THE ELECTRODEPOSITION OF TERNARY ALLOYS OF CADMIUM, COPPER AND TIN By R O B E R T C. OLSEN A THESIS S u b m itted to the F a cu lty o f M ic h ig a n State College o f A g ric u ltu re a n d A p p lie d Science in P a r t ia l F u lfillm e n t o f the requirements f o r the Degree o f Doctor o f Philosophy KED Z1E C H E M IC A L LABO R A TO R Y East Lansing, Michigan 193 6 ProQuest Number: 10008499 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. uest ProQuest 10008499 Published by ProQuest LLC (2016). Copyright of the Dissertation is held by the Author. All rights reserved. This work is protected against unauthorized copying under Title 17, United States Code Microform Edition © ProQuest LLC. ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106- 1346 THE ELECTRODEPOSITION OF TERNARY ALLOYS OF CADMIUM, COPPER AND TIN By R O B E R T C. O LSEN A THESIS S u b m itte d to the F a cu lty o f M ic h ig a n State College o f A g ric u ltu re a n d A p p lie d Science in P a r t ia l F u lfillm e n t o f the requirements f o r the Degree o f D octor o f Philosophy K EDZ1E C H E M IC A L LA BO R A T O R Y East Lansing, Michigan 193 6 P r i n t e d i n U.S.A. L ith o p rin te d by Edwards Brothers, In c ., Lith o p rin ters and Publishers Ann Arbor, M ich ig an , 1036 THE ELECTRODEPOSITION OF TERNARY ALLOYS OF CADMIUM, COPPER AND TIN The three metals, cadmium, copper and tin, have been electrolytically deposited singly and in pairs from solutions of their salts. The purpose of this investigation is to determine whether the three metals can be deposited simultaneously from an aqueous solution of the complex cyanides of cadmium and copper and sodium stannate, and to study the effects of metal ratio, tempera­ ture, current density and free cyanide content on the composition of the metal deposited. THEORETICAL The simultaneous electrodeposition of metals should take place when the single electrode potentials are nearly the same. Deposition will take place under these conditions if no other factors except the single electrode potentials are involved. The normal electrode potentials of the metals under consideration are: Copper Cadmium Tin Hydrogen +.344 -.401 -.136 .000 volts volts volts volts Substituting these values in the Nernst electrode potential equation we find that copper alone should be deposited from a solution normal with respect to the several ions; hydrogen would be discharged preferentially to cadmium and tin and in such a solution simultaneous deposition seems impossible. The Nerst electrode potential equation, F — pO RT -| E " E - Ef 1 c wherein E is the single electrode potential, E° is the normal electrode poten­ tial, R is the gas constant, T is the absolute temperature, n is the valence of the ion, F is Faraday’s constant and C is the concentration of the metal ion, shows that the single electrode potential may be changed by altering the ion concentration. Dilution and complex ion formation are the means of establishing a suitable metal ion ratio. The decrease in metal ion concentration upon dilu­ tion results in a corresponding decrease in conductivity and lower energy ef­ ficiency and results in gassing at the cathode and a low current efficiency. Complex ion formation is preferable to dilution in bringing about the same conditions of ionic concentration; it has similar disadvantages as to decreased efficiencies, but to a very much less extent. Measuring the electrode potentials of copper and cadmium in their complex cyanides and tin in sodium stannate, we have: Cu, CuCN (.1M) +KCN(.2M) Cu+ + e -> Cu E = -.61 volts Cd, CdCN2 (.lM) +KCN(.gM) Cd++ + 2e Cd E = -.71 volts Sn, Na2Sn03 (.lM) Sn+f+++ 4e —» Sn E = -.79 volts 2 THE ELECTRODEPOSITION OF TERNARY ALLOYS OF CADMIUM, COPPER AND TIN The deposition potentials of copper and cadmium become more elec­ tronegative with increase in free cyanide, with increase in current density and with decrease in temperature; the potential of tin remains nearly constant with increase in free cyanide, becomes more electronegative with increase in tempera­ ture and with increase in current density. Theoretical considerations show a possibility of the deposition of the three metals Simultaneously from an aqueous solution of the complex cya­ nides of copper and cadmium and sodium stannate. LITERATURE OF TERNARY-ALLOY ELECTRODEPOSITION Few references to the deposition of ternary alloys from aqueous solutions are recorded in the literature. Glasstone, (l) in his work on the electrolytic polarization of the iron group metals, nickel, cobalt and iron, studied the deposition potentials of the three metals, singly, in pairs and the three together. He drew the conclusions that the deposition potential (l) va­ ries directly with the metal concentration ratios, (2) varies directly with the temperature and (3) is independent of the hydrogen ion concentration. He used the sulfates of the metals, buffered with sodium acetate, boric acid or acetic— acetate mixture. Wernlund (2) patented a process of deposition of cadmium-zinc alloys from a solution of zinc cyanide, cadmium hydroxide, sodium cyanide and sodium hydroxide. The patent specified the addition of mercury to the electro­ lyte, making it a ternary system. The Electrochemical Rubber and Manufacturing Company (3) has patented the deposition of an alloy of copper, zinc and antimony from an elec­ trolyte of antimonyl trichloride and the complex cyanides of copper and zinc. They found that the antimony content of the deposit can be controlled by (l) varying the composition of the solution, (2) varying the anode composition and (3) varying the voltage. Fields (4) reported the deposition of an alloy of copper, nickel and zinc from cyanides of the metals. Yamazaki (5) obtained a bronze consisting of copper, zinc and tin by electrolyzing a solution of their cyanides. Stout and Faust, (6) working on the electrodeposition of iron, copper and nickel alloys from cyanide solutions state: (l) the deposition of copper is favored over that of nickel and iron, especially at low current den­ sities, (2) very high concentration of iron is required in solution to obtain even small iron content in deposits, (3) the metal content of the deposit does not depend directly on the percent of that metal in the solution, but upon its concentration relative to each of the other metals, (4) the percent of copper and nickel in the deposit is relatively greater than that in the bath, (5) in­ crease in current density favors the deposition of nickel and iron at the ex­ pense of the copper, (6) increase in copper to nickel ratio in the bath causes an increase in the copper to nickel ratio in the plates, (7) the ratio of copper to nickel in the plate is unaffected by the amount of iron in the bath, (8) it is necessary to use very low concentrations of free cyanide to obtain the ter­ nary alloys. Ernst and Mann, (7) investigating the ternary alloys of copper, cadmium and zinc from cyanide baths concluded: (l) the copper in the deposit increases as the potassium cyanide decreases or the sodium bisulfite increases, increases as the cadmium in the solution and deposit decreases, and increases as the zinc in the solution and deposit increases, (2) the cadmium in the de­ posit increases as the potassium cyanide increases or the sodium bisulfite ROBERT C. OLSEN 3 decreases, increases as the copper in the solution and deposit decreases and in­ creases as the zinc in the solution and deposit decreases, (3) the zinc in the deposit increases as the potassium cyanide decreases or the sodium bisulfite in­ creases, increases as the copper in the solution and deposit increases and de­ creases as the cadmium in the solution and deposit increases, (4) the effect of free cyanide is the most important factor in cyanide deposition, (5) increasing the current density increases the percentage of cadmium and zinc and decreases the percentage of copper in the deposit, (6) with increasing temperature the per­ centage of cadmium increases, while the percentage of copper decreases and the percentage of zinc remains fairly constant. Faust and Montillon (8) deposited alloys of copper, nickel and zinc from a solution of their cyanides. They found the following: (l) zinc is more readily deposited than nickel and both metals are more readily deposited than nickel, (2) the percent of copper in the deposit is relatively greater than the percent of copper in the bath, (3) the percent of nickel in the deposit is relatively much less than the percent of nickel in the bath, (4) the percent of zinc in the deposit is nearly the same as that of the bath, (5) increase in cur­ rent density favors the deposition of zinc and nickel over copper, and zinc de­ posits more readily than nickel with increase in current density, (6) increase in temperature causes an increase in percent of copper in the deposit, (7) in­ crease in temperature causes a relatively greater decrease in the percent of zinc in the deposit than the percent of nickel, (8) at about 50°C. there ia a rearrangement of the factors controlling deposition which causes a reversal in the slope of curves plotted for percent of copper and percent of zinc versus the percent of these metals in the bath. Stout and Goldstein (9) deposited alloys of cadmium, zinc and antimony from asolution of antimonyl tartrate and the complex cyanides of cad­ mium and zinc. Their conclusions were: (l) deposition of zinc and antimony are favored over the deposition of cadmium, (2) a comparatively large cadmium con­ centration in the bath is required to produce an appreciable amount of cadmium in the deposit, (3) the effect of an increase in concentration of one metal in the bath is to increase the content of that metal in the deposit, (4) an in­ crease in current density at 20°C. produces an increase in antimony content of the deposit when the cadmium and zinc concentrations are low and a decrease in the antimony when the cadmium and zinc contents are high, (5) an increase in current density at 20°C. causes a slight decrease in the zinc content of the deposit, (6) the effect of temperature on the composition of the deposit is al­ most identical with the effect of current density. Stout and Agruss (10) deposited ternary alloys of cadmium, tin and zinc from abath consisting of complex cyanides of cadmium and zinc and sodium stannate. They concluded from their study: (l) deposition of cadmium is favored over the other two metals, (2) a comparatively large amount of tin is necessary in the bath to produce an appreciable amount of tin in the plate, (3) an increase in the cadmium and tin concentrations in the bath produces an in­ crease in their compositions in the deposit, (4) at low current densities in­ crease of zinc in the bath decreases the metal content of the plate, but at higher current densities zinc behaves as the other two metals, (5) at a current density of two amperes per square decimeter the tin and zinc contents of the deposit increase while the cadmium decreases with increasing temperature and (6) at half an ampere per square decimeter the zinc content of the deposit increases with increasing temperature while the content of tin and cadmium does not change. 4 THE ELECTRODEPOSITION OF TERNARY ALLOYS OF CADMIUM, COPPER AND TIN EXPERIMENTAL All chemicals used in this investigation were of C.P. quality. The individual baths were made up by mixing measured volumes of the following stock solutions: 44.8 g/L, CuCn 1 10.0 g/L, NaOH 13.2 g/L, Na2C03 () (2) CdO CdC03 16.0 g/L, 21.6 g/L, (3) Na2 SnO. NaOH Na C0„ 26.6 g/L, 10.0 g/L, 13.2 g/L. Sufficient sodium cyanide was incorporated in each of the stock solutions to give the desired amount of free cyanide after complete solution. Three sets of stock solutions were made up of .50, .75 and 1.00 normal in free cyanide. All stock solutions and the resulting individual baths were .5 normal in metal con­ tent, .25 normal in NaOH and .25 normal in carbonate. The individual baths were made up of the following volumes of the stock solutions and the resulting ratios of equivalents of metal: Bath A B C D E F G H I J cc. Stock Sn Soln 600 900 1275 1500 450 255 150 450 255 150 cc. Stock Cd Soln 600 450 255 150 450 255 150 900 1275 1500 Metal ratio cc. Stock Cu Soln 600 450 255 150 900 1275 1500 450 255 150 1 2 5 10 1 1 1 1 1 1 1 1 1 1 1 1 1 2 5 10 1 1 1 1 2 5 10 1 1 1 The electrolytic cell consisted of a rectangular glass jar 9 cm. by 15 cm. by 15 cm. deep. Four cells, wired in series were placed in a water bath maintained at a constant temperature within an error of .5° C. The baths were agitated by air-driven glass stirrers. Sheet steel anodes were placed seven centimeters from each side of the chromium-plated cathodes. The anode and cathode areas were the same, one square decimeter. Current was supplied by a motor generator. The surrent was measured with an ammeter graduated to onetenth of an ampere. Voltage was measured with a high resistance voltmeter. After electrolysis the cathode was transferred to a beaker; the plate was removed under water by wiping with a rubber-tipped glass rod; the metal was filtered through a previously weighed Gooch crucible, washed with water and alcohol, dried and weighed. To determine the effect of temperature on composition of deposit, baths C and F, with a free cyanide content of .75 normal were electrolyzed at a current density of two amperes per square decimeter at temperatures of 20°, 40°, 60° and 80°C. All other runs were carried out at a temperature of 60 + .5°C. The major part of the investigation was to determine the effect of metal ratio at current densities of 0.5, 2.0 and 4.0 amperes per square decimeter in baths of .50, .75 and 1.00 normal in free cyanide. ROBERT C. OLSEN Only the stock solutions were analyzed. The free cyanide content was determined by titration to turbidity with silver nitrate. The carbonate was precipitated with barium chloride and titrated with standard acid. The metal con­ tent was determined by electrolysis in a Braun cabinet after the cyanide had been destroyed, tin from oxalate solution, copper from sulfate and cadmium from cyanide solution. Analysis of deposits consisted of sulfide separations and electro­ lytic determinations by methods adopted by the American Society of Testing Mate­ rials. A sample was dissolved in mixed hydrochloric and nitric acids, evaporated to dryness on a water bath-, digested with sodium hydroxide, oxidized by hydrogen peroxide, ammonium oxalate and oxalic acid added and the copper and cadmium pre­ cipitated as sulfide. The filtrate was electrolyzed for tin. The residue was dissolved in nitric acid, made alkaline with sodium hydroxide, sodium cyanide added and the cadmium precipitated as sulfide. The filtrate was boiled with sulfuric acid, neutralized with sodium hydroxide, nitric acid added and copper electrolyzed. The residue was dissolved in hydrochloric acid, made alkaline with sodium hydroxide, the precipitate just dissolved with sodium cyanide and the cad­ mium electrolyzed. In cases of very small amounts of tin, the alloy was dis­ solved in nitric acid, evaporated to dryness, baked, taken up with hot water and the metastannic acid filtered, ignited and weighed. DATA AND RESULTS The data taken is recorded in the following eight tables. Tables I and II state the conditions under which deposition was carried out to deter­ mine the effect of temperature on the composition of deposit. Tables III, IV and V give the conditions governing the investigation of the effect of metal ratio in the bath, current density and normality of free cyanide on the composi­ tion of plate and Tables VI, VII and VIII the results of analysis and a compari­ son between normality of metal in the bath and the percentage of metal in the deposit. Table I Effect of Temperature Bath Temp C C C c 20 40 60 80 F F F F 20 40 60 80 Time Volts Weight 2.0 2.0 2.0 2.0 10 10 10 10 3.4 3.0 2.7 2.3 .231 .452 .522 .565 2.0 2.0 2.0 2.0 10 10 10 10 3.3 3.2 2.7 2.4 .281 .465 .497 .657 Amps 6 THE ELECTRODEPOSITION OF TERNARY ALLOYS OF CADMIUM, COPPER AND TIN Table II Effect of Temperature Bath Temp C C C C 20 40 ’ 60 80 N CN 0.75 0.75 0.75 0.75 F F F F 20 40 60 80 0.75 0.75 0.75 0.75 Composition of Bath N Cu N Sn N Cd .071 .356 .071 .071 .356 .071 .356 .071 .071 .356 .071 .071 .071 .071 .071 .071 .071 .071 .071 .071 .356 .356 .356 .356 Plate Analysis % Cd % Sn % Cu 98.1 0.0 1.9 95.8 1.3 3.0 81.4 4.3 14.4 64.4 23.0 12.6 0.4 0.7 1.7 2.0 98.3 92.7 84.0 75.5 1.3 6.6 14.3 22.5 Table III Effect of Metal Ratio of Bath on Plate Composition 0.5 amp/ sq. dm. Bath Free CN Ratio Sn/Cd Ratio Sn/Cu Ratio Cu/Cd ' Volts A A A B B B C C C D D D E E E p F F G G G H H H I I I J J J 1.00. 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1 1 1 2 2 2 5 10 5 10 10 10 1 1 1 1 1 1 1 1 1 .5 .5 .5 .2 .2 .2 .1 .1 .1 1 1 1 2 2 2 5 5 5 10 10 10 .5 .5 .5 .2 .2 .2 .1 .1 .1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 2 2 2 5 5 5 10 10 10 .5 .5 .5 .2 .2 .2 .1 .1 .1 1.8 1.8 1.8 1.9 1.9 1.9 2.0 2.2 2.2 2.2 2.2 2.1 1.9 2.1 1.9 1.9 1.9 2.1 2.0 2.1 2.0 1.9 1.9 1.8 1.9 1.9 1.9 1.8 2.0 1.7 Time 60 60 60 60 60 60 60 ’ 60 60 60 60 60 60 60 87 60 60 87 60 60 87 60 60 87 60 60 60 60 60 60 Weight Plate 1.173 1-.092 1.001 0.968 1.051 1.005 1.042 0.984 0.943 0.885 0.848 0.840 1.099 1.121 1.511 1.110 1.121 1.490 1.041 1.077 1.351 0.980 1.024 1.462 1.051 1.057 1.003 1.042 1.043 0.948 7 ROBERT C. OLSEN Table IV Effect of Metal Ratio of Bath on Plate Composition S.O amps/sq.dm. Temp 60° C. Bath Free CN Ratio Sn/Cd Ratio Sn/Cu Ratio Cu/Cd Volts Time A A A B B B C C C D D D E E E F F F G G G H H H I I I J J J 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1 1 1 2 2 2 5 5 5 10 10 10 1 1 1 1 1 1 1 1 1 .5 .5 .5 .2 .2 .2 .1 .1 .1 1 1 1 2 2 2 5 5 5 10 10 10 .5 .5 .5 .2 .2 .2 .1 .1 .1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 2 2 2 5 5 5 10 10 10 .5 .5 .5 .2 .2 .2 .1 .1 .1 2.2 2.4 2.4 2.3 2.4 2.4 2.8 2.9 2.9 2.8 2.8 2.8 2.7 2.7 2.5 2.8 2.7 2.5 2.8 2.7 2.6 2.4 2.3 2.2 2.2 2.2 2.4 2.1 2.2 2.3 20 20 21 20 20 21 20 20 21 20 20 21 20 21 20 20 21 20 20 21 20 20 21 20 20 20 20 20 20 20 Weight Plate 1.169 1.188 1.403 1.230 1.253 1.387 0.845 0.891 1.017 0.621 0.818 0.760 1.157 1.118 1.166 0.777 1.004 1.214 0.676 0.826 0.931 1.255 1.387 1.377 1.315 1.163 1.386 1.309 1.245 1.367 8 THE ELECTRODEPOSITION OF TERNARY ALLOYS OF CADMIUM, COPPER AND TIN Table V Effect of Metal Ratio of Bath on Plate Composition 4.0 amps/sq .dm. Bath A A A B B B C C C D D D E E E F F F G G G H H H I I I J J J Temp 60° C. Free CN Ratio Sn/Cd Ratio Sn/Cu Ratio Cu/Cd Volts Time 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1 1 1 2 2 2 5 5 5 10 10 10 1 1. 1 1 1 1 1 1 1 .5 .5 .5 .2 .2 .2 .1 .1 .1 1 1 1 2 2 2 5 5 5 10 10 10 .5 .5 .5 .2 •< fr C .2 .1 .1 .1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 2 2 2 5 5 5 10 10 10 .5 .5 .5 .2 .2 .2 .1 .1 .1 2.8 2.6 2.9 2.9 2.9 3.1 3.2 3.3 3.4 3.3 3.3 3.4 3.2 3.1 3.0 3.2 3.3 3.1 3.2 3.2 3.1 2.6 2.8 3.0 2.6 2.7 2.8 2.6 2.8 2.6 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Weight Plate 1.174 1.166 1.313 1.154 1.141 1.124 0.793 0.813 0.860 0.442 0.521 0.571 0.997 1.064 1.105 0.730 0.812 1.125 0.526 0.669 1.019 1.215 1.361 1.301 1.350 1.357 1.301 1.349 1.379 1.264 ROBERT C. OLSEN 9 1 Table VI Effect of Metal Ratio of Bath on Plate Composition 0.5 amp/sq. dm. Bath N CN A A A B B B C C C D D D E* E E F F F G G G H H H I I I J J J Composition of Bath N Sn N Cd N Cu 1.00 1.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 .166 .166 .166 .249 .249 .249 .355 .354 .355 .418 .416 .419 .125 .125 .125 .071 .071 .071 .042 .042 .042 .125 .125 .125 .071 .071 .071 .042 .042 .042 .156 .156 .156 .116 .116 .116 .065 .066 .064 .039 .038 .037 .117 .117 .116 .066 .063 .063 .038 .037 .037 .241 .240 .241 .345 .346 .345 .408 .409 .409 .166 .166 .166 .165 .125 .125 .071 .071 .071 .042 .042 .042 .250 .250 .249 .355 .355 .354 .419 .419 .415 .125 .125 .125 .071 .071 .071 .042 .042 .042 Temp 60° C. Plate Analysis % Sn % Cd % Cu 0.0 0.0 0.4 0.0 0.3 0.8 1.4 7.1 0.3 8.9 17.3 17.9 0.0 0.0 0.8 0.0 0.0 1.1 0.9 0.8 0.8 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 100.0 100.0 99.3 100.0 99.7 99.2 98.6 92.9 99.7 91.1 82.4 81.7 100.0 100.0 98.0 100.0 100.0 80.7 88.2 88.6 56.8 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 0.0 0.0 0.3 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.3 0.4 0.0 0.0 1.2 0.0 0.0 18.2 10.9 10.5 42.4 0.0 0.0 0,0 0.0 0.0 0.0 0.0 0.0 0.0 10 THE ELECTRQDEPOSITION OF TERNARY ALLOYS OF CADMIUM, COPPER AMD TIN Table VII Effect of Metal Ratio of Bath on Plate Composition 2.0 amps/sq.dm. Bath A A A B B B C C C D D D E E E F F F G G G H H H I I I J J J Temp 60° C. Composition of Bath N Sn N Cd N CN N Cu Plate Analysis % Cd % Cu % Sn 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 .166 .166 .166 .125 .125 .125 .071 .071 .071 .042 .042 .042 .250 .249 .249 .355 .355 .351 .418 .418 .409 .125 .125 .125 .071 .071 .071 .042 .042 .042 2.0 4.5 0.8 3.6 4.2 2.2 14.1 16.8 13.5 18.0 29.0 24.2 4.5 2.7 2.3 2.5 1.8 1.4 1-*.9 2.3 2.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 .166 .166 .166 .249 .249 .249 .355 .353 .355 .417 .413 .416 .125 .125 .125 .071 .071 .071 .042 .042 .042 .125 .1-25 .125 .071 .071 .071 .042 .042 .042 .146 .146 .146 .106 .106 .106 .055 .056 .055 .032 .031 .032 .106 .106 .101 .055 .054 .055 .029 .028 .030 .231 .230 .226 .334 .335 .335 .398 .398 .390 98.0 94.0 99.2 96.4 95.2 97.8 83.6 78.9 82.4 80.7 68.6 70.7 90.4 95.6 92.4 73.5 83.9 65.9 75.3 64.5 38.2 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 0.0 1.5 0.0 0.0 0.6 0.0 2.3 4.3 4.1 1.5 2.4 5.1 5.1 1.7 5.3 24.0 14.3 32.7 22.8 33.2 61.8 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 ROBERT C. OLSEN 11 Table VIII Effect of Metal Ratio of Bath on Plate Composition 4.0 amps/sq.dm, Bath A A A B B B C C C D D D E E E F F F G G G H H H I I I J J J Temp 60° C. Composition of Bath N .CN N .Sn N .Cd N .Cu Plate Analysis % Sn % Cd % Cu 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 1.00 0.75 0.50 .166 .166 .166 .125 .125 .125 .071 .071 .071 .042 .042 .042 .250 .250 .250 .356 .356 .356 .420 .420 .420 .125 .125 .125 .071 .071 .071 .042 .042 .042 1.9 2.1 2.0 3.3 3.9 3.4 10.9 11.4 10.8 22,9 14.2 12,8 3.6 3.5 1.6 2.1 2.2 1.0 0.0 0.0 0.0 1.4 1.1 1.0 0.0 0.6 0.6 0.0 0.3 0.0 .166 .166 .166 .250 .250 .250 .356 .356 .356 .420 .420 .420 .125 .125 .125 .071 .071 .071 .042 .042 .042 .125 .125 .125 .071 .071 .071 .042 .042 .042 .166 .166 .166 .125 .125 .125 .071 .071 .071 .042 .042 .042 .125 .125 .125 .071 .071 .071 .042 .042 .042 .250 .250 .250 .356 .356 .356 .420 .420 .420 97.7 97.4 97.4 96.6 95.9 96.2 87.3 85.7 86.7 75.5 83.5 84.8 92.8 92.7 93.6 77.1 83.2 75.0 74.3 72.6 47.2 98.6 99.0 98.8 100.0 99.4 99.5 100.0 99.7 100.0 0.4 0.5 0.6 0.1 0.2 0.4 1.8 2.9 2.5 1.6 2.3 2.4 3.6 3.8 4.8 20.8 14.6 24.0 25.7 27.4 52.8 0.0 0.0 0.2 0.0 0.0 0.0 0.0 0.0 0.0 £rf£cr or rsAtrseATtKE OA/ % Af££Al5 /A/ OEAOS/T /oo - BATH C .75N CN 90 -- ZAMF/5QM 8070 • CD 60 5040 3020 10' • 0 - zo 40 SO TFMFFFATNFE °C BATH F 7 J N CN /<«? - ? 60 TFMFFFATUFE °C. F/G. / so ffffct of mr/v. fat/o /n bam ON X T/N l/V DFFOS/T /.O N ZD- 10 - /o 20 - /o .72) A/ .SON /.ON /o FIG. Z ££££CT or N£/Al £AT/0 /fitBAT// o n >i corrse /n orros/r ~w I M i /o 60, Z AMF3/5Q.m %cu4 0 \ 30 f ZO/o - /o ZAT/O Cl//CD /o F / C . J EFFECT OF HETAL FAT/O /N BATH ON % CADM/ON W DEFOS/T 700 . /Mi 90 - %ca 8o- 70 £0 Jo\ 40 t- / z E /o /O DA7ZO CD/CD DA7/0 M /C D £ AM FS/^a DM /OOj %ca 80■ /z s /Z /o DAT/D DM/CD J /o e/ir/o c^/cD /OOt %ca do70' SON 60 - JO40 / z f /o /z s /o £A T /0 CU/CD £ A W JA7/C77 F/G .4 £FF£CT OF CMN/OF COAATSAAT OA/ % T/Af AAA DFF03/T ZS 4 AMPJ/5Q D M BAT// D ZO ,5M /s BAT// C /O BAT// B BAT//A S o JO .7J /o AVOHHAL/TY AAA£ £ £ £ CYANADE 2S/O - BATH D BATHC BATH B BATH A AO A/OEMAL/TY /A / HEEE CYAN/D£ ZS- S AA/T/JQ BAf. ZO- %5N. AS" AO­ BATH B S' 0 BATH C. ■JO .FJ A v o e M A L /rr w F /G .S /£) h e e e cyaaa/ d e EFFECT OF CYAN/DE CONTENT ON % COFFEE /N DEFOS/T 4AM FJ/J#nH jo 40 JO BATHG BATH F 10 /o BATH £ 0 ,J0 /o NoewAL/rr 40 w ££££ c m m - /0-FS wefif/mrr /O w ££££ c ta h /d t .5 AMD/JO. DM. BATH G BATH F BATH £ /.o NOJBMAL/TF //[/£ £ £ £ CYAN/D£ F/G. 6 £FF£CT OF CFAN/DF COA/TFNT ON % CADM/UM /N DFPOS/T 4AMFJ/JE.M & %co. .50 A/oemun .75 /£> /m fe e e cyan/de %ca 60- /.o .75 A/OEMAL/FY //V FEEE CYAN/DE A