.L. and Montillon, G.H. "The Electrodeposition of Copper-NiCkcl-Zinc.Alloys from Cyanide Solutions.III." Trans. Electrochem. Soc._15, 417-4L1 (1926). 477. 478. 479. 480. 482. - 194 - Fulforth, F. "Bright Nickel." Product: Einishinc EA Lo.f, 17-21 (1553;, Helbir, 1.“. ”activz QC Carion in Electroylatinfi Solutions.” B19133]. Ind. (l‘sieYe) E, 555-5 (1938), Hothersall, A.“. and Gardam, G.E. "The Value of an Alterna- ting Bend Test in the Examination of Nickel Deposits." J} Electrodepositor's Tech. Soc. 14, (1938). Hothersall,.a.u. and Hammond, n.A.F. "The Causes of Porosity in Electrodefositefi Coatings, “swecially of-Lickel on Steel." Trans. Electrochem. Soc. 72, 449-474 (lQCS). . '~ -‘~_ _ _ ‘ ‘ ‘ n-w -\ -, . . Lainey, V.L. ”LC onztunovsLara, L.G. alcctrooogo51tion of -. , H Coyperbhicxel Alloys. Korroziya i Bor'ba s Lei g, Ho.1, E-SO (19:8). Maker'eva, 8. "Effect of Conyosition of Electrolyte, the Curr- ent Density, and Bath.Tonpcrature on the Proper Ties of Electro- lytic Kickel." Bu11.Acad.Sci.U.R.S.S.,Classe sci.matn.nat.,Ser.chim.Il§§§,l2ll- 2 (in English 1223-4). 483. 484. 485. 466. 487. 488- - 195 - Mathers, F.C. and Johnson, 21.”. "Electrodeposition of Silver Alloys from Aqueous Solutions." Trans. Electrochem. Soc. 14, 229-250 (1988). Mattacotti, V. "Purification of (Nickel) Solutions by Elec- tro1y3150" Monthly liev. Am. Electroplater's Soc. _2_5_, 513-20 (1938). Meyer, \‘i.h. "Methods of Mixing: Filter Aids with Plating; Solu— tions." Metal Ind. (N.Y.) g9” 556-9 ( 938), Neusorov, isol- "h’xyid nickel Plating of Printor's Typo." Poligraf. lroizvodstvo 192 10.5, 20-1. il‘ex'.rark Branch (AoE.S.) "‘u’etting A{-‘cnts in Nickel Plating Solutions." Proc. Am. Electrolalater's Soc. _2_§, 22::.—257 (1938). Parks, ‘~.'=J.G. and Lebaron, Lil. "Codeposition of Metals of Unlike Valence in Acid Solutions." J. Phys. Chem. 42, 125-21 (1938). 489. 490. 491. 492. 494. - 196 - Pinner,‘W.L. and Borehert, L.0. "The Importance of PrOper Anode Corrosion in the Electrodeposition of Nickel." Proc. Am. Electroplater's Soc. fig, 84-90 (1938). Pinner, W.Lo and Borehert, L.0. "Further Notes on Nickel- Anode Corrosion." Monthly Rev..Am. Electroplater's Soc. gg, 909-10 (1938). Pollack, A. "The Aging of Plating Baths." ll Oberflachentech..l§, 41-3 (1938). Pozzi,Escot "Action of Ethanolamines on Solutions of Various Metallic Salts; Salts of Copper, Mercury, Cadmium, Cobalt and Ni ckel o " Rev. cienc. (Peru) 49, No.424, 203-7 (1938). Q Soderberg, G. "Bright Nickel Plating." Proc. Am. ElectrOplater's Soc. as, 74-83 (1938). Springer, Rm " The Recovery of Metals from Wastes." Z.Metall.-u. Schmuckwaren-Fabrik.Verchrom. 12, No.7, 11-12; No.9, 11-12 (1938). 495. 496. 497. 498. 499. - 197 - Tour, S. "Influence of Trace Elements on Characteristics and PrOperties of Metals." Iron Age 141, No.1, 137-44 (1938). Weisberg, Lo "Commercial Electrodeposition of Cobalt-Nickel Alloys." Trans. Electrochem. Soc. 1:1, 43"-444 (1938). Wesley, W.A. "Physical Preperties and Uses of Heavy Nickel DQ081133." Monthly Rev. Am. ElectrOplater's Soc. g5_, 581-603 (1938). Proc. Am. Electroplater's Soc. 36, 58-73 (1938). West, AoC. "Nickel Plating." Can. Metals Met. Inds. 1, 84-7 (1938). West, A.0. "The Use of Nickel Sulfate _in ElectrOplating." Trans. Can. Inst. Mining Net- 4.1.. (in Can. Mining Islet. Bull. No.318), 453-60 (1938). 500. 501. 502. 503. 504. 505. - 198 - 1939 Ballay, M. "Electrolytic Deposits in France." Proc. Am. Electmplater's Soc. 31, 30-37 (1939). Belke, V1.33. "Development of Filters for Plating Solutions." Metal Ind. (NOYO) L7,. 27-50 (1939). Cambi, L. and Piontelli, R. "Sulfanate Baths for the Electro- deposition of Metals." Bend. ist. lombardo sci. Z_2_, No.1, 128-32 (1939). Choguill, H.S. "Electrodeposition of Some Metals from Solu- tions of their Sulfamates." Trans. Kansas Acad. Sci. 32,, 213-15 (1939). Eckardt, W. "NickeléPlating on Zinc." Z. MetalL-u. Schmuclnvaren.—Fabr. Verchrom. &, 275—6 (1939). Esin, O. and Loshkarev, LI. "Cathode Polarization of Nickel." J. Phys. Chem. (U.S.S.R.).l§, 186-93 (1939). 506. 507. 508. 509. 510. - 199 - Evlannikov, Bold. and Neiman, 11.5. "Nickel Plate Free from Pin- holes." Trans. Leningrad Ind. Inst. 1939, No.1, Sect.Met. No.1, 3-23. Finnie, E. "Practical Plating Sugestions." Products Finishing _4, No.2, 44 (1939). Francis-Carter, C. "Recent Developments in British Plating Practice." Proe. Am. Eleetmplater's Soc. 21, 9-16 (1939). Gardam, G.B. "Experiments on the Distribution of Electro- deposits, On a Cup-Shaped Cathode." Proc. Am. Electroplater'e Soc. 31, 16-24 (1939). Gernes, 13.0., Lorenz, G.A. and Montillon, G.H. "Single Metal Deposition of Capper Cadmium, Zinc and Nickel from Thiosulfate Solutions." Trans. Electrochem. Soe. _'7_Z, 177-203 (1939). 511. 512. 513. 514., 515. - 200 - Gindlin, V.K. "Nickel-Plating." Naueh.Zapiski Khar'Kov Poligraficheskogo Inst. 1939, No.3, 243- 256. Khim. Referat. Zhur. 4, No.3, 82 (1941). C.A. 7, 4307 (1943). Glazunov, A. "The Formation of Anodic Deposits." Chem. Listy 313, 183-6 (1939) (English Summary). Greene, G.U. "The Rate of Decomposition of Hydrogen Perozide in Nickel Sulfate Plating Baths.“ Trans. Electrochem. Soc. _7_5_, 391-399 (1939). Grube, G. and Croatto, V. "The Polarization of the Electroly- tic Hydrogen Evolution on Alloys of Nickel with Iron and Cobalt in Alkaline Solution." 2. Elektroehem. $8, 815-3) (1939). Hogaboom, G.B. "Water in the Plating Room." Metal Ind. (ITeYe) :12, 165-7 (1939). 516 . 517. 518. 519. 51). 5210 -201- Hothersall, AJV. and Gardam, 6.3. "The Structure and Proper- ties of Bright Nickel Deposits." J. Electrodepositors Tech. Soc. 15, 127-40 (1939). Hothersall, 1.3-7. and Gardam, G.E. "Bright Nickel Deposits- Their Structure and PrOperties.“ Metal Ind. (London) _5__5_, 458-8, 493-5 (19:59). Izgaryshev, N.A. and Ravikiovich, 3511.11. "The Electrolytic Preparation of Copper-Z inc-Nickel Alloys." J. Gen. Chem. (U.s.s.n.) 2, 1445-55 (1939). Jeveli, E.S. "Purifying Bright-Nickel Solution." Monthly Rev. Am. Electmplater'e 30.. 25 195-3 (1939). Kochergin, 8.11. "The Theory and Practice of Nickel Elec- troplating." J. Applied Chem. (U.S.S.R.) 3, 44-5 (in French 45) (1939). Kohlsehutter, V. and Eggenbergev, H. "Formation of Somatoidal Elements of Structure in the Electrolytic Deposition of Metals." Helv. Chim. Acts _2_2_, 283-310 (1939). 522. 524. 525. 526. 527. - 202 - Roster, J.,ZKniekerbocker,.R.G., Garst,O.C., Evans, T.E.,Cody, W.E. "Beeovery of Nieke1,Copper, and Precious Metals from Domestic Ores by a Combined Electrothermal and Electrolytic Method." - U.S.Bur. Mines, Rept. Investigations 3483 (1939). Krause, H. "Nickel-Plating Stainless Steel." Z. iietall-u. Schmcin'.?are;_-Fabrik. Cerchrom. _gg, 419-21 (1939). Lemens, J. and Dupont, J. "Nickel Plating; on Cast Iron." Ing. Chim._§§, 73-104, 120-41 (1939). Machu, Willibald "The Influence of Colloid: on the Struc- ture of Electrodeposits. " u , Osterro Chem. -Ztg._g§, 244-7 (1939). Mathers, F.C. "Complex Cations as the Important Influence in Plating Baths." Proc. Am. Electroplater's Soc. _2_'Z_, 134-142. (1929). Mattacotti, V. "Impurities in Plating Solutions." 11958.1 Ind. (NeYe) _3‘_7_, 259-54: (1939)e 528 , 529. 530. 531. 533. - 203 - LicDuffie, R.O. and McFarlane, T.P. "A Study of Nickel Anode Corrosion and the Loose Nickel Phenomenon." Proc. Am. Eleetmplater's See. .31. 87-94 (1939). Meyer, W.R. "Filtration of Eleetmplating Solutions." Metal Ind. (NeYe) 3, 117-121 (1939)e lionselise, C.G. "Electrolytic Production of Very Pure Nickel from its Alloys." Helv. Chim. Acta. 3.3, 935-7 (1939). Piontelli, B. "Effect of Gas Bubbles on the Electrodeposition of Metals. " Rend. ist. lombardo sci. 12, 10-35 (1939). Piontelli, B. and Giulotto, A. "Electrodeposition of Metals from Solutions with Sulfamic Acid or its Salts." Chimica e industria (Italy) 21, 478-91 (1939). Puri, U°S' and Bhatla. U35. "The Action of Inorganic Colloids on the Electrodeposition of Nickel." J0 Indian Chem. SOC. lg, 71-4 (1939)e 534. 535. 536. 5:7. 539 . Raub, E. and "u‘iittu, ii. "Cadmium and Arsenic in Nickel Baths." Korrosion u. metallschutz .12. 127-30 (1939). Shcherbakov, I.G., Loshkarev, N.A. and Loshkarev, A.F. "Effect of Organic Impurities in the Electrolyte Used in hefining Nickel. I." Tsvetnye Metal. 1939, No.9, 77-84. Shcherbakov, I.G., Loshkarev, N.A. and Loshkarev, A.F. "Effect of Organic Impurities in the Electrolytes Used in Refining Nick- 810" Tsvetnye Metal 1.939, No.12, 87-91. Shlyamberr, Y.A. "The Nickel Plating of Hard Lead Stereotype Plates." Poligraf. Proizvodstvo 1939, No.6, 32-5. Smith, C.W. "Purification and Filtration of Plating; Solutions." Monthly Rev. Am. Electroplater's Soc. _2_£§,, 687-95 (1939). Smith, C.W. "Cleaning of Plating Solutions. A Discussion of Purification and Filtration Methods." Metal Ind. (London) _5__5_. 415-17 (1939). 1) l .IIIIIII II!!! l‘lll'r‘lrllll i 540. 541. 542. 543. 544 . 545- -205- Stocker, DoA. "Bright Nickel Plating." Monthly Rev. Am. Electroplater's Soc. .2151. 111-21 (1939). Weisberg, Lo uPurifying of Bright Nickel Solutions.” Monthly Rev. Am. Electroplater's Soc. 3_5.. 122-3 (1939). Weisberg, L. "Rapid Methods for Heavy Nickel Plating. " Monthly Rev. Am. Electroplater's Soc. §_6_, 929-36 (1939). Werner, E. "The Use of other Protective Coatings in Place of Nickel Plating." Werkstatt u. Betrieb. 1_2_, 2-7 (1939). Wittum, M. "The Effects of Cadmium and Arsenic in Nickel Plating Solutions." ‘ " Mitt. Forsch.-Inst. Edelmetalle Staatt. Hohern Fachschule Schwinn. Gimmd, June 1939, 13-17. Wood, Do "Agitation." Proc. Am. Electroplater's Soc. June 31, 147-49 (1939). 546. 547. 548. 549 . 550. 5510 Young, G.B.F. "The Effect of Certain Wetting Agents on Nickel DQpOIits." Proc. Am. Electmplater's Soc. June .21, 187-92 (1939). 1940 Belyaev, P.P. 31d Lipovetskaya, A.I. "ElectrOplating with Tungsten and Molybdenum." Korroziya i Borba s Mei 8, No.2, 47 (1940). Broughton, WAY. "Modern Practice in (l‘fickel)P1ating Zinc Alloy Die Castings." Monthly Rev. Am. Electroplater's 21, 346-52 (1940). De Nora, V. "Investigation of the Electrodeposition of Nickel- 21116 Alloys." Met. ital. _8_g,187-92 (1940). Downie, C.C. "Direct Bright Nickel Plating." Elee. Times 91, 446 (May 23, 1940). Fadeeva, S.M. "Nickel-Plating of Electrolyzer Parts at High Current Dene ities." Trudy Tsentral. Lab. Zavoda "Bol'shevik" 1_9_4LO_, 115-26. Khim. referat. zhur. 4, No.5, 86 (1941). C.A. g7, 5911 (1943)- 552. 554. 555. 556. 557. -203- Faust, C.L. "Electmdeposition of Alloys, 1930 to 1940." Trans. Electrochem. Soc. 18, 383-417 (1940). Fischer, H. "Modern Problems and Processes of Electrochemic- try." Elektrotech. Z. _6_1_, 121-5, 147-9 (1940). Fiseher, J. "Savings in Material and Time in Electroplating." Maschinenbau—Betrieb 33, 77-80 (1940). Glazunov, A. "The Cause of the Greater Covering Power of Metals Deposited from Solutions of Complex Salts." Chem. Listy 3.14, 2-4 (1940). Green, R.J. "Advanced Filtration." Monthly Rev. A11. Electroplater's Soc. 31, 670—3 (1940). Hanaker, 11.0. and Verwey, D.J.W. "Role of the Forces Between the Particles in Electrodepositions and other Phenomena." Trans. Faraday Soc. 314. 180-5 (1940). 559. 560 . 561. 562. -209 - Hartshorn, D.S.Jr. "Surface ri‘ension of Plating Solutions." Metal Finishing.- gs, 476-8 (1940). Hogaboom, G.B. "The Trends of E1ectroplating.’ Proc. Am. Electroplater's Soc. gfi, 40-44 (1940). Izgaryshev, N.A. "New Methods fbr Protecting Metals from Corrosion." Trudy Soveshcarmiya Voprosam Korrozii 1243, 1615-72. Khim. Referat. Zhur. 1239” No.7, 152—3. C.A. gs, 6126 (1942). Izgaryshev, N.A. "Electrodeposited Metal Films and the Theory of Electrode Processes." Trudy Vtoroi Konfersntsii Korrozii Metallov.l, 45—59 (1940). Khim. Referat. Zhur. 4, No.5, 86 (1941). C. . ”7, 5911 (1943). U — Krauso. H. "Electroplating Stainless Steel." Korrosion u. fietallsohutz_l§, 304-8 (1940). 563. 564. (TI 03 ('3‘ o 566. 567. 568. - 210 - .Kushner, J.B. "Modern Bright Plating." Metal.Progress §§J 781-5 (1940). Leffinewell, G. and Lesser, lon "Glycerol in metal Processing." Metal Ind. (Isnoq'o) a, 79-81, 8: (1940). Mathers, F.C. and Guest, w.J. "Effect of Glycerol on the Throw- ing Power ofIPlating Baths." Trans. Electrochem. Soe._Z§, 529-342 (1940). I' Morkhov, 11.1. and Atohi, L-P. "Electrodeposition of Nickel in Presence of Iron." Korroziya i Bor'ba s Nei é, No.5-6, 10-15 (1940). Khim. Referat. Zhur. _4, No.7-8, 91 (1941). 0.21. gs, 684 (1944). Q | Morokov, h.I., Stepanov, D.V. and moroko, S. "Electrodeposltion of Nickel in the Presence of Arsenic." J. Applied Chem. (11.3.8.1i.) 1;, 1222-5 (111 French 1225) (1940). Pesin, Ya.m. and Andreeva, 0.1. "Purifying Nickel Electrolyte." Russian 57,817 Aug. 21, 1940. 569 . 570. 571. 572. 57 ~21].- Philligs, tH.121. "Effect of Nevins: Cathodes." Proc..Am. Electroplater's Soc. as, 87-91 (1940). Puri, v.3. and Juneja, C.G. "Effect of Inorganic Colloids on Electrodeposition of Nickel on Coyper." J. Indian Chem. Soc. _1_'L, 561-5 (1940). Puri, v.5. and Li'filrmod Alvi, 19.1). "Electrodeposition of Nickel on Iron and the Effect of Colloids on the Nature of the Deposit." Raub, E. and iv'ittum, M. "The Influence of Organic Compounds in Nickel Plating: Solutions.“ Z. fur. Elektrochem. u. angels. phys. chcmie g6, No.2, 71-82 (1940)- Iuietfll Ind. (1278.5) :3, 206-8, 210 (1940). Metal Finishing it}, 315-317, 429-422 (1940). Richards, E.T. "Twenty-Five Rules for the Nickel-Plating 01' Zinc D ie-Cast ings . " Werkstattstech. u. Werksleiter _5_2, 117-18 (1940). 574. 575. 576. 577. 578. -212 - Sz-lmartsev, A.G. "Passivstion Phenomena During:- the Electrolytic Crystallization of Metals." Trudy Vtoroi Konferentsii Korrozii Metallov 1, 132-47 (1940). lihim. liefcrat. Zhur. 3, No.5, 119 (1941). one. _s_7, 5912 (1942-). Samuel, John 0. "Removing Iron Impurities from Nickel and Cobalt Solutions." Brit. 516, 657 Jan. 8, 1940. Shcherbakov, I.G., Loshkarev, N.A. and Loshkarev, A.F. "Effect of Organic Impurities in the Electrolyte Used in Refinine‘ Nickel. III. Methods of Purification of Electrolytes." Tsvetnye metal 1940, No.2, 61-4. Shcherbakov, I.G., Loshkarev, A.G. and Loshlcarev, LA. "ligleri— mental Electrolytic Refining of COpper-Nickel Anodes at the Ufalei ‘é'ori's (Russia)." Tsvetnye Metal. 1940, No.8, 75—8. Skalozubov, ELF. and Goncharova, LA. "Cathodic Deposition of I ron-Chro mium-Ix?‘ ickel Alloy. " Izvest. Novocherkasskogo Ind. Inst. im. 3. Ord-Zho.li};odze é, SerJChim. 24-8 (1940). 579. 580. 581. 582. 585. 584. -213 - Skalozubov, ILF. and Vlasova, A.3. "Cathodic Deposition of Chromium-Lickel Alloy." Irvcst. Novocherkasskogo Ind. Inst. im. 8. ordzhonikidze 6, Ser Khim 15-18 (1940). Sklgarcnko, 8.1. Drazhina, 0.8. and Hasal'tseva, iofi. "Elec- trodeposition of Tungsten and its Practical'Utilization." J. Applied Chemo (133.919.) 1;,1226-31 (in French, 1221) (1940). Sterling, JoGo 'Tlickel Plating." Metal Ind. (London) .56, 14-15 (1940). Weisberg, L. "Cobalt-Nickel Plating Solutions." Metal Finishing g9, 218-320 (1940). Weisberg, L. "Recent History of Certsin Cobalt-hickel Alloy Plating Solutions." Trans. Electrochem. Soc. 11, 223-229 (1940). Wernick, S. "Factors in the Production of Perfect Nickel Platins." iletal Ind. (Lone-on) g1, No.26, 514-17 (1940). J. Electrodepositor's Tech. Soc. 6, 55-44 (1940). 585. 586. 587. 588. 589. - 214 - Wernick, S. andSilman, H. ”The Technique of Filtering Plating Solutions." J. Electrodepositor's Tech. Soc..1§, 89-114 (1940). Metal Ind. (London) £8, 553-6, 59, 26-8 (1941). Wesley, W.A. and Carey, J.W. "The Electrodeposition of nickel from Nickel Chloride Solution." Metal Ind. (h.Y.) gs, 127-47 (1940). 'Wesley,‘W.A. and Cirey, Jow. "Electrodeposition of Nickel from Nickel Chloride Solutions.I." Products Finishing g, No.5, 9-12, 14,16,18,20 No.6, 18-20,22,£ , 26-27, 30,22,54 (1940). Wittum, M. "The Behavior of Lead in Nickel Baths." '1 Mitt. Porsch. -Inst. Probieramts Edelmetalle staatl. hoheren Fachschule schwgb. Gmflnd 11, 73-7 (1940). WynneAWilliams..A.I. "The Filtration of Plating Solutions." Metal Ind. (London) g1, 18-16 (1940). 590. 591. 59 2. 595. wynne-Williams, A.I. "Filtration of Electrolytes in Electro- deposition." J. Electrodepositor's Tech. Soc. 16$ 22-33 (1940). Young, G.B.F. "An Investigation of Electrodeposited Gold Alloys." Lletal Ind. (I‘é‘reYo) £29., 194-6 (194:0). Young, G.B.F. "Studies in BrightANickeléPlating'Processes." Proc. Am. Iflectroplater's Soc. 29, 124-32 (1940). Zhurin, A.I. and Kavitskaya, S. "Production of Nickel by Electrolytic Refining of Alpha-Garnierite matte." Tsvetnye. Metal 15, No.1, 80-5 (1940). 1941 Crows, J.B. "Sulfated Fatty Alcohol in Metal Cleaning and Plat— ing Baths." Products Finishing 6, No.2, 56-9 (1941). ‘Davis, R.F., WOlfc, KoM. and Grance, W.G. "Effects of Wetting Agents on the E1 ectrodeposition of Nickel." Ind. Eng. Chem. 35;, 1546-8 (1941). 596. 597. 598. 599. 600. 601. - 216 - 'Diggin, MeB. "The Effect of Water Impurities Upon Nickel Deposits." Metal Finishing g2, 18-15 (1941). Dipgin, MoB. "Nickel Plating Without Nickelchlorideo" Monthly Rev. Am. Electro later's Soc. jfid 793-5 (1941). Glazunov, A. "The Origin of Impurities in Metallic Coatings and their Influence on Corrosion." Kbrrosion u. Metallschutz. 11, 387-90 (1941). Green, ReJ. "Prevention of Modular and Porous Nickel Coatings." Metal Finishing £9, 559-60 (1941). Halls, E.E. "Bright Nickel Plating." Metal Treatment.l, 11-13 (1941). Halls, E.E. "Nickel and Cobalt Salts for Electroplating (of Metal 8) 0" Sheet Metal Ind. 15, 187-9 (1941). 602. 605. 604. 605. 606. 607. - 217 - Halls, E.E. "Modern Nickel Plating, I and II." Machinist (Eur.Ed.) as, 244-511, 2623 (1941). Helbig, WQA. "Physical Removal of Impurities in Plating Solu- tions." Proc. Am. Electroplater's Soc. 29, 68-76 (1941). Hogaboom, G.B. "A Study of Throwing Power of Plating Solutions." Proc. Am. Electr0plater's Soc. 22, 62-4 (1941). Linick. L-L- "Addition Agents in Nickel Plating." Metal Finishing g9, 611, 614 (1941). Maurer, P.A. "Cleaning and Bripht Plating Steel and Iron Parts of Electric Irons." Monthly Rev. Am. Electroplater's Soc. 28, 695-707 (1941). Meyer, W.R. "Effects of Imyurities in Plating Solutions." Proc. Am. Electroplater's Soc. 22” 65-68 (1 41). Metal Finishing g9, 869-72 (1941). 608. 609 . 610 . 611. 612. 613. ~218 - Pesin, Uya. 1.1., Andreeva, 0.I., Moreno, A.A. and Schmnzar, M.P. "Fractional Purification olei Electrolytes for the Removal of Fe and COO" Tsvetnye Metal. 16, No.8, 29-25 (1941). Pinner, \ihLo. Soderberg, G. and Baker, E.M. 'l‘iickel-Plating." Trans. Electrochem. Soc. 80, 539-568 (1941). Piontelli, R. and Livadori—Fonzi, M. "The heactions Between Metals and Agueous Electrolytes III. The Diaplacement Processes." ’Chimica e industria (Italy) as, 252-62 (1941). Pollack, A. "A Hundred Years of the Electrodeposition of Alloys." Oberfllichentech. lg, 171-2 (1941). Puri, U.S. and Seth, S.R. "Effect of Colloids on the Electro- deposition of Nickel on Coypero" J. India-v. Chem. Soc. 1.8.. 465-8 (1941). Snellins', B. J. and Thews, E.R. "The Procedure of Plating Hard Nickel and Chromium Deposits." Metallwaren-Ind. Galvano-Tech. 552, No.11, 241-5 (1941). 614. 615. 616. 617. 618. 619. - 219 - Soderberg, G., Pinner, W-L., and Baker, E.M. "Cobalt Platingo" Trans. Electrochem. Soc. §QJ 579—586 (1941). Solanki, D.N. and Singh, D. "Some Physical Factors in the Elec— trodeposition of Nickel on Iron." J. Indian Chem. Soc. _1_g, 422-45 (1941). Stepanov, D.V., and Kyashchenkn, I.P. "Hard and Bright Nickel Plating." Jo Applied Chem. (U.S.S.R.) lg, 281-90 (in German 290) (1941}- Stocker, O.A. "Chemical and Electrochemical Methods for the Purification of Plating Solutions." Proc..Am. Electroplater's Society as, 76-86 (1941). Stocker, O.A. "Purification of Plating Solutions. Chemical and Electrochemical Methods." Metal Finishing fig, 579-82 (1941). True, O.S. "Rubber-Its Application to Electr0plating." Monthly Rev. Am. Electroplater's Soc. ge, 554-60 (1941). III" I 620. 621. 622. 624. - 220 - Tucker, W}M0 "NlCKeléPlatinfi, 01d and New." Monthly Rev. Am. Electrogilater's Soc. 3;, 881-8 (1941). Vertsman, Ya. L. "Decorative Chromium-Plating: of Sendblasted Iron Articles on 3. Connor I'xidercoat." J0 Applied Chem. (U0303030) Lg, 507-16 (1941)0 Wagner, H. "The Character of Alloys from the Viewlvo int of the Electrodepositor." Z. Lietall-u. Schmuchwarcr.-Fabri,, sowie Verchrom. __2_2_, 596-7, 444, 448 (1941). Wemer, E. "Surface Treatment of Zinc." Metallwirtschaft §_O_, 853-5 (1941). Werner, E. "Hydrogen Pits in Nickel Deposits." Metallwirtschaft 22, 1142-7 (1941). 625. 626. 627. 626. 629. - 221 - 1942 Fink, COG. Trans. Electroch. Soc. go, 587 (1942). Gernes, D.C. and Mbntillon, G.H. "Single Metal, Binary and Ternary Allog,r Deposition from Thiosulfate Solutions. II. Binary Alloy Deposition of Copper-Nickel, Cogipcr-Cadmium, and COpper—Zinc Alloys from thio Sulfate Solutions." Trans. Electrochem. Soc. 33;, 221-248 (1942). Hendricks, J.A. "An Interpretation of the Mechanism of Brie-ht Electroplating. " Trans. Electrochem. Soc. ea, 118-131 (1942). Holt, ILL. and Nielsen, 1.1.1.. "Electro-Deposition of Nickel Tungsten Alloys from an Acid Plating- Bath." Trans. Electrochem. Soc. §_I_3_, 193—203 (1942). Kush-ner, JOB 0 "Drag..1n. ” Monthly Rev. Am. ElectrOplater's Soc. g2, 751-70 (1942). 0. 651. 4. -222 - Loose, ‘3.S. 'Nickelilatirg Magnesium Alloys." Trans. Electrochem. Soc. _8_1, 213-229 (1942). Muller, F. "The Effect of Colloids on the Electrodeposition of Met 8.18 . " K0110 id-Ze 00, 159-62 (1942) o Nielsen, 1.1.L. and Holt, ILL. "Cathode Films in Tungstate con- taining Plating? Baths." Trans. Electrochem. Soc. gg, 217-226 (1942). Piontelli, R. "Electrodeposition of Alloys. 1. General Con- siderations." “8130 1138.10 &, 242-4 (1942)0 Piontelli, B. "Iflectrodeposition of Alloys. II. Nickel—Co- balt Alloys from S'ulfamic Acid Baths." Met. ital. gg, 245-9 (1942). Planer, 13.1". "Crystallization of Metals from Aqueous Solu- tion. " Iron Age 149, No.24, 66-9 (1942). 656. 628. 640. 641. - 223 - Pollack, A. "Nickel Baths Containing Na2804o" Oberflgchentech. 15;, 91—2 (194:). Baskin, J.B.. "Conservation of Plating Materials." Monthly Rev. Am. Electroplater's Soc. 29;, 652-66 (1942). Products Finishing 6, No.9, 42-4, 46, 48-50, 52., 54—5 (1942). Thomas, G. "Origin of Pits in Electrolytically Deposited Metals." Compt. rend. 214, 480- (1942). Watts, O.P. "A Strange Phenomenon in (Nickel) Plating." Trans. Electrochem. Soc. 82, 55-57 (1942). Wesley, W.A. and Roehl, E.J. "The Electrodeposition of Hard Nickel." Trans.- Electrochem. Soc. _8__2_, 27-52 (1942). Products Finishing _7_, No.2, 10-12, 14-16, 18, 20, 22., 24, 26, 28, 30, 32 (1942). Yates, R.F. "Plated Aluminum in the War Program." Metal Finishing 3341, 295-6 (1942). 6420 642. 644. 645. 646. 647. - 224 - YOlmg, CoBoFo "Plating Alloys." Iron Age ;49, £0.7, 52-7, No.8, 46-8 (1942). 1948 ApBoberts, J.P. “Problems and Methods for Plating on Magnesium." Mbnthly Rev. Am. Electroplater's Soc. go, 275-83 (1943). Fischer, H. "The Role of Inhibitors in the Electrodeposition of Metals." z. Elektrochemo 2g, 242-56, 376-82 (1943). Hepburn, J.B.I. “Alloy Deposition." J. Electrodepositor's Tech. Soe..;2, 1-12 (1943). Lustman, B. "The Deposition Potentials and Microstructures of Electrodeposited Nickel-Zinc Alloys." Trans. Electrochem. Soc. 84, 3 2-375 (1943). Meyer. W.R. "BlaCkeningrof Nonferrous Metals." Proc. Am. Electroplater's Soc. g1, 90-2 (1943). 648. 649. 650. 651. 652. 653. - 225 - Mol ine, ill-E. "Black-ii‘i-Platingr. .. Proc. Am. Electroplater's Soc. 8 , 21-3 (1948»). Morri son, 37.5. "Synthetic Cation and Anion Exchange Resins as New Research Tools in the Field of Electrodeposition and Related Art." Monthly Rev. Am. ElectrOplater's Soc. go, 702-18 (1948‘). Piontelli, R. "Sulfmnic—Acid Baths for Electroplating: and Anodi- sing." Korrosion u. Metallschutz, 12, 110-15 (1942-). Pollack, A. 'Tlickel-Plating Baths Containing; Organic Acids." Scheif-u. Poliertech. 20 , 111-12 (1942’). Poor, J.G. "Black Nickel-Plating." Metal Finishing 4 , 694-6, 769-71 (1943). Schore , E. "Black Nickel." Metal Finishing fl, 77-9 (1943). 53.432237 mass 654. 655. 657. 658. 659. - 226 - 'WattS, OoPo "Kbvelties in.Eflectroplating." Trans. Electrochem. Soc. 84, 347-850 (1942). Wiesner, H.J. "The Colloidal State and Precipitation of Cer— tain Metallic Hydroxide in Concentrated Solutions of Nickel Sul— fate." Thesis for Ph.D. degree Michigan State Collars. (1948). 1944 ‘DuBose,.A.H., and Pine, Roh. "New Nickel-Iron.Alloy for Elec- troplating." Steel 114, No.24, 124 (1944). Martin, B. "Stress in the Electrodeposition of Nickel." Proc. Am. Electr0plater's 503., June Q2, 206-17 (1944). Shepard, H.M. and Knierim, C.A. "Removal of Iron froniNickel Sulfate Solutions." U080 2,256 918: Aug. 22, 194:4. Ioffe, v.3. "Internal Resistance in Electrodeposition of metals." USpekhi IChim 12;, 48-63 (1944). 660. 661. 663. 664. 665. -227 - McFarlane, T. "Nickel Plating." Monthly Rev. Am. ElectrOplater's Soc._‘2_1 2541—9 (1944). 811mm, H. "‘u'etting Arents-Their Use in Electr0platina and Allied Processes." J. Electrodepositor's Tech. Soc. _1_9_, 151-46 (1944). Fischer, H. "The Role of Addition Agents in the Electrodeposition Of Metals. II." Kolloid-Z. 106, 50-62 (1944). 1945 Case, B.C. "€5,181 ity Nickel Deposits Maintained by Continuous Sol- ution Purification." Monthly Rev. Am. Eleotroplater's Soc. g2, 788-90 (1945). Dig-grin, Myron B. "The Purification of Electroplating Solutions." Talk before Detroit Branch, American Electroplater's Society November 2, 194-5. Pinner, ESL. and Kinnaman, 11.13. "High-Speed Nickel Plating." Monthly Rev. Am. Electroplater's Soc. 22, 227-8. (1945). -228- 666 . ‘Jr'ai te , v.11 . "B right Nickel Plat ins: . " Monthly Rev. Am. Electroplater’s Soc. g2, 467-9 (1945). 1111InIII!11111111111111111 31293 02244 8215