US3326782A - Bath and method for electroforming and electrodepositing nickel - Google Patents

Bath and method for electroforming and electrodepositing nickel Download PDF

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US3326782A
US3326782A US368651A US36865164A US3326782A US 3326782 A US3326782 A US 3326782A US 368651 A US368651 A US 368651A US 36865164 A US36865164 A US 36865164A US 3326782 A US3326782 A US 3326782A
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nickel
bath
current density
sulfamate
cathode
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Richard J Kendrick
Sidney A Watson
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Huntington Alloys Corp
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International Nickel Co Inc
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/16—Regeneration of process solutions
    • C25D21/18—Regeneration of process solutions of electrolytes

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  • the present invention is directed to a new nickel plating bath and method for electrodepositing nickel and, more particularly, to a nickel sulfamate plating bath and method for electrodepositing nickel which provides a wide variety of desirable results in regard to the electrodeposition of nickel.
  • the bath may be made by direct solution of pure nickel sulfamate
  • nickel sulfamate is usually obtained as a concentrated solution and the bath is formed by diluting and then purifying the concentrated solution.
  • This purification which is essential in order to minimize pitting and to give deposits of the best quality, is usually carried out by electrolysis at a low current density and then by prolonged electrolysis at conventional current densities.
  • treatment with activated carbon may be required.
  • a buffer which is nearly always boric acid
  • a substance which promotes anode corrosion which is nearly always nickel chloride
  • agents are added to prevent hydrogen pitting or to convert the internal tensile stress to compressive stress.
  • the concentration of the nickel sulfamate in the solution used as the electrolyte has varied in practice from 250 to 370 grams per liter (g.p.l.) as a general rule but a solution containing 450 g.p.l. nickel sulfamate has sometimes been used. It is well known that in electroplating the higher the cathode current density the greater is the speed of deposition but under given plating conditions there is a practical maximum current density above which so-called burning occurs. The value of this practical maximum current density depends not only on the temperature of operation but also on the rate of agitation and the disposition of the anode and the cathode in the plating vat. With sulfamate baths in which the temperature of operation varies from 25 C.
  • the invention is based on the discovery that by working with more highly concentrated nickel sulfamate solutions than hitherto, it is possible to obtain various advantageous results in accordance with the current density used.
  • curve A illustrates the effect of sulfamate concentration in the bath against practical maximum cathode current density
  • curve B illustrates the effect of sulfamate concentration in the bath against internal stress level in the deposit at a given cathode current density.
  • the invention comprises a special aqueous nickel sulfamate electroplating bath of high concentration and a method for electrodepositing nickel therefrom.
  • the nickel sulfamate bath contains at least about 500 to about 700 g.p.l. of nickel sulfamate.
  • the concentration of nickel sulfamate in the bath more suitably is from about 550 to about 650 g.p.l. since Within this range higher deposition rates are possible and lower stress values in the deposit obtainable. Particularly advantageous results in these respects are obtained when the concentration is about 600 g.p.l.
  • the bath is operated at a pH of about 4 with a pH range of 2.0 to about 5.5 being satisfactory.
  • pH adjustment is preferably made by addition of sulfamic acid. Usual means of agitation, e.g., air agitation, may be employed.
  • the bath preferably contains a buffering agent such as boric acid in usual amounts up to saturation, e.g., from about 10 g.p.l. up to 30 or 45 g.p.l. of boric acid, and may also contain nickel chloride in amounts up to 30 g.p.l., e.g., about 3 to about 30 g.p.l. of nickel chloride (NiCl .6H O).
  • a buffering agent such as boric acid in usual amounts up to saturation, e.g., from about 10 g.p.l. up to 30 or 45 g.p.l. of boric acid, and may also contain nickel chloride in amounts up to 30 g.p.l., e.g., about 3 to about 30 g.p.l. of nickel chloride (NiCl .6H O
  • the-bath is maintained at a temperature of about 50 C. to about 80 C. and, more advantageously, is operated in the temperature range of about 60 C. to about C. It is found that unsatisfactory results from the standpoint of control of stress level of the deposit are obtained below 50 C. or, from the standpoint ofthermal control of the solution, above C.
  • the special electroplating method provided in accordance with the invention makes available great flexibility in operation, permits close control of the internal stress level and hardness in nickel electrodeposits, and enables the production of bright deposits without the addition 3 of special brightening agents to the bath for this purpose, all through control of the cathode current density em ployed.
  • the bath provides a means for electrodepositing nickel at hitherto unobtainably high rates of deposition since, in special cases, cathode current densities as high as 800 a.s.f. can be employed.
  • the temperature of operation has a material effect on the result. If the temperature is reduced from 60 C. to 50 C., the internal stress moves rapidly in the tensile direction. Below 50 C. the tensile stress in the deposit is so high, and the maximum practical current density so reduced that the use of the solution offers no significant advantage over conventional solutions. If the solution is heated to 70 C., curve A is moved upwards and the maximum current density is raised to the remarkable level of 800 a.s.f. Increase in the temperature of the solution displaces curve B in the direction of increased compressive stress and, therefore, at any given current density the compressive stress is higher or the tensile stress lower for a higher temperature of the solution,
  • the invention can advantageously be employed in electroforming. It is well know-n that a deposit produced in electroforming should have low internal tensile stress if it is to have the dimension stability which is required for many purposes. For example, in the preparation of the metal discs with which phonograph records are stamped, a tensile stress as high as 8,000 pounds per square inch (p.s.i.) is tolerated but zero stress would, in fact, be much preferred. For some other purposes, compressive internal stress is actually desirable. Working at 60 C. and at 600 g.p.l., an electrodeposit having an internal tensile stress of 8000 p.s.i.
  • a current density of about 230 a.s.f. can be produced with a current density of about 230 a.s.f.; a deposit having zero internal stress can be produced with a current density of about 170 a.s.f.; and a deposit having a compressive internal stress of 14,000 p.s.i. can be produced with a current density of 50 a.s.f. without the use of addition agents.
  • a low current density such as 50 a.s.f.
  • the electrolyte contains no addition agents, the deposit is highly stressed in compression with the advantage that the resistance to fatigue of components plated with such a deposit is increased. If the temperature is increased to 70 C. at the same concentration, deposits of substantially zero internal stress may be obtained with current densities as high as 300 a.s.f.
  • control of internal stress level in the deposits is achieved by correlating cathode current density and bath temperature without the use of a stress-reducing agent in the bath as set forth in the following table:
  • the internal stress levels obtained with higher current densities than those shown in the foregoing table are higher than those shown.
  • internal stress levels up to about 18,000 p.s.i. tensile are obtained at current densities up to 250 a.s.f.
  • at 60 C. internal stress levels up to about 22,000 p.s.i. tensile are obtained at current densities up to 400 a.s.f.
  • at 65 C. internal stress levels up to about 18,000 p.s.i. tensile are obtained at current densities up to 600 a.s.f.
  • at 70 C. internal stress levels up to about 12,000 p.s.i. tensile are obtained at current densities up to 800 a.s.f.
  • current densities lower than the minima given in the table at the given temperatures give lower, i.e., more strongly cornpressive, internal stresses than 2,000 p.s.i. compressive stress.
  • a high current density e.g. 350 a.s.f.
  • a brightening agent any of the brightening agents commonly used in conventional bright nickel solutions based on the Watts bath, e.g., p-toluene sulfonamide, saccharin, aryl sulfonic acids, acetylenic alcohols, etc., in the amounts commonly used, may be employed.
  • nickel sulfamate solutions containing from 500 to 700 g.p.l. nickel sulfamate it is desirable to use reactive nickel anodes such as those containing a small proportion of sulfur to promote uniform corrosion.
  • Nickel chloride may advantageously be incorporated into the solution to promote smooth dissolution of the anode. If the anode is not reactive, the current density at the anode cannot be increased beyond about 200 a.s.f. without causing the evolution of gas even in the presence of the advantageous quantity of nickel chloride, namely, about 5 g.p.l. If it is desired to plate an article at a cathode current density of about 400 a.s.f. using an anode which does not contain sulfur, the surface area of the anode must be some two to three times greater than the cathode surface area of the article, and, if a cathode current density of 800 a.s.f.
  • the ratio of the surface areas will need to be as much as 5:1. It will readily be appreciated that it is difiicult to arrange for the anode area to be as much as twice or more the cathode area where conforming anodes are used, that is to say, anodes whichtake the shape of the cathode.
  • the anode current density can be increased to 540 a.s.f. if the concentration of nickel chloride in the solution is 30 g.p.l.
  • nickel chloride is to increase the stress in the deposits formed and for this reason the concentration should be kept as low as practicable, the coatings formed at the highest current densities are under considerable stress already and the increase in stress is not of such great importance.
  • Nickel sulfamate plating solutions provided in accordance with the invention have certain additional advantages over conventional plating solutions. Inparticular, the throwing power of the electrolyte is superior to that of conventional sulfamate solutions and the Wattstype solutions.
  • a method for measuring throwing power using a Hull cell is described in the paper entitled The Throwing Power of Nickel and Other Plating Solutions, by Dr. S. A. Watson, Transactions of the Institute of Metal Finishing, 1960, vol. 37, pages 28 to 39. Throwing power generally decreases as the current density is increased in nickel plating solutions.
  • a solution according to the invention containing 600 g.p.l. nickel sulfamate and approximately 5 g.p.l. nickel chloride was compared at 60 C.
  • nickel sulfamate solutions containing from 500 to 700 g.p.l. nickel sulfamate is satisfactory.
  • the conductivity of an all-chloride solution is better than the conductivity of solutions of the present invention but solutions according to the present invention have higher conductivities than either a conventional Watts solution or a conventional nickel sulfamate solution.
  • the hardness of the deposits obtainable varies inversely with the current density.
  • the hardness at 200 a.s.f. is of the order of 220 Vickers Pyramid Number (V.P.N.).
  • the hardness is 300 V.P.N. but when the current density is reduced to 30 a.s.f., the hardness is 400 V.P.N.
  • V.P.N Vickers Pyramid Number
  • a thin, very hard layer of nickel may first be deposited upon a matrix, followed by a more substantial layer of lower hardness so as to give an electroformed product with a hard face upon removal thereof from the matrix.
  • hydrolysis of the nickel sulfamate should be avoided.
  • An increase in the temperature of the solution increases the rate of hydrolysis as do also a decrease in the pH of the solution and a decrease in concentration of nickel sulfamate over the range used in the invention.
  • the increase in rate of hydrolysis if the solution is kept at 70 C. as distinguished from 60 C., is quite acceptable in practice. For example, if a solution containing 600 g.p.l.
  • nickel sulfamate and having a pH of 4 is kept at a temperature of 65 C.
  • the rate of accumulation of ammonium ions is of the order of l g.p.l. per year. If a similar solution is stored at 70 0, this rate of accumulation rises to only 5 to 6 g.p.l. per year. This is produced by breakdown of only approximately one one-hundredth of the original nickel sulfamate. It is possible to plate from a solution which is at a temperature as high as 80 C. but the improvement in properties obtained is largely offset by difficulties which have to be overcome in the thermal control of the solution so in practice it is advantageous to work at temperatures not exceeding about 70 C.
  • each, lead shuold not exceed about 0.002 g.p.l., and chromium should not exceed about 0.02 g.p.l.
  • the foregoing impurities all have deleterious effects upon nickel electro deposits produced from nickel plating baths containing the same as is discussed, for example, at page 35 in the handbook Practical Nickel Plating, second edition, 1959, published by The International Nickel Company, Inc.
  • the conversion factor 5.503 is to be employed.
  • a nickel sulfamate concentration of 600 g.p.l. corresponds to an equivalent nickel concentration of 109 g.p.l.
  • the cathode current efiiciency obtained in accordance with the invention is very high, i.e., on the order of 100%. This factor enables eflicient use of the high plating currents contemplated in accordance with the invention.
  • cathode materials plated in accordance with the invention can take any of the usual forms, e.g., flat and/ or curved surfaces and the like, without any impairment in results attributable to cathode shape.
  • the high operating cathode current densities made possible in accordance with the invention provide the very practical advantage that electroforms and other types of nickel platings can be produced in very short times.
  • nickel electroforms, etc. can be produced according to the invention in an equivalent or shorter time than that required to produce similar electrodeposited objects in other metals such as copper.
  • the method for electrodepositing nickel which comprises passing a current at a cathode current density up to 800 amperes per square foot through an aqueous acid bath consisting essentially of at least about 500 and up to about 700 grams per liter of nickel sulfamate from an anode to a cathode immersed therein while maintaining the bath pH between about 2.0 and about 5.5, and while maintaining the bath temperature between about 50 C. and about C.
  • the method for electrodepositing nickel at a controlled internal stress level between about 2,000 pounds per square inch compressive and about 8,000 pounds per square inch tensile which comprises passing a current from an anode to a cathode immersed in an aqueous acid bath having a pH of about 2.0 to 5.5 and consisting essentially of at least about 550 and up to about 650 grams per liter of nickel sulfamate, a buffering amount up to saturation of boric acid, and up to about 30 grams per liter of nickel chloride, and controlling the cathode current density and the bath temperature such that at a bath temperature of 55 C. the cur-rent density is about to 175 amperes per square foot, at 60 C. the current density is about 150 to about 230 amperes per square foot, at 65 C. the current density is about 200 to about 330 amperes per square foot, and at 70 C. the current density is about 250 to about 450 amperes per square foot.
  • the method for electrodepositing nickel at a controlled internal stress level between about 1,000 pounds per square inch compressive and about 4,000 pounds per square inch tensile which comprises passing a current from an anode to a cathode immersed in an aqueous acid bath having a pH of about 2.0 to 5.5 and consisting essentially of at least about 550 and up to about 650 grams per liter of nickel sulfamate and controlling the cathode current density and the bath temperature such that at a bath temperature of 55 C. the current density is about 110 to about 150 amperes per square foot, at 60 C.
  • the current density is about 160 to about 200 amperes per square foot, at 65 C, the current density is about 210 to about 245 amperes per square foot, and at 70 C. the current density is about 260 to about 340 amperes per square foot.
  • the method for electrodepositing nickel at a controlled internal stress level between about 1,000 pounds per square inch compressive and about 1,000 pounds per square inch tensile which comprises passing a current from an anode to a cathode immersed in an aqueous acid bath having a pH of about 2.0 to .5 and consisting essentially of at least about 550 and up to about 650 grams per liter of nickel sulfamate and controlling the cathode current density and the bath temperature such that at a bath temperature of 55 C. the current density is about 110 to about 125 amperes per square foot, at 60 C. the current density is about 160 to about 180 amperes per square foot, at 65 C. the current density is about 210 to about 240 amperes per square foot, and at 70 C. the current density is about 260 to about 290 amperes per square foot.
  • a method for electrodepositing a bright nickel deposit which comprises passing a plating current through an aqueous bath devoid of organic brightening agents and consisting essentially of at least about 500 and up to about 700 grams per liter of nickel sulfamate to a cathode immersed therein at a cathode current density not exceeding about 70 amperes per square foot while maintaining the bath pH between about 2.0 and about 5 .5 and while maintaining the bath temperature between 55 C, and 70 C.
  • a method for electrodepositing a bright nickel deposit which comprises passing a plating current through an aqueous acid bath devoid of organic brightening agents and consisting essentially of at least about 550 and up to about 650 grams per liter of nickel sulfamate to a cathode immersed therein at a cathode current density not exceeding about 70 amperes per square foot while maintaining the bath pH between about 2.0 and about 5.5, and while maintaining the bath temperature between 55 C. and 70 C.
  • a method for electrodepositing a bright nickel deposit which comprises passing a plating current through an aqueous acid bath devoid of organic brightening agents and consisting essentially of about 600 grams per liter of nickel sulfamate to a cathode immersed therein at a cathode current density not exceeding about 70 amperes per square foot while maintaining the bath pH between about 2.0 and about 5.5, and while maintaining the bath temperature between 60 C. and 70 C.
  • a method for electroforming nickel to provide an electroformed deposit wherein the internal stress level does not exceed zero comprises passing a current through an aqueous bath having a pH of about 4 and consisting essentially of about 600 grams per liter of nickel sulfamate and having a temperature of about 70 C. to a cathode immersed therein at a cathode current density not exceeding about 300 amperes per square foot.
  • the method for electroforming nickel to provide an electroformed deposit wherein the internal stress level does not exceed 1,000 pounds per square inch tensile which comprises passing a current through an electrolyte consisting essentially of water, about 500 to about 700 grams per liter of nickel sulfamate and having a pH of about 2.0 to about 5.5 to a cathode immersed therein and controlling the cathode current density and the bath temperature such that at a bath temperature of 55 C. the cathode current density does not exceed amperes per square foot, at 60 C. the cathode current density does not exceed 180 amperes per square foot, at 65 C. the cathode current density does not exceed 240 amperes per square foot, and at 70 C. the cathode current density does not exceed 290 amperes per square foot.
  • the method for electroforming nickel to provide an electroformed deposit wherein the internal stress is about 8000 pounds per square inch tensile which comprises passing a current through an electrolyte consisting essentially of water and about 600 grams per liter of nickel sulfamate, about 10 to about 45 grams per liter of boric acid, about 5 grams per liter of nickel chloride, and having a pH of about 4 to a cathode immersed therein and controlling the cathode current density and the bath temperature such that the bath temperature is about 60 C. and the cathode current density is about 230 amperes per square foot.
  • a method for electroforming nickel to provide an electroformed deposit wherein the stress level is about Zero comprises passing a current through a bath having a pH of about 4 and consisting essentially of water and about 600 grams per liter of nickel sulfamate, a buffering amount of boric acid and about 5 grams per liter of nickel chloride, and having a temperature of about 60 C. to a cathode immersed therein at a cathode current density not exceeding about amperes per square foot.
  • a method for electroforming nickel to provide a deposit having a low internal stress at a high nickel deposition rate which comprises passing a current through a bath consisting essentially of water and about 600 grams per liter of nickel sulfamate to a cathode immersed therein at a cathode current density not exceeding about 300 amperes per square foot while maintaining the bath pH at about 4, and while maintaining the bath temperature at about 70 C.
  • a method for electrodepositing a bright nickel deposit which comprises passing a plating current through a bath consisting essentially of water, at least about 550 and up to about 650 grams per liter of nickel sulfamate, a buffer, and an effective amount of at least one organic brightening agent to a cathode immersed therein at a cathode current density up to about 350 amperes per square foot while maintaining the bath pH between about 2.0 and about 5.5, and while maintaining the bath temperature between 50 C. and 80 C.
  • An electroplating bath capable of depositing high quality nickel electrodeposits at cathode current densities as high as 800 amperes per square foot comprising an aqueous acid solution consisting essentially of about 600 grams per liter of nickel sultamate, boric acid in an amount up to saturation, up to about 30 grams per liter of nickel chloride, and having a pH of about 4.
  • An electroplating bath capable of depositing high quality nickel electrodeposits at cathode current densities as high as 800 amperes per square foot comprising an aqueous acid solution consisting essentially of at least about 550 and up to about 650 grams per liter of nickel sulfamate, boric acid in an amount up to saturation, up to about 30 grams per liter of nickel chloride, and having a pH of about 2.0 to about 5.5
  • An electroplating bath capable of depositing high quality nickel electrodeposits at cathode current densities as high as 800 amperes per square foot comprising an aqueous acid solution consisting essentially of at least about 500 and up to about 700 grams per liter of nickel References Cited UNITED STATES PATENTS 5/1943 Cupery 204-49 4/1966 Stephenson et a1. 204-3 X 10 OTHER REFERENCES Barrett, Richard C.: Nickel Plating From the Sulfamate Bath, Plating, vol. 41, No. 9, pp. 1027-1033, September 1954.

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  • Materials Engineering (AREA)
  • Metallurgy (AREA)
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  • Electroplating And Plating Baths Therefor (AREA)
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US368651A 1963-05-22 1964-05-19 Bath and method for electroforming and electrodepositing nickel Expired - Lifetime US3326782A (en)

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GB20443/63A GB999117A (en) 1963-05-22 1963-05-22 Electrodeposition of nickel
GB3774863 1963-09-25
GB26621/65A GB1101093A (en) 1963-05-22 1965-06-23 Electrodeposition of nickel

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GB (2) GB999117A (xx)
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3360445A (en) * 1965-01-04 1967-12-26 Du Pont Electrodeposition of nickel from the sulfamate bath
US3374154A (en) * 1965-07-12 1968-03-19 Int Nickel Co Electroforming and electrodeposition of stress-free nickel from the sulfamate bath
FR2183944A1 (xx) * 1972-05-08 1973-12-21 Xerox Corp
US3891542A (en) * 1973-11-05 1975-06-24 Ford Motor Co Method for insuring high silicon carbide content in elnisil coatings
US3939046A (en) * 1975-04-29 1976-02-17 Westinghouse Electric Corporation Method of electroforming on a metal substrate
US3963587A (en) * 1975-05-19 1976-06-15 Xerox Corporation Process for electroforming nickel foils
US4160709A (en) * 1975-12-23 1979-07-10 Messerschmitt-Bolkow-Blohm Gmbh Process for the galvanic deposition of nickel from a nickel bath
US4290858A (en) * 1980-09-23 1981-09-22 The United States Of America As Represented By The United States Department Of Energy Process for forming a nickel foil with controlled and predetermined permeability to hydrogen
US6485542B2 (en) * 1998-05-20 2002-11-26 Japan Energy Corporation Ni-Fe alloy sputtering target for forming magnetic thin films, magnetic thin film, and method of manufacturing the Ni-Fe alloy sputtering target
US20130015074A1 (en) * 2011-07-12 2013-01-17 Gaydos Stephen P Methods for repairing steel components

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2053342A1 (en) * 1990-10-22 1992-04-23 Robert A. Tremmel Nickel electroplating process with reduced nickel ion build up
DE4109934A1 (de) * 1991-03-26 1992-10-01 Bosch Siemens Hausgeraete Vorrichtung und verfahren zum abschirmen eines freizuhaltenden bereichs eines werkstueckes beim eintauchemaillieren
FR2681080B1 (fr) * 1991-09-06 1995-02-17 Framatome Sa Procede de regeneration de bains de nickelage contenant du sulfamate de nickel et permettant une verification de l'aptitude du bain au nickelage.

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2318592A (en) * 1940-02-24 1943-05-11 Du Pont Electrodeposition
US3244603A (en) * 1962-06-08 1966-04-05 Gen Electric Electrodeposition of a nickel-manganese alloy

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2318592A (en) * 1940-02-24 1943-05-11 Du Pont Electrodeposition
US3244603A (en) * 1962-06-08 1966-04-05 Gen Electric Electrodeposition of a nickel-manganese alloy

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3360445A (en) * 1965-01-04 1967-12-26 Du Pont Electrodeposition of nickel from the sulfamate bath
US3374154A (en) * 1965-07-12 1968-03-19 Int Nickel Co Electroforming and electrodeposition of stress-free nickel from the sulfamate bath
FR2183944A1 (xx) * 1972-05-08 1973-12-21 Xerox Corp
US3891542A (en) * 1973-11-05 1975-06-24 Ford Motor Co Method for insuring high silicon carbide content in elnisil coatings
US3939046A (en) * 1975-04-29 1976-02-17 Westinghouse Electric Corporation Method of electroforming on a metal substrate
US3963587A (en) * 1975-05-19 1976-06-15 Xerox Corporation Process for electroforming nickel foils
FR2311864A1 (fr) * 1975-05-19 1976-12-17 Xerox Corp Procede d'electroformage de cylindres en feuille de nickel, de cobalt ou d'alliage nickel-cobalt et nouveaux produits ainsi obtenus
US4160709A (en) * 1975-12-23 1979-07-10 Messerschmitt-Bolkow-Blohm Gmbh Process for the galvanic deposition of nickel from a nickel bath
US4290858A (en) * 1980-09-23 1981-09-22 The United States Of America As Represented By The United States Department Of Energy Process for forming a nickel foil with controlled and predetermined permeability to hydrogen
US6485542B2 (en) * 1998-05-20 2002-11-26 Japan Energy Corporation Ni-Fe alloy sputtering target for forming magnetic thin films, magnetic thin film, and method of manufacturing the Ni-Fe alloy sputtering target
US20130015074A1 (en) * 2011-07-12 2013-01-17 Gaydos Stephen P Methods for repairing steel components
US8529747B2 (en) * 2011-07-12 2013-09-10 The Boeing Company Methods for repairing steel components

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NL6608686A (xx) 1966-12-27
DE1496847A1 (de) 1969-05-29
BE683005A (xx) 1966-12-23
CH422463A (fr) 1966-10-15
LU46134A1 (xx) 1964-07-22
DE1250712B (de) 1967-09-21
GB1101093A (en) 1968-01-31
LU51378A1 (xx) 1966-08-22
BE648307A (xx) 1964-11-23
GB999117A (en) 1965-07-21

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