US3502550A - Nickel electroplating electrolyte - Google Patents

Nickel electroplating electrolyte Download PDF

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Publication number
US3502550A
US3502550A US506005A US3502550DA US3502550A US 3502550 A US3502550 A US 3502550A US 506005 A US506005 A US 506005A US 3502550D A US3502550D A US 3502550DA US 3502550 A US3502550 A US 3502550A
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nickel
bright
bath
semi
plating
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US506005A
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Frank Passal
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M&T Chemicals Inc
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M&T Chemicals 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
    • C25D3/14—Electroplating: Baths therefor from solutions of nickel or cobalt from baths containing acetylenic or heterocyclic compounds

Definitions

  • a nickel plating solution for said process which consists essentially of an acidic aqueous nickel plating solution and including as semi-bright additive therein a composition consisting essentially of piperonal and a water-soluble acetylenic compound, and such compositions.
  • This invention relates to the electroplating of nickel. More particularly, it relates to the electroplating of a semi-bright nickel characterized by a uniformly finegrained structure over a wide current density range; excellent ductility; very low sulfur content; low tensile stress; freedom from tendency toward dendritic growths (treeing) on high current density edges and corners.
  • Semi-bright nickel obtained in accordance with this invention may also be easy to polish and buff to a high luster, if desired, with removal of a minimum of metal and with good flow characteristics permitting filling in of defects in basis metal.
  • the semi-bright layer may preferably contain an appreciably lower sulfur content than the bright nickel coating.
  • the lower sulfur content permits the bright nickel layer to become anodic to the semi-bright layer in corrosive media thereby increasing lateral corrosion and slowing down the rate of vertical penetration or corrosion down to the basis metal.
  • the vertical penetration may be slowed and any attack may proceed laterally along the interface of the semi-bright and bright nickel layers thus in effect protecting the basis metal.
  • the basis metal When the basis metal is relatively free of gross imperfections it may be plated with semi-bright nickel and bright nickel in thickness ratio of about 1:1 to 3:1 respectively and then usually followed by chromium plating. Since the higher thickness ratios are more common it is preferable that the semibright layer be fine-grained and uniform over a wide current density range so that the thinner bright nickel deposit can build up to its maximum luster over all significant areas. It is also preferable that the semi-bright nickel layer be so ductile and have such low tensile stress that spontaneous cracking in the high current density area down to the basis metal can be completely eliminated or minimized after bright nickeland chromium plating.
  • Another use of semi-bright, ductile, low tensile stressed nickel deposits may be in electroforming.
  • relatively thick layers of nickel are built up on a non-conductive matrix suitably conditioned by application of a prior conducting surface film of some metal such as copper or silver.
  • the thick nickel layer may be then isolated from the matrix to give a rigid article which is the exact negative replica of the surface contour of the original matrix.
  • the nickel have the ability to give as uniform a thickness as possible, i.e. that the thickness ratio between high and low current density areas be as low as possible.
  • the semi-bright layer has heretofore been deposited from various nickel plating bath formulations (Watts, sulfamate, Watts or sulfamate chloride-free etc.) which usually contain a plurality of cooperating additives (as grain refiners, stress relievers, anti-pitting agents etc.).
  • various nickel plating bath formulations Watts, sulfamate, Watts or sulfamate chloride-free etc.
  • cooperating additives as grain refiners, stress relievers, anti-pitting agents etc.
  • Another object of this in vention is to take advantage of the excellent physical properties of the deposits so as to permit their use in electroforming applications for nickel, particularly since the excellent throwing power permits the attaining of a uniformity of thickness distribution which has been found far superior to the prior art processes.
  • the novel process of this invention for electroplating a semi-bright, nickel plate onto a basis metal may comprise passing current from an anode to a metal cathode through an aqueous acidic nickel plating solution containing nickel compound providing nickel ions for electroplating of nickel, and including as semi-bright additive piperonal and a water-soluble acetylenic compound.
  • the basis metal onto which the semi-bright deposits of this process may be applied may include ferrous metals such as steel; copper, including its alloys such as brass, bronze, etc.; zinc, particularly in the form of die castings which may bear a plate of copper; thin metal coatings, e.g. of silver or copper on a non-conductive article which coating may be applied by reductive techniques; etc.
  • novel baths of this invention may typically include Watts-type baths, sulfamate-type baths, mixed Watts-sulfamate-type baths, fiuoborate-type baths, chloride-free sulfate baths, chloride-free sulfamate baths, chloride-free mixed sulfate-sulfamate baths, etc.
  • a typical Watts bath which may be usm in practice of this invention may include the following components in aqueous solution, all values being in grams per liter (g./l.) except for the pH which is electrometric:
  • a typical sulfamate-type bath which may be used in practice of this invention may include the following components:
  • a typical mixed Watts-sulfamate-type bath which may be used in the practice of the invention may include the following components:
  • a typical fiuoborate-type bath which may be used in the practice of the invention may include the following components:
  • TAB LE IV Component Minimum Maximum Preferred Nickel iluobol'ate 250 400 300 Nickel chloride hexahydra 45 60 60 Boric acid 30 pH 2 4 3
  • a typical chloride-free sulfate bath which may be used in the practice of the invention may include the following components:
  • a typical chloride-free sulfamate bath which may be used in the practice of the invention may include the following components:
  • a typical chloride-free mixed sulfate-sulfamate bath which may be used in the practice of the invention may include the following components:
  • the nickel plating bath there may be present in the nickel plating bath as semi-bright additive, (a) piperonal and (b) a watersoluble acetylenic compound.
  • This additive composition may cooperate with or be compatible with the nickel plating bath.
  • Piperonal also known as heliotropine, may be characterized by the following formula:
  • R may be hydrogen or an inert or non-reactive substituent.
  • the piperonal additive may be used in this invention as piperonal se, or with the piperonal ring bearing inert or non-reactive substituents in any of the 2, 5, or 6 position.
  • Typical inert or non-reactive substituents include alkyl, aryl, cycloalkyl, aralkyl, alkaryl, al kenyl, ether, halogen, ester, etc.
  • Typical specific substituents may be methyl ethyl, propyl, phenyl, cyclopentyl, cyclohexyl, benzyl, tolyl, vinyl, propenyl, ethoxy, chloro, bromo, carboethoxy, etc.
  • the preferred piperonal additive may be piperonal se.
  • the piperonal additive may be particularly useful in refining grain size promoting ductility, and reducing tensile stress.
  • Excellent semi-bright electrodeposits may be obtained when the piperonal additive is used in combination with a water-soluble acetylenic additive.
  • the water-soluble acetylenic compound may be particularly useful in enhancing uniformity and promoting leveling of the semibright nickel deposit.
  • Water-soluble acetylenic compounds which may be employed in this invention may be particularly characterized by a highly nucleophilic triple bond which is free from steric hindrance and thus has a clear and unimpeded path in approaching the cathode.
  • the preferred water-soluble acetylenic compounds which may be employed in the process of this invention to produce semi-bright nickel deposits may include asubstituted acetylenic compounds having the formula R2 R2CEC( lR it.
  • each of R and R may be substituents selected from the group consisting of hydrogen, alkyl, alkenyl,
  • R and R may together be a carbonyl oxygen
  • R may be a substituent of the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxy-substituted and alkoxy-substituted alkenyl and alkynyl groups, and substituted-alkyl groups having the formula incl di g hy yand alkoxyand alkyl-substituied aryl;
  • each of R and R may be substituents selected from the group consisting of hydroxy, alkoxy, carboxy-substituted alkoxy, formoxy, alkanoxy, halogen and polyoxy groups and R may also be an amino group including alkyl and aryl substituted amino group when R and R together form a carbonyl oxygen and R is an aryl group.
  • R is a substituted-alkyl group having the above-illustrated formula
  • the acetylenic compound may be termed an a,e'-disubstituted acetylenic compound, since both carbon atoms vicinal to the same acetylenic bond contain either the same or a different functional group.
  • novel semi-bright compositions or additives of this invention may preferably be used in nickel plating baths maintained at an acid electrometric pH, such as those of Tables IVII, typically the bath of Table I, in amounts of at least 0.02 g./l. of plating bath, preferably 0.02-1.2 g./l. Lower concentrations may give appreciable grain refinement but the deposits may be less glossy.
  • the most preferred concentration may be from 0.05-1 g./l. of additive in the plating bath; Typically there may be present combined additive in the amount at least 0.02 g./l. of plating bath, which additive includes 0.01-1 g./l. of piperonal (including piperonal se and inertly substituted derivative thereof) and 0.010.2 g./l.
  • acetylenic compounds which may be prepared in the instant invention include those containing at least one hydroxy moiety, and most preferably those which contain two hydroxy moieties, e.g. the beta-hydroxyethyl ether of 2-butyne-l,4-diol, i.e. l-(beta-hydroxyethoxy)-4-hydroxy-2-butyne, and the bis (beta-hydroxy ethyl ether) of 2-butyne-l,4-diol i.e. 1,4-bis (beta-hydroXy-ethoxy) -2-butyne.
  • the beta-hydroxyethyl ether of 2-butyne-l,4-diol i.e. l-(beta-hydroxyethoxy)-4-hydroxy-2-butyne
  • bis (beta-hydroxy ethyl ether) of 2-butyne-l,4-diol i.e.
  • Acetylenic compounds which may be employed in the instant invention also include the above compounds modified to include other substituents such as sulfonate groups or sulfate groups.
  • Typical of such acetylenic compounds are the monoand di-sulfated products which may he formed by reaction of the beta-hydroxy-ethyl ether of 2-butyne-1,4-diol and sulfamic acid or of the bis-(beta-hydroxy-ethyl ether) of 2-butyne-l,4-diol and sulfamic acid.
  • the addi' tive may typically include 0.01-1 g./l., say 0.0l-0.l g./l., of piperonal and 0.01-0.1 g./l., say 0.01-0.05 g./l., of the acetylenic compound.
  • the electrometric pH may typically be 25, preferably 3-4.
  • a preferred nickel plating solution may be a mixed Watts-sulfamate bath maintained at an electrometric pH of 4.0 containing g./l. of nickel sulfate heptahydrate, g./l. of nickel sulfamate, 45 g./l. of nickel cloride hexahydrate, 45 g./l. of boric acid, 0.05 g./l. of piperonal and 0.05 g./l. of the bis-(beta-hydroxy-ethyl ether) of 2-butyne-1,4-diol.
  • the additive components may be added to nickel plating baths as individual components or may be dissolved in separate solutions, e.g. 20-50 g./l., say 30 g./l. of
  • nickel compounds which may be employed in solution with the acetylenic compound as mold inhibiting components may include nickel chloride hexahydrate and nickel sulfamate. This solution may be added to the nickel plating solution in addition to any nickel compound already present therein.
  • Semi-bright nickel plating in accordance with this invention may be carried out by immersing a basis metal cathode into a nickel plating bath as hereinbefore disclosed.
  • the anode may be either a soluble anode, typically nickel metal, or an insoluble anode, typically lead. If nickel is used as the anode, it is preferably SD type of nickel.
  • Plating may be carried out typically in chloridecontaining baths for 10-60 minutes, say 30 minutes, at -60 C., say C., with mechanical or air agitation.
  • the cathode current density may typically be 2.5-5 amperes per square decimeter (a.s.d.), preferably 5 a.s.d.
  • medium or very high-speed electroplating of semi-bright nickel may also be effected by a process comprising passing direct current from a substantially non-polarizing anode to a metal cathode through an aqueous nickel plating solution including at least one nickel compound capable of providing nickel ions for electroplating nickel, and including as semi-bright additive piperonal and a water-soluble acetylenic compound; maintaining the cathode current density during said plating at a level of at least 10 a.s.d., and maintaining a high relative velocity between said nickel plating solution and said metal cathode thereby obtaining a semi-bright, rapidly deposited nickel deposit.
  • the substantially non-polarizing anodes which may be used in the very high or medium speed electroplating aspect of this invention may preferably be insoluble anodes, such as lead which have very little tendency to polarize, even at very high current density, or certain soluble anodes, such as the commercially available SD type of nickel which has less tendency to polarize than other soluble nickel anodes and may be used at current densities as high as 40 a.s.d.
  • the SD type of nickel is an electrolytic nickel containing a controlled amount of sulfur as nickel sulfide. When an insoluble anode is used the bath typically should be chloride-free. Such a bath may be replenished in nickel metal content and have its pH adjusted by the addition, of an alkaline oxide, hydroxide or carbonate of nickel, preferably in a separate regenerating tank.
  • Plating carried out in this manner may permit deposition of predetermined thickness of semi-bright nickel in a time which is as little as 10% or less of the time required when ordinarily used plating conditions with soluble nickel anodes are used.
  • production of a semi-bright nickel plate 25 microns thick according to this aspect of the invention may require 3 minutes in contrast to 30 minutes for usual plating conditions.
  • a high relative velocity may be maintained be tween the bath and the cathode to replenish the cathode film with nickel ions as they are plated out therefrom.
  • the high relative velocity between the bath and the cathode is maintained at a level equivalent to 60-320, say cm./ second.
  • the agitation may be produced by vibration (including ultrasonic), rotation of the cathode relative to the solution, by pumping the electrolyte through the system and over the cathode surface or by very vigorous and directional agitation of the electrolyte with appropriately positioned propellers or other devices, etc.
  • the novel process of this invention may permit attainment of a 12.5 to 50 microns, say 25 microns, semibright nickel plate characterized by its fine grain, high ductility, hi h gloss, uniform appearance, and high covering power.
  • the plate may also be characterized by its essentially sulfur-free character.
  • the plating baths may also contain optional additional constituents such as anionic wetting agents to reduce any tendency toward hydrogen pitting.
  • anionic wetting agents such as sodium lauryl sulfate may be used in conjunction with mechanical agitation; and low foaming anionic Wetting agents such as sodium dialkyl sulfosuccinates may be used with air agitation.
  • these wetting agents may commonly contain sulfur, unexpectedly, no increase in the sulfur content of the deposits may be observed when they are used with the additives of this invention.
  • the wetting agents may typically be present in amounts of 0.1-1 g./l. of plating solutlon.
  • the novel semi-bright nickel additive composition may be used in combination with other semi-bright additives in order to augment and extend advantageous features imparted by such other additives.
  • Typical examples of such other additives which may have their characteristics extended are chloral hydrate, coumarin and coumarin derivatives such as oxyomegasulfohydrocarbon-di-yl coumarins, e.g. potassium 7-oxyomegasulfopropyl coumarin.
  • semi-bright nickel plate obtained from a sulfamate plating bath having an electrometric pH of 4.0 containing 375 g./l. nickel sulfamate, 45 g./l. nickel chloride, 45 g./l.
  • boric acid and 0.8 g./l. of potassium 7-oxyomegasulfopropyl coumarin, in 10 minutes at 6 a.s.d. and 60 C. may be characterized as highly leveled, very fine grained, of low tensile stress, and very ductile. These characteristics may be increased even more if 1 ml./l. of a 1:1 isopropanol water solution of 15 g./l. of the his (beta-hydroxy-ethyl ether) of 2- butyne-1,4-diol and 0.25 g./ l. of piperonal are added to the sulfamate plating bath.
  • Oxyomegasulfohydrocarbon-di-yl coumarins such as are disclosed supra may be prepared by reacting in a solvent dispersion eg of methanol, a hydroxy coumarin, a compound of the formula MOH wherein M is a metal, and a hydrocarbon sultone or by reacting a hydroxy coumarin with a salt of a hydroxy hydrocarbon-di-yl sulfonate such as sodium isethionate.
  • 0.05 gram of piperonal and 0.05 gram of the bis (beta-hydroxy-ethyl ether) of 2-butyne-l,4-diol may then be mixed into the bath and the plating test repeated. This time, a beautifully fine grained, very ductile deposit of high gloss and very uniform appearance may be obtained.
  • This deposit may also be characterized as being substantially free of tensile stress and as being substantially free of sulfur (i.e. as containing less than 0.003% by weight of sulfur).
  • the bath may be thermostatically controlled at 55 C. and air agitated, 0.05 gram of piperonal and 0.05 gram of the beta-hydroxy-ethyl ether of 2-butyne-1,4-diol may be mixed into the bath and electroplating carried out at a current of 5 amperes and at 55 C. for 30 minutes using a bagged SD nickel anode and a highly polished brass cathode strip pleated in 45 angles.
  • the deposit obtained may be noted as being finely grained, very ductile, of high gloss, of very uniform appearance, desirably low in tensile stress and substantially free of sulfur.
  • the bath may be thermostatically controlled at 55 C.
  • 0.2 gran1 of potassium 7-0xyomegasulfo-propyl coumarin may be mixed in the bath and electroplating carried out at a current of 5 amperes, at 5 C. for 30 minutes using a bagged SD nickel anode and a highly polished brass cathode strip pleated in 45 angles.
  • the deposit obtained may be very fine grained, well leveled, very ductile, and lustrous with only a slight haze.
  • the above experiment may be repeated with the further addition to the bath of 1 ml. of a 1:1 isopropanol solution containing 30 g./l. solution of his (beta-hydroxyethyl) ether of 2-butyne-1,4-diol and 50 g./l. of piperonal.
  • the characteristics of the deposit obtained are augmented and extended beyond the characteristics of the deposit produced in the first part of the example.
  • the later produced deposit may be noted as being even more fine grained, more ductile, still well leveled, and glossy and having low tensile stress.
  • the bath may be thermostatically controlled at 54 C. and mechanically agitated with propellers.
  • 0.05 gram of piperonal, 0.2 gram of phenyl propiolamide, 0.2 gram of the disulfated reaction product of the bis (B-hydroxyethyl ether) of 2-butyne-l,4-diol and sulfamic acid and 0.5 g./l. of sodium lauryl sulfate wetting agent may be mixed into the bath and electroplating carried out at a current of 2.5 amperes at 54 C. for 30 minutes using a bagged SD nickel anode and a copper plated die cast handle having a surface area of about sq. cm. which may be scribed with a single pass of a 1.2 cm. wide zerogrit emery paper. Within 15 minutes a semi-bright deposit may -be obtained of remarkably high luster and fine grain size having scratched band virtually completely filled in.
  • the bath may be thermostatically controlled at 66 C. and mechanically agitated with propellers.
  • 0.5 gram of a high foaming wetting agent, sodium lauryl sulfate, may be added to the bath.
  • 0.1 gram of phenyl propiolamide may then be mixed in the bath and electroplating carried out at a current of 5 a.s.d. at 60 C. for 30 minutes using a bagged SD nickel anode and a highly polished brass cathode strip pleated in 45 angles.
  • the deposit obtained may be a good, fairly fine-grained semi-bright deposit, but not quite adequate in grain size to permit building up luster rapidly upon bright nickel plating.
  • Theabove experiment may be repeated with the further addition to the bath of 0.5 g./l. of piperonal.
  • the deposit obtained is much improved and may be characterized as being more fine grained, level, ductile, uniform in appearance, substantially free of tensile stress, substantially free of sulfur. Further the deposit may permit rapid build-up of luster upon bright nickel plating.
  • a nickel plating solution consisting essentially of an acidic aqueous nickel plating solution including a nickel compound capable of providing nickel ions for electrodeposition of nickel on a basis metal cathode and including as semi-bright additive 0.011 g./l. of said plating solution piperonal and 0.010.2 g./l. of said plating solution of a water-soluble acetylenic compound selected from the group consisting of the bisQS-hydroxy-ethyl ether) of 2-butyne-1,4-diol and the fi-hydroxy-ethyl ether of 2-butyne-1,4-dio1.

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US506005A 1965-11-01 1965-11-01 Nickel electroplating electrolyte Expired - Lifetime US3502550A (en)

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SE (1) SE324092B (cs)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4062738A (en) * 1974-10-04 1977-12-13 E. I. Du Pont De Nemours And Company Acid nickel electroplating additive therefor and method of making said additive
US4416741A (en) * 1981-03-06 1983-11-22 Langbein-Pfanhauser Werke Ag Method and bath for the electrodeposition of palladium/nickel alloys
US20040222099A1 (en) * 1999-12-28 2004-11-11 Tetsuo Tanaka Method of producing metal ferrules, and device therefor
CN102953094A (zh) * 2011-08-26 2013-03-06 比亚迪股份有限公司 一种半光亮镍电镀液添加剂、半光亮镍电镀液和半光亮镍电镀方法
CN103820823A (zh) * 2014-03-12 2014-05-28 延康汽车零部件如皋有限公司 一种防止电镀珍珠镍产品发白的方法
CN119640348A (zh) * 2025-01-23 2025-03-18 中国恩菲工程技术有限公司 一种电解法生产镍箔的方法
CN119640348B (zh) * 2025-01-23 2025-11-25 中国恩菲工程技术有限公司 一种电解法生产镍箔的方法

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US2800440A (en) * 1955-10-04 1957-07-23 Udylite Res Corp Electrodeposition of nickel
US2800441A (en) * 1955-10-04 1957-07-23 Udylite Res Corp Electrodeposition of nickel
US2900707A (en) * 1954-08-06 1959-08-25 Udylite Corp Metallic protective coating
GB871276A (en) * 1959-02-26 1961-06-28 Hanson Van Winkle Munning Co Improvements in electrodeposition of nickel
US3002902A (en) * 1958-09-26 1961-10-03 Hanson Van Winkle Munning Co Electrodeposition of nickel
US3002904A (en) * 1958-09-26 1961-10-03 Hanson Van Winkle Munning Co Electrodeposition of nickel
US3108933A (en) * 1961-02-28 1963-10-29 M & T Chemicals Inc Process and composition for chromium plating
US3140988A (en) * 1960-03-21 1964-07-14 Udylite Corp Electrodeposition of nickel
US3367854A (en) * 1964-12-21 1968-02-06 M & T Chemicals Inc Nickel plating

Patent Citations (11)

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Publication number Priority date Publication date Assignee Title
US1564414A (en) * 1924-10-06 1925-12-08 Grasselli Chemical Co Cadmium plating
US2795540A (en) * 1954-04-05 1957-06-11 Udylite Res Corp Electrodeposition of nickel
US2900707A (en) * 1954-08-06 1959-08-25 Udylite Corp Metallic protective coating
US2800440A (en) * 1955-10-04 1957-07-23 Udylite Res Corp Electrodeposition of nickel
US2800441A (en) * 1955-10-04 1957-07-23 Udylite Res Corp Electrodeposition of nickel
US3002902A (en) * 1958-09-26 1961-10-03 Hanson Van Winkle Munning Co Electrodeposition of nickel
US3002904A (en) * 1958-09-26 1961-10-03 Hanson Van Winkle Munning Co Electrodeposition of nickel
GB871276A (en) * 1959-02-26 1961-06-28 Hanson Van Winkle Munning Co Improvements in electrodeposition of nickel
US3140988A (en) * 1960-03-21 1964-07-14 Udylite Corp Electrodeposition of nickel
US3108933A (en) * 1961-02-28 1963-10-29 M & T Chemicals Inc Process and composition for chromium plating
US3367854A (en) * 1964-12-21 1968-02-06 M & T Chemicals Inc Nickel plating

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4062738A (en) * 1974-10-04 1977-12-13 E. I. Du Pont De Nemours And Company Acid nickel electroplating additive therefor and method of making said additive
US4416741A (en) * 1981-03-06 1983-11-22 Langbein-Pfanhauser Werke Ag Method and bath for the electrodeposition of palladium/nickel alloys
US20040222099A1 (en) * 1999-12-28 2004-11-11 Tetsuo Tanaka Method of producing metal ferrules, and device therefor
US7090761B2 (en) * 1999-12-28 2006-08-15 Smk Corporation Method of producing metal ferrules, and device therefor
CN102953094A (zh) * 2011-08-26 2013-03-06 比亚迪股份有限公司 一种半光亮镍电镀液添加剂、半光亮镍电镀液和半光亮镍电镀方法
CN102953094B (zh) * 2011-08-26 2015-05-13 比亚迪股份有限公司 一种半光亮镍电镀液添加剂、半光亮镍电镀液和半光亮镍电镀方法
CN103820823A (zh) * 2014-03-12 2014-05-28 延康汽车零部件如皋有限公司 一种防止电镀珍珠镍产品发白的方法
CN103820823B (zh) * 2014-03-12 2016-02-24 延康汽车零部件如皋有限公司 一种防止电镀珍珠镍产品发白的方法
CN119640348A (zh) * 2025-01-23 2025-03-18 中国恩菲工程技术有限公司 一种电解法生产镍箔的方法
CN119640348B (zh) * 2025-01-23 2025-11-25 中国恩菲工程技术有限公司 一种电解法生产镍箔的方法

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DE1496926A1 (de) 1969-08-14
NL6615310A (cs) 1967-05-02
GB1172220A (en) 1969-11-26
SE324092B (cs) 1970-05-19
CH479714A (de) 1969-10-15
ES332766A1 (es) 1967-12-01
DE1496926B2 (de) 1976-04-15
GB1169559A (en) 1969-11-05
NL156195B (nl) 1978-03-15

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