US2822293A - Chemical nickel plating processes and baths therefor - Google Patents

Chemical nickel plating processes and baths therefor Download PDF

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US2822293A
US2822293A US479088A US47908854A US2822293A US 2822293 A US2822293 A US 2822293A US 479088 A US479088 A US 479088A US 47908854 A US47908854 A US 47908854A US 2822293 A US2822293 A US 2822293A
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plating
nickel
bath
ions
hypophosphite
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Gutzeit Gregoire
Talmey Paul
Warren G Lee
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General American Transportation Corp
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Gen Am Transport
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites

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  • the present invention relates to improved processes of chemical nickel plating of catalytic materials employing baths of the nickel cation-hypophosphite anion type and to improved baths therefor, and more particularly to such processes and baths involving a continuous system of the character of that disclosed in U. S. Patent No. 2,658,839, granted on November 10, 1953, to Paul Talmey and William J. Crehan.
  • This application is a continuation-in-part of the copending application of Gregoire Gutzeit, Paul Talmey and Warren G. Lee, Serial No. 478,492, filed December 29, 1954; and the lastmentioned application is, in turn, a continuation-in-part of the abandoned application of Gregoire Gutzeit, Paul Talmey and Warren G. Lee, Serial No. 376,968, filed August 27, 1953.
  • the chemical nickel plating of a catalytic material employing an aqueous bath of the nickel cation-hypophosphite anion type is based upon the catalytic reduction of nickel cations to metallic nickel and the corresponding oxidation of hypophosphite anions to phosphite anions with the evolution of hydrogen gas at the catalytic surface.
  • the reactions take place when the body of catalytic material is immersed in the plating bath, and the exterior surface of the body of catalytic material is coated with nickel.
  • the following elements are catalytic for the oxidation of hypophosphite anions and thus may be directly nickel plated: iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum.
  • the following elements are examples of materials which may by nickel plated by virtue of the initial displaceme'ntdeposition of nickel thereon either directly or through a galvanic effect: copper, silver, gold, beryllium, germanium, aluminum, carbon, vanadium, molybdenum, tungsten, chromium, selenium, titanium and uranium.
  • non-catalytic materials which ordinarily may not be nickel plated: bismuth, cadmium, tin, lead and zinc.
  • the activity of the catalytic materials varies considerably and the following elements are particularly good catalysts in the chemical nickel plating bath: iron, cobalt, nickel and palladium.
  • the chemical nickel plating process is autocatalytic since both theoriginal surface of the body being plated and the nickel metal that is deposited on the surface thereof are catalytic; and the reduction of the nickel cations to metallic nickel in the plating bath proceeds until all of the nickel cations have been reduced tometallic-nickel, in the presence of an excess of hypophosphite anions, or until all of the hypophosphite anions have been oxidized to phosphite ions, in the presence of an excess of nickel cations.
  • the reactions are sloweddown rather rapidly as time proceeds because the anions, as contrasted with the cations, of the nickel salt that is dissolved in the plating bath combine with the hydrogen cations to form an acid, which, in'turn, lowers the pH of the bath, and the reducing power of the hypophosphite anions is decreased as the pH value of the bath'decreases.
  • another practical difficulty is encountered in the continuous plating process that is not encountered in the batch plating process in that there is a considerable build-up of the 'by-product phosphite therein as time proceeds and as aconsequence of the cycling of the bath.
  • nickel hypophosphite is readily soluble in anaqueous solution
  • nickel phosphite is much less'soluble in an aqueous solution; whereby there is a tendency, as the phosphite concentration of the plating bathbuilds-up, for nickel phosphite to be precipitated therein, and thereby provide the solid particles that serve as nuclei for the formation of the black precipitate therein, previously mentioned.
  • the initiation of the precipitation of nickel phosphite in the plating bath is indicated byturbidity thereof, visible in a Tyndall beam.
  • the continuouszsystem-Idisclosed in the Talmey and Crehan patent may be employed; which system involves periodic or continuous regeneration of the plating bath by the addition thereto of appropriate ingredients for the purpose of-maintaining substantially constant the composition of the bath, as previously noted. More specifically in this system, there are provided a plating chamber and a reservoir; preferably one portion of the plating solution is stored at a relatively low temperature well below the boiling point: thereof in the reservoir; and preferably another portion of the plating solution is held as a bath at a relatively high temperature slightly below the boiling point thereof in the plating chamber.
  • the solution is continuously circulated at a low rate from the reservoir to the .platingschamber and then back to the reservoir, the solution being heated substantially to the relatively high temperature after withdrawal thereof from thereservoir and before introduction thereof into thev plating chamber, and the solution being cooled substantially to the relatively low temperature after withdrawal thereof from the platingchamher and before return thereof to the reservoir?"
  • Thebody that is to be nickel plated is immersed in the bath in the plating chamber andis subsequently withdrawn from the bath in the plating chamber after a time interval corresponding to the thickness of the nickelplating thereon that is desired; and during such-time"interval' soluble reagents are added to the solution inthe reservoir to maintain in the bath in the plating chamber during such time interval substantially thepredetermined composition of the bath previously mentioned, so as to compensate for the ingredients of the 'bath thatare exhausted during-the time interval in the platingchamberl
  • This regeneration of the solution in the "reservoir consists essentially of adding thereto appropriate-amounts of soluble nickel-containing and hypo
  • the threshold of precipitation of the insoluble nickel phosphite begins when the (HPO concentration attains a value above the solubility of its simple nickel salt or its double nickel-alkali salt; i. e., above 0.03 to 0.07 m. p. 1.; and in order to obviate this defect, there are disclosed in the previously mentioned abandoned application of Gregoire Gutzeit, Paul Talmey and Warren G. Lee, Serial No. 376,968, filed August 27, 1953, modified plating baths of the nickel cation-hypophosphite anion type containing both complexing agents and exalting additives.
  • the complexing agents serve to tie-up the nickel ions, thereby preventing precipitation of nickel phosphite until a high concentration of phosphite ions (about 1.0 m. p. l.) is reached in the plating bath in the continuous plating system; and the exalting additives serve to increase the normally low plating rates of these baths containing the complexed nickel ions.
  • those forming water-soluble chelates are most efiicient; and, within that group, the hydroxycarboxylic acids have several practical advantages, such as: ready availability, low price and high buffering capacity.
  • nickel ions are very strongly tied-up (i. e., if the chelate is very stable), they are actually removed from the plating process, and no longer available for deposition; whereas, if the complex bond energy is at a lower level, an equilibrium is reached between the dissociation rate of the nickel complex ion and the deposition rate of metallic nickel.
  • the stability of nickel chelates with various hydroxycarboxylic acid additives is not only a function of the number of hydroxyl and carboxyl groups in the acid molecule, but also of molecular structure and steric factors, as may be better appreciated from a consideration of the structure of the more common. of these acids:
  • Glycollic acid (hydroxyacetic acid) H2CC OH OH Malic acid (monhydroxysuccinic acid) 0 H Hi l-o 0 on E2 (3-0 0 o H Lactic acid (alpha-hydroxypropionic acid) CH; HO-(BH coon Tartaric acid (dihydroxysuccinic acid) OH HiJ-O 0 0H HCC 0 OH Citric acid HaC- c 0 o H 110- o-o 0 on H2 0- c 0 o E It is obvious that tartaric acid having two hydroxyl and two carboxyl groups will give the most stable complex; and it is also normal that glycollic and lactic acid complexes will show the least stability, both being monohydroxy-monocarboxylic acids. On the other hand, the lactic chelate of nickel is less stable than the glycollic complex; and this is due to a structural factor, i; e., the
  • chelate stability is also determined by the number of carboxyl groups in the molecule so that the nickelmalic acid complex (a monohydroxy-dicarboxylic compound) is more stable than the corresponding chelates of both glycollic and lactic acids (monohydroxy-monocarboxylic acids), while the citric acid complex is the most stable of all.
  • the resulting plating rate will be an inverse function of chelate stability; however, on the other hand, the more stable the nickel complex, the higher a phosphite ion concentration can be built-up before precipitation of nickel phosphite occurs.
  • the plating baths disclosed in the Gutzeit, Talmey and Lee application, Serial No. 478,492 comprise relatively stable complexing agents in combination with powerful exalting additives dicarboxylic acids, aminocarhoxylic acids and certain monocarboxylic acids) to increase the normally low plating rates of these baths.
  • the present invention is predicated upon the discovery that in a plating bath of the nickel cation-hypophosphite anion type described, while the nickel chelating function of lactic acid is directly proportional to the concentration thereof in the bath, the effect thereof upon the plating rate of the bath is not inversely proportional to the concentration thereof as is the general case with the other hydroxycarboxylic acids); rather within a given range of concentration, lactic acid is a definite exaltant in the bath, substantially increasing the plating rate thereof.
  • the mechanism of this exalting effect is not fully understood, but the effect is very pronounced; and it is most unusual and entirely unexpected that lactic acid unlike the other common hydroxy-earboxylic acids) should possess this particular characteristic.
  • the general composition of a plating bath in accordance with the'present invention essentially comprises an aqueous solution of a nickel salt, a hypophosphite, and lactic acid or a salt thereof; wherein the absolute concentration of hypophosphite anions in the bath is in the range 0.15 to 1.20 m. p. l., the ratio between nickel cations and hypophosphite anions in the bath expressed in molar concentrations is within the range 0.25 to 1.60, and the ratio between nickel cations and lactic ions in the bath expressed in molar concentrations is within the range 0.15 to 0.35.
  • the pH of the bath is normally in the range 4.0 to 5.6; and the bath is employed in the plating chamber of the continuous plating system at a temperature above C., ordinarily slightly below the boiling point thereof and at about 97 to 99 C.
  • the bath has a nickel plating rate of at least 1 mil/hour (0.00l"/hour), or expressed in c. g. s. units of at least 3.5X10- gm./cm. /min.; and no precipitation of nickel phosphite takes place therein even at a phosphite ion concentration in some cases very close to 1.0 m. p. 1. Further, the plating appearance on both metals and nonmetals is excellent (bright, smooth and non-porous); and
  • adhesion of the nickel plating on both metallic and nonmetallic bodies is excellent (no flaking of the nickel coat ing in bending, abrading and shock tests).
  • the plating bath of the composition specified is preferably employed in the continuous plating system of the character previously described, whereby the lactic acid additive is present therein in the optimum range specified so. that it serves both the complexing or chelating function with respect to the nickel ions and also the function of increasing the otherwise relatively low plating rate of the bath.
  • This complexing of the nickel cations in the plating bath prevents the formation of precipitated phosphite therein, thereby rendering the bath of exceedingly long life in spite of the build-up of phosphite ions therein to a concentration even in excess of one molar.
  • This complex'of nickel in the plating bath is water-soluble and of medium stability resulting in a bond strong enough to prevent the 'nickel cations from forr iiing -insoluble nickel compounds, but having a stability constant low enough to release the nickel cations required for the nickel plating operation to effect a plating rate of the bath of at least 35x10" gm./cm. /min., as previously explained.
  • Another object of the invention is to provide an improved aqueous chemical nickel plating bath that may be employed with advantage in the practice of the improved process.
  • Another object of the invention is to provide an improved nickel plating process of the character described
  • a further object of the invention is to provide an improved nickel plating process of the continuous type involving an improved plating bath of the nickel cationhypophosphite anion type, so that the useful life of the bath is greatly extended in that it remains clear, notwithstanding the presence therein of a phosphite anion concentration approaching one molar.
  • a still further object of the invention is to provide an improved nickel plating bath of the character described that involves a novel range of lactic ion addition.
  • Figure l is a series of curves illustrating the relationship between the plating rates of a number of plating baths of the nickel cation-hypophosphite anion type and the concentrations of several common hydroxy-carboxylic acids contained therein;
  • Fig. 2 is a curve illustrating the relationship between phosphite tolerance of a plating bath of the type mentioned and the concentration of lactic acid contained therein.
  • the article to be nickel plated and normally having a catalytic surface is properly prepared by mechanical cleaning, degreasing and light pickling substantially in accordance with standard practices in electroplating processes.
  • a suitable acid such as hydrochloric acid.
  • the article is then immersed in a suitable volume of the plating bath containing the proper proportions of nickel cations, hypophosphite anions and lactic ions, the pH of the bath having been, if necessary, adjusted to an optimum value by the addition of an appropriate acid or base, and the bath having been heated to a temperature just below its boiling point, such as 99 C. at atmospheric pressure. Almost immediately, hydrogen bubbles are formed on the catalytic surface of the steel article and escape in a steady stream from the plating bath, while the surface of the steel article is slowly coated with metallic nickel (containing some phosphorus).
  • the steel article is subsequently removed from the bath after an appropriate time interval corresponding to the required thickness of the nickel coating deposited thereon that N 6 is desired; and'ulti'matelythe steel "article is rins'ed'otf with water, so that it is ready for use.
  • the nickel cations may be derived from nickel chloride, nickel sulfate, etc., or various combinations thereof;
  • the hypophosphite anions maybe derived from sodium hypophosphite, potasium hypophosphite, etc., or various combinations thereof;
  • the lactic ions may be derived from lactic acid, or various lactates, or various combinations thereof.
  • the desired pH of the bath is established by the eventual introduction thereinto of hydrochloricacid or an alkali, such as sodium hydroxide, sodium carbonate or sodium bicarbonate.
  • cation, anion and ion as employed herein, except where specifically noted, include the total quantity of the corresponding elements that are present in the plating bath, i. e., both undissociated and dissociated material. In other words, 100% dissociation is assumed wnen the terms noted are used in connection with molar ratios and concentrations in the plating bath.
  • first and second series of reference plating tests (10 minute rate tests) were conducted employing standard steel samples that had been given a standard pretreatment. More particularly, steel samples (Dayton Rodgers) of 20 cm. total area were vapor degreased, cleaned by an alkaline soak and lightly pickled in 1:1 hydrochloric acid. The steel samples thus prepared were then plated at 981- 1 C. in 50 cc. of different plating baths each containing nickelcations (as nickel sulfate) 0.08 m. p. l. hypophospnite anions (as sodium hypophosphite) 0.224 m. p. l. and the indicated amounts of organic additives (acetate ions or hydroxycarboxylic ions), the latter being equivalent with respect-to their hy droxylgroups, and the pH being adjusted with NaOH'to about 4.7.
  • nickelcations as nickel sulfate
  • hypophospnite anions as sodium hypophosphite
  • each 111018 of nickel requires at as 0.03 m. p. l. in the baths. a least two carboxyl groups and at least one hydroxyl group.
  • the low plating rate of the nickel cahoh-hypophhsphite ahhm yp the amounts h fifth l ti b h of T bl 11 h b h containing of hydroxycarboxylic acids sufficient to achieve complete no organic additive) is, of course, due to the rapid rise stoichiomeh'ic complexihg of the nickel are Set forth in in hydrogen ion concentration (reduction in pH), there table below! being no buffering action so that the reducing efficiency of TABLE V the hypophosphite is rapidly decreased, plating stopping altogether at a pH below about 3.0.
  • lactic acid a weak chelating agent
  • the advantages inherent to all hydroxycarboxylic anions as far as preventing phosphite precipitation is concerned, and in addition thereto the function of an exaltant.
  • the alkali salts of lactic acid are good buffers in the proper pH range.
  • a further series of plating tests were conducted under conditions identical to the second and third series of reference plating tests described above, except that in the plating baths variable concentrations of lactic acid anions stat were employed. The results of these ing rate is exalted by an increased concentration of lactic acid in the platingbath.
  • the plating rate 5 is a function of pH; and in order to demonstrate this igg iiggf fg i M8 16 0.24 030 M0 M0 characteristic, stillanother series of plating tests were conlriVleaigillllt .2 0.0503 0.0759 0.0701 0. 0706 0.0092 0.0002 ducted em loying steel samples (Dayton Rodgers Shimfi fi 282 380 396 M3 M6 01 stock) of 20 cm. total area that had been vapor degreased,
  • h e l of h se plating tests are represented p In these baths,. the relatively high concentration of lacal y yt t 13 in 1, employing the data of tie. ions is necessary for stability (prevention of formation Table VII a ve;.w y the relationship between the of. black precipitate) at elevated .pH values employed in plating rate andthe concentration of lactic acid is unique h l i t a d i th plating te t the pH of the in.that there is a defini m m m pl ing r wi h baths were adjustedwith NaOH. The results of these Ni++ /lactic ion ratios at about 1:3. plating tests are shown in the table below:
  • the preferred pHis between of acetic anions has a phosphite tolerance of only 0.05 4.4 and 5.6 despite a lower plating rate. .Howevel, the m. p. 1.; whereas a substantially identical plating bath conbath is useful over, the relatively wide approximate pH taining as little as 0.10 m. p. l. of citric acid has a phos- 5 range 4.0 to 5.6. phite tolerance in excess of 2.0 m. p. 1.
  • the initial pH of Bath III was adiusted to 4.55 with caustic soda; and at the conclusion of the dynamic run, it was determined that the average plating rate upon the samples was 0.9 mil/hour, that the hypophosphite utilization was the usual 33.33%, and that the phosphite tolerance was 0.953 m. p. l.
  • the plating was analyzed as 90.5% nickel and 9.2% phosphorus; the hardness of the plating was from.500 to 600 Vickcrs number, with 70% of the samples being 537 V.
  • the phosphite concentration buildsup to a point where a slight excess of (HPO despite the presence of a complexing agent, will result in nickel phosphite precipitation; in other words, a threshold is reached where the solubility of nickel phosphite, even in the presence of a nickel chelating agent, is exceeded.
  • HPO hydrogen phosphite
  • cycles 1 to 5, inclusive, of this plating test two of the panels specified having a total area of 290 cm. were plated; whereas in cycles 6 to 10, inclusive, of this plating test, only one panel specified having a total area of 145 cm. was plated. Furthermore, at the beginning of cycle 8 of this plating test, an extra 4.0 gm. of NiSO .6H O was added, as an analysis showed that the nickel content of the plating bath was low. Also, the plating rates obtained in cycles 6 and 7 of this plating test were clearly indicative of the circumstance that the total content of Ni++ was running lower than that desired.
  • the level of concentration of the phosphite in a plating bath of this type must be mainthe plating bath must be discarded for further use, when about one-half to. three-fourth of the phosphite tolerance thereof is reached, thereby to insure that in the plating 13 operation there is no formation of black precipitate in the plating bath.
  • these baths may advantageously contain as a separate and independent exalting additive a simple short chain saturated aliphatic monocarboxylic acid, preferably propionic acid, as disclosed in, the previously mentioned copending divisional application of Gutzeit, Talmey and Lee.
  • These plating baths are particularly welladapted for use in a continuous plating system, as they exhibit a fast plating rate, have an exceedingly long life, are productive of entirely satisfactory plating quality, and maintain nickel phosphite in solution in concentrations approaching one molar.
  • the process of chemically plating with nickel a body essentially comprising an element selected from the group consisting of iron, cobalt, nickel, aluminum, copper, silver, gold, palladium and platinum which comprises contacting said body with a bath consisting essentially of an aqueous solution of nickel ions, hypophosphite ions, and a complexing agent selected from the group consisting of lactic acid and salts thereof, wherein the absolute concentration of hypophosphite ions in said bath expressed in mole/liter is within the range 0.15 to 1.20, the ratio between nickel ions and hypophosphite ions in said bath expressed in molar concentrations is within the range 0.25 to 1.60, the absolute concentration of lactic ions in said bath expressed in mole/liter is within the range 0.25 to 0.60, and the initial pH of said bath is within the approximate range 4.0 to 5.6.
  • a bath for the chemical plating of a catalytic material with nickel consisting essentially of an aqueous solution of a nickel salt, a hypophosphite, and a complexing agent selected from the group consisting of lactic acid and salts thereof, wherein the absolute concentration of hypophosphite ions in said bath expressed in mole/liter is within the range 0.15 to 1.20, the ratio between nickel ions and hypophosphite ions in said bath expressed in molar concentrations is within the range 0.25 to 1.60, the absolute concentration of lactic ions in said bath expressed in mole/liter is within the range 0.25 to 0.60, and the pH of said bath is within the approximate range 4.0 to 5.6.
  • a bath for the chemical plating of a catalytic material with nickel consisting essentially of an aqueous solution of a nickel salt, a hypophosphite, and a complexing agent selected from the group consisting of lactic acid and salts thereof, wherein the absolute concentration of hypophosphite ions in said bath expressed in mole/liter is within the range 0.15 to 1.20, the ratio between nickel ions and hypophosphite ions in said bath expressed in molar concentrations is within the range 0.25 to 1.60, the absolute concentration of lactic ions in said bath expressed in mole/liter is within the range 0.25 to 0.45, and the pH of said bath is within the approximate range 4.4 to 5.6.
  • the process of chemically plating with nickel a body essentially comprising an element selected from the group consisting of iron, cobalt, nickel, aluminum, copper, silver, gold, palladium and platinum which comprises contacting said body with a bath consisting essentially of an aqueous solution of nickel ions, hypophosphite ions and lactic ions, wherein the absolute concentration of hypophosphite ions in said bath expressed in mole/liter is within the range 0.15 to 1.20, the ratio between nickel ions and hypophosphite ions in said bath expressed in molar concentrations is within the range 0.25 to 1.60, and the absolute concentration of lactic ions in said bath expressed in mole/liter is within the range 0.25 to 0.60.
  • a bath for the chemical plating of a catalytic material with nickel consisting essentially of an aqueous solution of a nickel salt, a hypophosphite and a lactate, wherein the absolute concentration of hypophosphite ions in said bath expressed in mole/liter is within the range 0.15 to 1.20, the ratio between nickel ions and hypophosphite ions in said bath expressed in molar concentrations is within the range 0.25 to 1.60, and the absolute concentration of lactic ions in said bath expressed in mole/liter is within the range 0.25 to 0.60.

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US479088A US2822293A (en) 1954-12-31 1954-12-31 Chemical nickel plating processes and baths therefor
ES0225736A ES225736A1 (es) 1954-12-31 1955-12-22 UN PROCEDIMIENTO DE NIQUELADO QUiMICO SOBRE UN CUERPO DE MATERIAL CATALiTICO
DK428555AA DK105572C (da) 1954-12-31 1955-12-30 Nikkelpletteringsbad og fremgangsmåde til kemisk nikkelplettering af en genstand af katalytisk materiale under anvendelse heraf.
US569815A US2822294A (en) 1954-12-31 1956-03-06 Chemical nickel plating processes and baths therefor

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3211578A (en) * 1961-11-27 1965-10-12 Gen Am Transport Chemical nickel plating of magnesium and its alloys
US4483711A (en) * 1983-06-17 1984-11-20 Omi International Corporation Aqueous electroless nickel plating bath and process

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2532283A (en) * 1947-05-05 1950-12-05 Brenner Abner Nickel plating by chemical reduction
US2658842A (en) * 1951-01-04 1953-11-10 Gen Am Transport Process of chemical nickel plating and bath therefor

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2532283A (en) * 1947-05-05 1950-12-05 Brenner Abner Nickel plating by chemical reduction
US2658842A (en) * 1951-01-04 1953-11-10 Gen Am Transport Process of chemical nickel plating and bath therefor

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3211578A (en) * 1961-11-27 1965-10-12 Gen Am Transport Chemical nickel plating of magnesium and its alloys
US4483711A (en) * 1983-06-17 1984-11-20 Omi International Corporation Aqueous electroless nickel plating bath and process

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