Electrodeposition

and Surface

Treatment

199

Elsevier Sequoia S.A., Lausanne - Printed in Switzerland

ELECTRODEPOSITION PRESENT STATE

OF ALLOYS

OF THE ART

A. KROHN and C. W. BOHN

Department of Chemistry, University of Toledo, Toledo, Ohio 43606 (U.S.A.)

(Received June 19, 1972)

SUMMARY* Recent

literature

on the electrodeposition

of alloys is critically

reviewed. The

discussion emphasizes binary alloys deposited from aqueous media and their practical applications, but dispersion-strengthened alloys and composite electrochemical materials, ternary alloys and alloys plated from fused salt electrolytes also are mentioned. Alloy plates continue their applications as decorative and protective coatings, but have found additional usefulness in magnetic alloy films for the computer industry, in electroforming, in the electronics industry and for the plating of plastics.

The electrodeposition of alloys up to 1960 was covered Brenner in his comprehensive monographl. Later review articles and progress in the field2-s. It is the purpose of this paper to update on alloy electrodeposition and to delineate the present state of the
NEW BINARY ALLOYS

thoroughly by indicate trends the information art.

Figure 1 summarizes the electrodeposition of binary alloys from aqueous solutions reported in the literature up to June 1, 1972. A count shows that 117 were reported up to 1960, 19 were reported between 1961 and 1964, and 65 have been added since 1964. Of these newer alloys, those of silver with rhenium, first reported in 1965, were granted a U.S. patent in 19678 and now have been developed into an industrial processa. The alloys are plated from solutions containing silver cyanide, sodium perrhenate, potassium carbonate and potassium cyanide. Applications range from solid film lubrication, grease retention-secondary lubrications, swaged in situ
* R&urn6 en franGais ?+la fin de larticle. Deutsche Zusammenfassung
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am Schluss des Artikels.

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A. KROHN, C. W. BOHN

Fig. 1. Binary alloys which have been electrodeposited from aqueous solution: I indicates alloys reported up to 1960, l indicates alloys electrodeposited for the first time between 1961 and 1964, and A indicates alloys reported since 1964.

bearings, electrical rotary switches and fretting corrosion-resistant coatings. Sodium molybdate can be substituted for the perrhenate to obtain a silver-molybdenum deposit, but the silver-rhenium alloy was found to be superior to other silver or gold alloys in wear life and lubrication propertieslO. Considerable interest has been shown in various ruthenium alloys. Wearresistant nickel-ruthenium and cobalt-ruthenium alloys may be deposited from acid chloride solutionsll-13. Sulfate or sulfamate baths have been used to produce bright coatings of electrodeposited alloys of ruthenium with indium14,15. Ruthenium also has been codeposited with palladium and platinum. Deposits of platinum with 5-80% ruthenium are reported to have very high chemical resistancenj. They are almost insoluble in acids and bases during anodic polarization or in aqua regia on boiling. Platinum alloys with copper, mercury, iron, tin, zinc, cadmium, cobalt or nickel electrodeposited from HCl solutions on titanium or titanium alloy cathodes can be used in the electrolysis of aqueous alkali metal chloride electrolytes for the preparation of chlorine, hypochlorites or chlorates. They were found to have low and constant chlorine overvoltage characteristics17.
Electrodepos. Surface Treat., 1 (1972/73)

ELECTRODEPOSITION

OF ALLOYS

201

Nickel-selenium corrosion resitancels.

alloys are used for composite nickel coatings with improved By using selenic acid tagged with %e, the codeposition of

selenium from various electrolytes was studied lg. Acid electrolytes produced alloys with chromium, nickel or zinc, and alkaline-cyanide solutions formed alloys with copper or gold. Nitric acid solutions yield uniform coatings of a selenium- bismuth alloy20, while selenium-antimony alloys were obtained from tartrate-citrate baths21. Thin layers of cadmium-selenium deposits22 and selenium-tellurium layers were found to have semiconductor properties23.
REFERENCE SOURCES

Brenner accurately predicted that the blank spaces in his 1964 chart would be filled largely by Russian scientists. Of the 65 added alloys in Fig. 1, 38 were first reported by Russian investigators. The United States was a poor second with 9, Germany produced 5 and Great Britain 4. The remainder came from Indian or Czechoslovakian sources. Of the over 1000 abstracts dealing with alloy electrodeposition reported in Chemical Abstracts from January, 1964 to May, 1972, about half were Russian in origin. Again, the U.S. was second with about 200 publications or patents and the Japanese were third with 82. German, French and Indian sources had 40 to 50 articles each, and the remainder were from miscellaneous sources.
PRIOR BINARY ALLOYS

Among the binary alloys deposited prior to 1965, the greatest interest since that time, as indicated by the number of publications, was in iron-nickel alloys. About 120 papers and patents related to these alloys, mainly because of their use in producing magnetic coatings for various computer and recording devices. Cobalt-nickel plating ranked second with 45 listings, many dealing with electroforming applications. Other frequently mentioned alloys and their numbers of reports are : nickel-tin and chromium-nickel (3 I-40) ; lead-tin (26-30) ; copper-tin, copper-zinc, cobalt-tungsten and nickel-zinc (21-25); gold-copper, gold-nickel, cadmium-zinc, tin-zinc, iron-zinc and nickel-tungsten (16-20). All others were mentioned 15 or less times. Recent developments for those of present or potential practical value will be discussed in the following sections under their fields of application. Protective and decorative coatings In the field of commercial alloy plating, brass probably accounts for as much volume as all other alloys combined. The use of a layer of brass deposit, higher in copper content than previously used, between the copper and nickel layers gives automobile bumpers exceptional durability2*. A number of changes in platElectrodepos. Surface Treat., I (1972173)

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A. KROHN,

C. W. BOHN

ing conditions and the use of addition agents have been investigated to improve or modify the deposition of brass from cyanide bathsz5e2*. Baths using triphosphate2g, pyrophosphate30 and tripolyphosphate ions31 as complexing agents have been formulated. Organic complexing agents such as polyethylenepolyamine32, ethylenediamine33-35 and cyclohexanone36 have been reported, and the electrolytic production of brass powder described3. The mechanism of electrodeposition and properties phosphate electrolytes have been studied 38,3g by several of bronzes from pyroRussians, while others

have detailed bronzing of steel strips from a phenolsulfonic electrolyte4o and the production of corrosion-resistant white bronze coatings*l. Cadmium is highly effective in the protection of base metals from corrosion, but because of its cost it is frequently combined with a cheaper metal to obtain an alloy which has essentially the same properties. Alloys containing 20% zinc have the same anticorrosion properties as pure cadmium42. Recent changes in traditional cadmium-zinc plating baths involve the use of surface-active agents such as ethylenediamine43, EDTA44,45 and electrolytes containing Trilon B46 and polyethylenepolyamine47,4s. Cetyltrimethylammonium bromide is reported to be an effective addition agent for sulfamate baths4g. Deposits from these baths are dense, smooth, fine grained, have good adhesion and covering power, and polish to a high luster. of cadmium-titanium Japanese investigators50 claim the electrodeposition alloy coatings by rotary barrel plating which are several times as anticorrosive as the usual cadmium coating. High strength springs and wires have been coated with similar alloys which are reported as being adhesive, corrosion-resistant, and produce very little hydrogen embrittlement51. Good results for the protection of steel by electrolytic zinc-nickel coatings have been reported52-54. Coatings containing l&20/, nickel have the most favorable protective and mechanical characteristics. Their resistance to sea water and humidity is claimed to be 6-7 times higher than that of zinc plate55p56. Alloys containing higher nickel content tend to become brittle. but those with 7-9% nickel have internal stresses small enough to permit the plated steel to be formed, rolled or drawn without rupturing the plate 57. Periodic reversal of the current increased the adherence of the deposit and improved the decorative value and uniformity of distribution of the deposits 58. Either nickel or chromium can be plated on nickel-rich alloy surfaces, but not on zinc-rich alloy5. The chrome plated coatings axe useful for automobile bumpers and trim. The recent severe shortage of nickel has prompted the development and commercial use of processes for depositing bright cobalt and cobalt-nickel alloys in all proportions60. These processes were perfected for broad industrial use and accepted by numerous firms within a period of months. However, the durability of such coatings leaves some doubt about their acceptance after long periods owing to some impairment of their decorative function, although from purely
j3ectrodepos. Surface Treat., I (1972/13)

ELECTRODEPOSITION

OF ALLOYS

203 content alloys appear to be

protective considerations, many of the high cobalt superior to comparable nickel coatings. Cast and wrought nickel-chromium corrosion resistance, electrical resistance

alloys give excellent wear resistance, and high hot strength. Electrodeposited

alloy coatings probably have similar properties and would allow a cheap substrate to be used, thus eliminating the need for more expensive cast or wrought alloys, so numerous attempts have been made to develop a suitable commercial plating process. Reviews by Arrowsmithal and Chisholms2 indicate that no such process has been perfected. However, good quality deposits were recently reported from a bath containing potassium chromium sulfate, nickel formate, trisodium citrate, boric acid, sodium fluoride and glycine 64. The current efficiency of the process is not high. A patent on a bath containing dipolar organic compounds claims that chromium-nickel coatings can be electrodeposited over a wide range of current densities at adequate current efficiencies 65. Studies on the outdoor corrosion resistance66p67 and the behavior of Ni-Cr electrodeposits in industrial, marine and urban environments68 indicate the value of such plates when used for decorative purposes. A case history of the electrodeposition of heavy tin-bismuth deposits on the inside diameter of oil well pipe couplings reviews the operation of a commercial installation for ten years. The tin serves as a lubricant during make up of the joint and assures a leak-proof joint throughout repeated cycles of high temperature and pressure. It also protects the threads from corrosion in storage6g. Electrodeposited lead-tin alloys have three major applications, namely the protection of steel from corrosion, running surfaces for sleeve bearings (both in the range of 610% tin) and solderable coatings (50-70% tin)O. Fluoroborate baths usually are employed with peptone or animal glue73 as addition agents. Still in a preliminary stage is a method for producing bright tin-lead solder plating for printed circuit boards74. Low cost, corrosion-resistant, very bright and easily soldered tin-lead coatings may be deposited in both rack- and barrel-plating directly on steel, copper, similarly coated76. brass or other copper alloys75. Copper wire may be

The jewelry industry uses alloys of rhodium and palladium77 and patents have been obtained for the electrochemical production of bright, high carat alloys of gold with cobalt7s, nickel 7g--81and silvers2. Bright white cadmium-silver-nickel alloys electroplated on surfaces of jewelry, instruments, automobile trim, etc. provide adherent coatings resembling those of rhodiums3. They are reported to resist ordinary wear, abrasion, scuffing and tarnishing even in sodium sulfide at 50 C for 30 minutes.
Magnetic alloys

The electrodeposition of nickel-iron alloys has received considerable attention during the past decade from the computer industry. Particular emphasis has
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A. KROHN,

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been placed on the effects of the deposition conditions on the magnetic properties of Permalloy (80% Ni-20% Fe) films with a thickness of less than 2000 A*4-86. Patents have been granted for plating of magnetic alloys on wiress7-s0, and on nonconductive substratesgl. Single-crystal electrolytically deposited Ni-Fe films have been reportedQ2. More uniform films with constant composition were prepared by discharging electrodepositiong3. a capacitor across the electrolytic cell at the beginning of the

Morral has reviewed the magnetic properties of electroless and electroplated cobalt and cobalt alloys g4 . Cobalt alloys havjng magnetic properties include those with nickel5-g7, tungstens8, and chromiumgg. Nickel-rhenium films are also reported to have an electromagnetic effectloo. An improved method of edge-plating large coupled film memory been patentedlol, and the time instability of the magnetic parameters chemically deposited thin films reviewedlo2. devices has of electro-

Electrical and electronics uses For details of electronics applications of electroless and electrodeposited alloys, the reader is referred to papers presented at the American Electroplaters Society Plating in the Electronics Industry Symposiumro3, and to recent reviews of electroplating techniques in the electronics industrylo4. As previously noted, tin-lead alloys are widely used in the manufacture of printed circuits105-108. Th e use of gold-nickel or gold-cobalt plating of terminals instead of gold plate has produced excellent results from a corrosion and solderability standpointlOp~llO. Brittleness and subsequent failure of the joint due to alloying of gold and the solder is eliminated by use of the alloys. Precision resistors can be made by coating an insulating substrate first with a sensitizing layer, followed by a Ni-P solid solution deposited by electroless platinglll. Nickel-rhenium films have been studied for applications as film resistors112 and electrical point contacts1r3, and the effect of atmospheric exposure on the contact resistance of plated tin alloys investigated1r4. An electrodeposited alloy of silver with 3% antimony is recommended as being suitable for contact components115, and a silver-tungsten alloy is reported to meet the requirements for precision resistance116. Corrosion-resistant, high frequency conducting coatings of gold containing 5-20x silver can be applied to electrical components from cyanide baths containing EDTAn7. Hardness and wear resistance The hardness and wear resistance of gold is increased by alloying it with graphite118, antimonyllg. palladium120 and nickel, cobalt or tin121. Electrodeposited silver-tin122 and silver-antimony 123alloys also possess these properties. Data compiled on the thick deposits of rhenium with the iron group metals show that smooth deposits of cobalt-rhenium and iron-rhenium alloys can be
Electrodepos. Surface Treat., 1

(I 972173)

ELECTRODEPOSITION

OF ALLOYS

205

obtained which could be considered for industrial applications12*. The cobaltrhenium alloys exhibit a significant increase in microhardness after heat treatment at 315C. The nickel-rhenium system was found to be less satisfactory. However, heat-treated nickel-tungsten alloy plates showed abrasion resistance nearly the same as that of hard chromium platinglz6. Electrolytic tin-manganese126 and lead-manganese alloys12 possess good antifriction properties and are resistant to corrosion by sulfuric acid or sea water. The abrasion resistance of chromium-molybdenum alloys is reported to be 2-3 times that of hard chrome plating128, while metal surfaces with good sliding characteristics are obtained by electrodepositing a gold-copper, indium-copper or cadmium-copper alloy on steel or aluminium and then heat treating to obtain phase segregation in the electrodeposited layer12g.
DISPERSION STRENGTHENED AND COMPOSITE ELECTROCHEMICAL MATERIAL-S

With the burgeoning interest in electroforming and printed circuitry, dispersion strengthened alloys for these applications have been formed by codeposition of metals with fine particulate matter such as alumina, titania, silica, zirconia, barium sulfate, silicon carbide, titanium carbide, kaolin, glass powder or graphitel30-134

Patents have been obtained for the electrodeposition of composite coatings of metals from an electrolyte containing dispersed particles of dry lubricant materials such as MoS, or WS, encapsulated in metal coatings about 0.0001 inch thick136, and for incorporating particles of zirconium diboride in a chromium or chromium alloy matrix136. Gold-copper composite surfaces are used for plated wire memory substrates13, and a composite electromagnetic shielding material described for making printed circuits138.
TERNARY ALLOYS

The electrodeposition of ternary alloys has been reviewed by Rama Char and coworkers13g.140. Emphasis of new work is on the improvement of magnetic properties of nickel-iron and nickel-cobalt alloys by codeposition with a third element such as iron141* 142,molybdenum 143* l** or phosphorus145. Other areas of current interest involve precious metal plating, such as alloys of goldcopper-cadmium14s, gold-silver-copper147* l**, gold-silver-indium14g~ 150and gold-silver-antimony151. Recent publications include reviews and experimental studies on the deposition of nickel-chromium-iron alloys from aqueous electrolytes162*153.The electrolytic production of these stainless-steel type alloys would offer the possibility of economic advantages where a thin alloy coating could be deposited on a cheap substrate. The most promising bath for future commercial development involves additions of EDTA and its sodium salt to chloride baths.
Electrodepos. Surface Treat., 1 (1972173)

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FUSED SALT ELECTROLYTES

A. KROHN, C. W. BOHN

In addition to the plating of alloys from aqueous solutions, some 35 recent references indicated the use of fused salt electrolytes and one involved the combined electrodeposition of gallium and cadmium from a glycerol electrolyte1j4. the most promising is a highly corrosion-resistant aluminium-manganese One of alloy

plated on a base metal from a chloride melt at the comparatively low temperature of 175P5. The process produces a very attractive alternative to cadmium plating in terms of corrosion resistance, cost and absence of pollution due to cyanide wastes. Chloride melts also have been used to produce an iron-aluminium alloy15j, a lead-bismuth alloy15 and alloys of refractory metals such as titanium158-1G0 and tantalum161. Most refractory metals and their alloys can be deposited in a coherent and compact form from molten alkali fluoride mixtureP. Less conventional procedures produced a molybdenum based alloy by carrying out the plating process in molten sodium containing powdered Mo-Zr (1: 1) in an argon atmosphere163. Melts of SiO, and A&O, dissolved in cryolite deposited silicon and aluminium simultaneously at high current densitieP4. Large single crystals of tungsten oxide bronzes can be formed in Na,WO,/WO, meltP5. Molten electrolytes also yielded alloys of samarium166 and yttrium16.
CONCLUSION

Activity in alloy deposition has shown a continuing expansion in recent years. Most of the new alloys reported apparently do not have any commercial application as yet, but some, such as silver-rhenium, are now in commercial production. Alloy plating for protective and decorative purposes continues to be prominent. The principal newer areas of interest for practical usage are magnetic diverse articles alloys for various computer applications nj8pljg, for electroforming from intricate electronics hardware to large parts for use in the aircraft and aeroon plastics173. It is apparent that alloy space industries170-172 and for electroplating plating will continue to fill a need of technology for special items which cannot be produced in any other way.
REFERENCES 1 A. Brenner, Electrodeposition of Alloys, Principles and Practice, Academic Press, New York, 1963. 2 A. Brenner, Plating, 52 (1965) 1249. 3 N. P. Fedotev, P. M. Vyacheslavov and N. A. Grekova, Zh. Prikl. Khim., 44 (1971) 515; Chem. Abstr., 75 (1971) 14001 m. 4 A. Krohn and C. W. Bohn, Plating, 58 (1971) 237. 5 N. Hall, Metal Finishing, 69 (1) (1971) 46. 6 N. Hall, Metal Finishing, 70 (2) (1972) 34. 7 E. W. Turns and R. D. Krienke, Plating, 52 (1965) 1149.
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207

8 9 10 11 12
13

14
15

16
17

18 19
20 21

22
23 24 25

E. W. Turns, J. W. Head, H. C. Hoffman and A. C. Porter, U.S. Pat. 3,342,708, 1967. E. W. Turns, Plating, 58 (1971) 127. H. R. Thornton and Z. R. Wolanski, Lubrication Eng., 23 (7) (1967) 271. L. I. Kadaner and R. B. Avakyan, USSR Pat. 264,096, 1970; Chem. Abstr., 73 (1970) 10184j. R. B. Avakyan and L. I. Kadaner, Paluchenie Tverd. Iznosostoikikh Galvanichnykh Pokrytii, 1970, p. 86; Chem. Abstr., 76 (1972) 30022~. L. I. Kadaner and R. B. Avakyan, USSR Pat. 246,249,1969; Chem. Abstr., 71(1969) 119033u. R. Henzi and A. R. Mayer, Ger. Pat. Appl. 2,014,122, 1970. R. Henzi, S. Losi and A. Meyer, Ger. Pat. Appl. 2,114,119, 1971. 0. A. Petrii and V. E. Kazarinov, Elektrokhim., 1 (1965) 1389; Chem. Abstr., 64 (1966) 7673a. D. Lee and A. Scrutton, &it. Put. 1,244,850, 1971. A. H. DuRose and W. J. Pierce, U.S. Pat. 3,355,263, 1967. E. Raub and S. Pahlke, Metalloberfiiiche, 23, (1969) 37. I. V. Yanitskii, E. Pacauskas and S. Riselis, USSR Pat. 314,818, 1971; Chem. Abstr., 76 (1972) 9843d. 1. Janickis, E. Pacauskas and I. Lasaviciene, USSR Pat. 310,950, 1971; Chem. Abstr., 75 (1971) 147165q. E. Pacauskas, J. Janickis and A. Saudargaite, Lietuvos TSR Mokslu Akad. Darbai, Ser. B(4) (1969) 75; Chem. Abstr., 72 (1970) 85584~. E. Pacauskas, J. Janickis and D. Mickevicius, Lietuvos TSR Mokslu Akad. Darbai, (3) (1970) 107; Chem. Abstr., 74 (1971) 70812t. W. A. Donakowski and W. S. Springer, Plating, 58 (1971) 1094. K. Aotani, I. Kaneko, S. Takahashi and M. Oiwa, Kinzoku Hyomen Gijutsu, 22 (1971) 496;

Chem. Abstr., 76 (1972) 67318x. 26 M. Kurachi and T. Suzuki, Denki Kagaku, 38 (1970) 519; Chem. Abstr., 74 (1971) 60099b. 27 T. Chocianowicz-Biestkowa, Prace Inst. Mech. Precyzyjnej, 18 (4-B) (1970) 10; Chem. Abstr., 75 (1971) 706202. 28 D. R. France, U.S. Pat. 3607,683, 1971. 29 V. S. Galinker, P. V. Savenko, M. V. Matsola and 0. K. Kudra, USSR Pat. 282,879, 1970; Chem. Abstr., 74 (1971) 82556a. 30 V. V. Orekhova, F. K. Andryushchenko and L. P. Komar, USSR Pat. 305,207, 1971; Chem. Abstr., 75 (1971) 104539x. 31 V. S. Galinker, M. V. Matsola, P. V. Savenko and 0. K. Kudra, Zashchit. Metal., 7 (1971) 210; Chem. Abstr., 75 (1971) 29217k.

32 A. I. Vitkin, 0. A. Petrova, M. N. Nikolskaya, V. I. Abrosimova, M. Kotova and A. A. Gerasimenko, USSR Pat. 312,893, 1971; Chem. Abstr., 75 (1971) 157672s. 33 L. I. Logunova, I. N. Andreev and N. V. Gudin, Sb. Aspir. Rub., Kazan. Khim.-Tekhnol. Inst., Khim. Nauki 1970, p. 147; Chem. Abstr., 76 (1972) 80073h. 34 L. I. Logunova, N. V. Gudin and M. S. Shapnik, Zntensifik. Elektrolit. Protsessov Naneseniya Metallopokrytiyami, 1970, p. 118; Chem. Abstr., 75 (1971) 136480n. 35 J. A. Lisowski and F. B. Lisowski, U.S. Pat. 3,620,937, 1971. 36 K. Naganathan, P. L. Annamalai and R. Srinivasan, Trans. Sot. Advan. Electrochem. Sci. Technol., 5 (1970) 31. 37 E. Z. Napukh, E. A. Nechaev, N. T. Kudryavtsev and K. M. Tyutina, Issled.Elektroosazhdeniyu Rastvoreniyu Metal. 1971, p. 194; Chem. Abstr., 76 (1972) 30029c. 38 E. Z. Napukh, N. T. Kudryavtsev, K. M. Tyutina and L. V. Krylova, Elektrokhim. Protsessy Elektroosazhdenii Anodnom Rastvorenii Metal. 1969, p. 146; Chem. Abstr., 73 (1970) 83086~. 39 J. Bubelis, G. Svilpiene, A. Bernotas and J. Matulis, USSR Pat. 305,206,1971; Chem. Abstr., 75 (1971) 104553x. 40 L. A. Efremova, M. N. Nikolskaya and A. I. Vitkin, Elektroht. Osazhdenie Splavov, 2 (1968) 33; Chem. Abstr., 74 (1971) 18716a. 41 S. A. Gintsberg and A. F. Ivanov, Elektrolit. Osazhdenie Splavov, 2 (1968) 27; Chem. Abstr., 74 (1971) 18719d. 42 K. Aotani, K. Nishimoto and I. Sakate, Kinzoku Hyomen Gijutsu, 22 (1971) 422; Chem. Abstr., 75 (1971) 147054~.
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43 I. P. Dezidereva and E. A. Gubaidullina, Ref. Zh., Khim. 1964, Abstr. No. 20 L 171; Chem. Abstr., 62 (1965) 10069a. 44 L. Domnikov, Metal Finishing, 63 (10) (1965) 98. 4.5 V. S. Galinker and A. I. Saprykin, Ukr. Khim. Zh., 34 (1968) 1305; Chem. Abstr., 70 (1969) 102418e. 46 V. S. Galinker and A. I. Saprykin, Zh. Prikl. Khim., 37 (1964) 342; Chem. Abstr., 61 (1964) 298b. 47 N. R. Kokorev and B. A. Popov, USSR Pat. 185,659, 1966; Chem. Absfr., 66 (1967) 43235k. 48 A. V. Ryabchenkov and N. R. Kokorev, Zashchit. Metal., 5 (1969) 90; Chem. Abstr., 70 (1969) 83528x. 49 K. S. Indira and H. V. K. Udupa, Metal Finishing, 68 (4) (1970) 44 and 68 (5) (1970) 41. 50 K. Takada and T. K. Kabushikikaisha, Brit. Pat. 918,904, 1963. 51 S. Komura, Wire Prod., 43 (3) (1968) 68. 52 N. T. Kudryavtsev, K. M. Tyutina and S. M. Firger, Zh. Prikl. Khim., 35 (1962) 1035; Chem. Abstr., 57 (1962) 9573e. 53 N. V. Korovin, Electroplating Metal Finishing, 17 (5) (1964) 151. 54 L. Domnikov, Metal Finishing, 63 (3) (1965) 63. 55 N. T. Kudryavtsev, Elektrolit. Osazhdenie Splavov, Mosk. Dom Nauchn.-Tekhn. Propagandy 1961, p. 110; Chem. Abstr., 57 (1962) 1968h. 56 W. S. Lee and B. S. An, Chosun Kwahakwon Tongbo, 1967 (5), p. 32; Chem. Abstr., 69 (1968) 56463~. 57 E. J. Roehl, U.S. Pat. 3,420,754, 1969. 58 N. A. Marchenko and Zh. V. Batyuk, Zh. Prikl. Khim., 37 (1964) 595; Chem. Abstr., 61 (1964) 2716 g. 59 M. B. Hammond and G. B. Bowman, U.S. Pat. 3,064,337, 1962. 60 R. J. Clauss, R. W. Klein, R. A. Tremmel and N. C. Adamowicz, Plating, 58 (1971) 679; J. Glayman, Galvano, 36 (1970) 487. 61 D. J. Arrowsmith, Rept. Progr. Appl. Chem., 51 (1966) 62 and 53 (1968) 68. 62 C. U. Chisholm, Plating, 55 (1968) 735 and 59 (1972) 417. 63 C. U. Chisholm, Trans. Inst. Metal. Finishing, 46 (1968) 147. 64 B. A. Shenoi and S. Gowri, Metal Finishing, 70 (5) (1972) 96. 65 N. R. Bharucha and J. J. B. Ward, Brit. Pat. 1,213,556, 1970. 66 H. Brown, Proc. Conf Natl. Assoc. Corrosion Eng. 26th, 1970, p. 86. 67 C. J. A. Schilders, Tijdschr. Oppervlakte Tech. Metal., 14 (5) (1970) 144; Chem. Abstr., 74 (1971) 48907f. 68 L. A. Rubio Felipe, Rev. Met. (Madrid), 6 (1970) 532; Chem. Abstr., 74 (1971) 115098h. 69 J. C. Jongkind and F. B. Cargo, Plating, 57 (1970) 901. 70 J. B. Mohler, Metal Finishing, 69 (12) (1971) 45. 71 N. J. Spiliotis, Ger. Pat. Appl. 1,958,220, 1970. 72 M. Paunovic and R. Oechslin, Plating, 58 (1971) 599. 73 E. Ivanova and V. Mateev, Elektroprom. Priborostr., 6 (9) (1971) 344; Chem. Abstr., 76
(1972) 120701~.

74 G. B. Rynne, Plating, 58 (1971) 867. 75 R. Fath and F. Hasko, Koroze Ochrann Mater., 15 (5) (1971) 91; Chem. Abstr., 76 (1972) 107206t. 76 R. Fath, F. Hasko, A. DeBokay and A. Lafaye, Ger. Pat. Appl. 2,135,071, 1972. 77 A. Pianelli, Galvano, 40 (1971) 599; Chem. Abstr., 75 (1971) 93747k. 78 N. A. Smagunova and A. K. Yudina, USSR Pat. 287,483, 1970; Chem. Abstr., 75 (1971) 29384n. 79 D. G. Foulke, Ger. Pat. 1,621,162, 1971. 80 S. Yamamoto and Y. Onota, Japan. Pat. 7,109,921, 1971; Chem. Abstr., 76 (1972) 30198g. 81 K. Yamamura, Japan. Pat. 7,031,366, 1970; Chem. Abstr., 75 (1971) 14316t. a2 F. I. Nobel and B. D. Ostrow, U.S. Pat. 3,642,589, 1972. 83 G. T. Viglione, U.S. Pat. 3,547,626, 1970. 84 E. M. Levy, Plating, 56 (1969) 903.
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209

85 H. V. Venkatasetty, J. Electrochem. Sot., 117 (1970) 403. 86 E. Toledo and P. Sernienko, U.S. Put. 3,616,290, 1971. 87 W. G. Hespenheide, U.S. Put. 3,592,746, 1971. 88 S. Schweizerhof, U.S. Pat. 3,642,602, 1972. 89 S. Sakai and T. Hoshi, Japan. Pat. 70,22,001, 1970; Chem. Abstr., 74 (1971) 49085~. 90 H. B. Shukovsky and T. E. Torok, U.S. Pat. 3,639,217, 1972. 91 Telefunken Patentverwertungsgesellschaft m.b.H., Brit. Pat. 1,248,220, 1971. 92 W. Michalke and C. Spinarke, Phys. Status Solidi, A, 2 (1970) K245. 93 H. E. Austen, J. Electrochem. Sot., 117 (1970) 845 and U.S. Pat. 3,525,677, 1970. 94 F. R. Morral, Plating, 59 (1972) 131. 95 V. Tutovan and N. Velican, Thin Solid Films, 7 (1971) 219. 96 V. Tutovan and N. Velican, Ann. Stiint. Univ. Al. Z. Cuza Zasi, Sect. lb, 16 (1970) 195;
Chem. Abstr., 74 (1971) 92770e. 97 A Munteanu, A. Schiff, and C. Marcu, Rev. Phys. Acad. Rep. Populaire Roumaine, 15 (1970) 207; Chem. Abstr., 73 (1970) 50125x. 98 V. Racinskas, L. Saurukaite and B. Radziuniene, Zashchit. Metal., 6 (1970) 609; Chem. Abstr., 74 (1971) 8917~. 99 I. I. Potapov, N. T. Kudryavtsev and M. M. Melnikova, Elektrolit. Osazhdenie Splavov, 1 (1968) 65; Chem. Abstr., 74 (1971) 17295a. 100 B. S. Zolotkovskii, A. M. Pishikin and M. Ya. Popereka, Uch. Zap., Kulinin, Gos. Ped. Inst., 79 (1970) 139; Chem. Abstr. 75 (1971) 93875a. 101 G. S. Alberts and J. M. Brownlow, U.S. Pat. 3,622,469, 1971. 102 J. Kulikowski, Elektroniku, 12 (1971) 465; Chem. Abstr., 76 (1972) 10547Oa. 103 Electronics Symposium, Plating, 54 (1967) 5, 6; and A. F. Schmeckenbecher, Plating, 58 (1971) 905.

104 A. I. Bogenschuetz and J. L. Jostan, Gulvanotechnik, 61 (1970) 3; 61 (1970) 279; 61 (1970) 362. 105 J. J. Mazur, U.S. Pat. 3,528,892, 1970. 106 B. F. Rothschild, U.S. Pat. 3,554,878, 1971. 107 C. W. Nelson and J. F. Hinchey, U.S. Pat. 3,625,837, 1971. 108 V. A. Gutorov, M. I. Dmitrieva, and M. A. Zevakin, USSR Put. 320,089, 1971; Chem.
Abstr., 76 (1972) 4136Oe.

109 W. K. Lee, Plating, 58 (1971) 997. 110 E. S. Bruk, and R. G. Kovaleva, Elektrolit. Osazhdenie Splavov, 2 (1968) 73; Chem. Abstr., 74 (1971) 8927f. 111 U. Costa and G. Canegallo, French Put. 1,589,589, 1970. 112 A. M. Pishikin and M. Ya. Popereka, Uch. Zap., Kalinin. Gos. Ped. Inst., 79 (1970) 132;
Chem. Abstr., 75 (1971) 93864~.

113 G. Ya. Varlamov, A. M. Pishikin and M. Ya. Popereka, Uch. Zap., Kalinin. Gos. Ped. Inst., 79 (1971) 150; Chem. Abstr., 75 (1971) 93865x. 114 S. L. Phillips and C. E. Johnson, J. Electrochem. Sot., 117 (1970) 827. 115 V. P. Taranets, Tekhnol. Organ. Proizvod. 1970, No. 3, p. 64; Chem. Abstr., 74 (1971) 1502OOg. 116 I. D. Kudryavtseva and M. F. Skalozubov, Tr. Novocherk. Politekhn. Inst., 190 (1969) 44; Chem. Abstr., 74 (1971) 8908a. 117 E. Schmid and K. Schnur, Ger. Pat. Appl. 1,948,734, 1971. 118 A. G. Filatov, I. N. Klochkov and L. M. Belenkaya, USSR Put. 301,373, 1971; Chem. Abstr., 75 (1971) 83583q. 119 P. S. Melnikov, R. S. Saifullin and G. S. Vozdvizhenskii, Zushchit. Metal., 7 (1971) 354;
Chem. Abstr., Chem. Abstr., 75 (1971) 44196~.

120 S. N. Vinogradov,

N. T. Kudryavtsev

and N. F. Kulagina, Zushchit. Metal.,

8 (1972) 92;

76 (1972) 107201n.

121 V. A. Ilin and L. S. Fortovova, USSR Pat. 273,614, 1970; Chem. Abstr., 74 (1971) 27534s. 122 N. A. Grekova and P. M. Vyacheslavov, Zh. Prikl. Khim., 44 (1971) 1975; Chem. Abstr.,
76 (1972) 30050~.

123 N. P. Fedotev, P. M. Vyacheslavov

and G. K. Burkat, Elektrolit.

Osazhdenie

Splavov,

(1968) 64; Chem. Abstr., 74 (1971) 18718~. 124 V. P. Greco, Plating, 59 (1972) 115. Electrodepos. Surface Treat., I (1972173)

210

A. KROHN, C. W. BOHN

125 T. Miyashige and R. Suzuki, Kinzoku Hyomen Gijutsu, 22 (1971) 216; Chem. Abstr., 75 (1971) 157547e. 126 P. F. Kalyuzhnaya and V. B. Sobko, Ukr. Khim. Zh., 36 (1970) 403; Chem. Abstr., 13 (1970) 51472~. 127 P.F. Kalyuzhnaya, K. N. Pimenova and V. B. Sobko, Elektrolit. Osazhdenie Splavov, I (1968) 72; Chem. Abstr., 74 (1971) 8933e. 128 K. Aotani and K. Nishimoto, Kinzoku Hyomen Gijutsu, 21 (1970) 356; Chem. Abstr., 73 (1970) 94067j. 129 J. L. Polti, Ger. Pat. Appl. 2,011,374, 1970. 130 W. Metzger, R. Ott, G. Pappe and H. Schmidt, Ger. Pat. 1,621,206, 1971. 131 M. Viswanathan and K. S. G. Doss, Metal Finishing 70 (2) (1972) 83. 132 E. Kedward, B. Kiernan, and C. L. M. Cottrell, Brit. Pat. 1,265,472, 1972. 133 V. 0. Nwoko, Electroplating Metal Finishing, 24 (12) (1971) 28. 134 D. S. R. Brown and K. V. Gow, Plating, 59 (1972) 437. 135 B. Kiernan and E. C. Kedward, Brit. Pat. 1,220,078, 1971. 136 E. C. Kedward, B. Kiernan and R. A. Duffin, Brit. Pat. 1,220,331, 1971. 137 F. E. Luborsky, M. W. Breiter and B. J. Drummond, J. Electrochem. Sot., 119 (1972) 92. 138 I. J. Hutkin, U.S. Pat. 3,512,946, 1970. 139 M. Sarojamma and T. L. Rama Char. Electroplating Metal Finishing, 18 (2) (1965) 51. 140 R. Sivakumar and T. L. Rama Char, Electroplating Metal Finishing, 24 (1) (I 971) 14. 141 P. P. Semienko and E. Toledo, U.S. Pat. 3,533,922, 1970. 142 Honeywell Inc., Brit. Pat. 1,249,642, 1971. 143 I. Bursuc, I. Diaconu, and C. Cuciureanu, Thin Solid Films, 5 (1970) 297. 144 W. L. Wade, Jr. and G. Sands, J. Electrochem. Sot., 118 (1971) 1137. 145 P. E. McQuaid and A. J. Kolk, Jr., U.S. Pat. 3,573,571, 1971. 146 Deutsche Gold- und Silber-Scheideanstalt vorm. Roessler, French Pat. Appl. 2,011,755, 1970. 147 P. S. Melnikov, Zashchit Metal., 6 (1970) 365; Chem. Abstr., 73 (1970) 514762. 148 G. Bacquias, Gulvano, 40 (1971) 917. 149 N. A. Smagunova, N. N. Balashova and Z. N. Marakhtanova, USSR Pat. 280,154, 1970; Chem. Abstr., 74 (1971) 490932. 150 T. J. Menzel, Ger. Pat. Appl. 2,033,970, 1971. 151 L. Domnikov, Metal Finishing, 68 (12) (1970) 54. 152 C. U. Chisholm and R. J. G. Carnegie, Plating, 59 (1972) 28. 153 S. Gowri and B. A. Shenoi, Metal Finishing, 70 (6) (1972) 30. 154 Sh. Z. Khamudkhanova, V. B. Sheremeteva, A. M. Murtazaev and G. A. Tsyganov, Dokl. Akad. Nauk Uz. SSR, 27 (5), (1970) 33; Chem. Abstr., 75 (1971) 70633f. 155 E. J. Smith, M. G. Vucich and L. W. Austin, U.S. Pat. 3,268,422, 1966; Chem. Eng. News, 49 (6) (1971) 10. 156 M. V. Myshalov and N. G. Chovnyk, USSR Pat. 281,987, 1970; Chem. Abstr., 74 (1971) 106613~. 157 Yu. K. Delimarskii, 0. G. Zarubitskii, V. G. Budnik and 0. A. Salabai, USSR Pat. 291,983, 1971; Chem. Abstr., 75 (1971) 14320q. 158 Yu. Ya. Andreev, G. A. Kolobov, B. S. Lysov and N. S. Rychova, Isv. Vysshikh Uchebn. Zavedenii Tsvetn. Met., 13 (6) (1970) 82; Chem. Abstr., 74 (1971) 93774~. 159 S. Tokumoto and E. Tanaka, Ger. Pat. Appl. 2,017,204, 1970. 160 Yu. G. Olesov, V. I. Cherkashin and A. N. Rubtsov, Zh. Prikl. Khim., 44 (1971) 933; Chem. Abstr., 75 (1971) 44190q. 161 J. J. Rameau, Rev. Intern. Hautes Temp. Refract., 8 (1971) 59. 162 R. Darras, Nucl. Sci. Abstr., 25 (1971) 29783. 163 M. L. Chaevskii and M. S. Goikhmnak, USSR Pat.[298,701, 1971; Chem. Abstr., 75 (1971) 120807~. 164 G. Boe, K. Grjotheim, K. Matiasovsky and P. Fellner, Can. Met. Quart., 10 (1971) 281. 165 R. A. Fredlein and A. Damjanovic, J. Solid State Chem., 4 (1972) 94. 166 E. Morris, Jr., J. E. Murphy and T. A. Henry, Japan. Pat. 70,17,064, 1970; Chem. Abstr., 73 (1970) 68878e. Electrodepos. Surface Treat., I (1972173)

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OF ALLOYS

211

167 D. Bratland, G. H. Boll, K. Grjotheim, H. Rensvik and E. Aamland, Rev. Chim. Acad. Rep. Populaire Roumaine, 17 (1972) 41; Chem. Abstr., 16 (1972) 120714b. 168 J. S. Sallo, Plating, 54 (1967) 257. 169 J. S. Mathias and G. A. Fedde, Z.E.E.E. Trans. Magn., 5 (1969) 728. 170 W. H. Safranek, Plating, 53 (1966) 1211. 171 L. Winkler, Ober-aeche, 4 (1969) 127; 5 (1969) 175. 172 F. ONeill, Plating, 57 (1970) 205. 173 W. P. Innes, Plating, 54 (1967) 378.

Galvanisierung

von Legierungen

Die Aktivitaten auf dem Gebiet der elektrolytischen Abscheidung von Legierungen haben wahrend der letzten Jahre eine zunehmende Expansion verzeichnet. Nicht alle Legierungsabscheidungen, iiber die berichtet wurde, haben den Weg zu kommerziellen Anwendungen gefunden, einige jedoch, wie z. B. Silber-Rhenium-Ulberziige, sind bereits technisch eingesetzt. Legierungsabscheidungen sind sowohl fiir dekorative als such ftir schtitzende Zwecke hervorragend anzuwenden. Prinzipielle neue Anwendungsgebiete zeichnen sich ab fiir magnetische Legierungsiiberziige ftir Datenverarbeitungsanlagen, fi_ir die Elektroformung diverser Teile der Elektronik und grosser Teile fur die Luftfahrt- und Raketenindustrie und schliesslich beim Galvanisieren von Plastwerkstoffen. Ganz offenbar nehmen die Bedarfsfalle zu, bei denen Legierungsabscheidungen eine technologische Lticke schliessen und dort eingesetzt werden, wo andere Moglichkeiten nicht bestehen. Die neuere Literatur dieses Fachgebietes wurde kritisch analysiert. Die Diskussion beriicksichtigt vorwiegend Abscheidungen binarer Legierungen aus wasserigen Lijsungen und ihre praktischen Anwendungen, dispersionsgehartete Legierungen und Komposite, ternare Legierungen und Legierungsabscheidungen aus Salzschmelzen.
Le d&fit ilectrolytique des a&ages

La litterature

recente

sur le depot

Clectrolytique

dalliages

est examinee.

La discussion Porte principalement sur les systemes binaires deposes a partir de solutions aqueuses et leurs applications pratiques mais il est Cgalement fait mention des alliages durcis par dispersion et des mattriaux tlectrochimiques heterogenes, des systemes ternaires et des alliages deposes a partir delectrolytes a se1 fondu. Les depots dalliages, qui continuent a Ctre utilises comme rev&tements decoratifs et protecteurs, ont trouve en outre de nouvelles applications comme films en alliage magnetique pour lindustrie des ordinateurs, dans la galvanoplastie, dans Iindustrie electronique et dans le revCtement des plastiques.

Electrodepos. Surface Treat., 1 (1972173)