US3922209A - Electrode position of alloys of nickel, cobalt or nickel and cobalt with iron and electrolytes therefor - Google Patents

Electrode position of alloys of nickel, cobalt or nickel and cobalt with iron and electrolytes therefor Download PDF

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US3922209A
US3922209A US498947A US49894774A US3922209A US 3922209 A US3922209 A US 3922209A US 498947 A US498947 A US 498947A US 49894774 A US49894774 A US 49894774A US 3922209 A US3922209 A US 3922209A
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per liter
grams per
cobalt
nickel
hydroxy
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Frank Passal
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Arkema Inc
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M&T Chemicals Inc
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Priority to US498947A priority Critical patent/US3922209A/en
Priority to CA233,550A priority patent/CA1058553A/en
Priority to ZA00755278A priority patent/ZA755278B/xx
Priority to ES440326A priority patent/ES440326A1/es
Priority to BR7505302*A priority patent/BR7505302A/pt
Priority to CS755670A priority patent/CS187487B2/cs
Priority to AU84078/75A priority patent/AU493939B2/en
Priority to GB3446775A priority patent/GB1464483A/en
Priority to SE7509245A priority patent/SE416825B/xx
Priority to JP50101075A priority patent/JPS599637B2/ja
Priority to FR7525760A priority patent/FR2282488A1/fr
Priority to NL7509898A priority patent/NL7509898A/xx
Priority to DE19752537065 priority patent/DE2537065A1/de
Priority to IT9519/75A priority patent/IT1033839B/it
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Assigned to ATOCHEM NORTH AMERICA, INC. reassignment ATOCHEM NORTH AMERICA, INC. MERGER (SEE DOCUMENT FOR DETAILS). Assignors: ATOCHEM INC., A CORP. OF DE., M&T CHEMICALS INC., A CORP. OF DE., (MERGED INTO), PENNWALT CORPORATION, A CORP. OF PA., (CHANGED TO)
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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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt

Definitions

  • this invention relates to a process for the preparation of an electrodeposit which contains iron and at least one metal selected from the group consisting of nickel and cobalt which comprises passing current from an anode to a cathode through an aqueous plating solution containing an iron compound and at least one member selected from the group consisting of cobalt compounds and nickel compounds providing cobalt or nickel ions for electrodepositing alloys of iron with cobalt and/or nickel and containing in combination an effective amount of:
  • This invention relates to improved processes and compositions for the electrodeposition of semi-bright or bright iron alloys with nickel or cobalt or nickel and cobalt. More particularly, this invention relates to the use of a new additive to improve the plating of ironcontaining alloys of nickel, cobalt and nickel-cobalt.
  • this invention relates to a process for the preparation of an iron alloy electrodeposit which contains in addition to iron, nickel or cobalt or nickel and cobalt which comprises passing current from an anode to a cathode through an aqueous plating solution containing at least one iron compound and nickel or cobalt or nickel and cobalt compounds to provide nickel, cobalt and iron ions for electrodepositing alloys of nickel or cobalt or nickel and cobalt with iron.
  • M is a cation having a valence of 1-2; k is an integer 1-2 corresponding to the valence of M; and R is hydrogen or a monovalent aliphatic group of 116 carbon atoms;
  • primary brighteners such as diethoxylated 2 butyne-l,4-diol or dipropoxylated 2 butyne-l ,4-diol may be used in cooperation with a sulfo-oxygen secondary brightener, preferably saccharin, a secondary auxiliary brightener and an anti-pitter.
  • a fairly lustrous deposit with fair leveling may be obtained using as a primary brightener a nitrogen heterocyclic compound such as N-allyl quinolinium bromide at a concentration of about 5 to mg/l in cooperation 2 with a sulfo-oxygen secondary brightener, a secondary auxiliary brightener and an anti-pitter.
  • a nitrogen heterocyclic compound such as N-allyl quinolinium bromide at a concentration of about 5 to mg/l in cooperation 2 with a sulfo-oxygen secondary brightener, a secondary auxiliary brightener and an anti-pitter.
  • the substrates on which the nickel-iron, cobalt-iron or nickel-cobalt-iron containing electrodeposits of this invention may be applied may be metal or metal alloys such as are commonly electrodeposited and used in the art of electroplating such as nickel, cobalt, nickelcobalt, copper, tin, brass, etc.
  • Other typical substrate basis metals from which articles to be plated are manufactured may include ferrous metals such as steel; copper; alloys of copper such as brass, bronze, etc.; zinc, particularly in the form of zinc-base die castings; all of which may bear plates of other metals, such as copper, etc.
  • Basis metal substrates may have a variety of surface finishes depending on the final appearance desired, which in turn depends on such factors as luster, brilliance, leveling, thickness, etc. of the nickel-iron, cobalt-iron and nickel-cobalt-iron containing electroplate applied on such substrates.
  • primary brightener as used herein is meant to include plating additive compounds such as reaction products of epoxides with alpha-hydroxy acetylenic alcohols such as diethoxylated 2 butyne-l ,4-diol or dipropoxylated 2 butyne-l,4-diol, other acetylenics, N-heterocyclics, active sulfur compounds, dye-stuffs, etc.
  • plating additive compounds such as reaction products of epoxides with alpha-hydroxy acetylenic alcohols such as diethoxylated 2 butyne-l ,4-diol or dipropoxylated 2 butyne-l,4-diol, other acetylenics, N-heterocyclics, active sulfur compounds, dye-stuffs, etc.
  • plating additive compounds such as reaction products of epoxides with alpha-hydroxy acetylenic alcohols such as diethoxyl
  • secondary brightener as used herein is meant to include aromatic sulfonates, sulfonamides, sulfonimides, sulfinates, etc. Specific examples of such plating additives are:
  • Such plating additive compounds which may be used singly or in suitable combinations, have one or more of the following functions:
  • secondary auxiliary brightener as used herein is meant to include aliphatic or aromatic-aliphatic olefinically or acetylenically unsaturated sulfonates, sulfonamides, or sulfonimides, etc. Specific examples of such plating additives are:
  • secondary auxiliary brighteners one may also include ions or compounds of certain metals and metalloids such as zinc, cadmium, selenium, etc. which, although they are not generally used at present, have been used to augment deposit luster, etc.
  • Other cooperating additives of organic nature which may be useful are the hydroxy sulfonate compounds of US. Pat. No. 3,697,391 i.e. typically, sodium formaldehyde bisulfite, the function of which is to make baths more tolerant to primary brightener concentrations, to increase toler- 4 ance toward metallic impurities such as zinc, etc., and, in this invention, to make the bath more tolerant to the complexing agent used and its concentration and also to the content of iron in the bath.
  • anti-pitting agent as used herein is an organic material (different from and in addition to the secondary auxiliary brightener) which has surfactant properties and which functions to prevent or minimize gas pitting.
  • An anti-pitting agent may also function to make the baths more compatible with contaminants such as oil, grease, etc. by their emulsifying, dispersing, solubilizing, etc. action on such contaminants and thereby promote attaining of sounder deposits.
  • Antipitting agents are optional additives which may or may not be used in combination with one or more members selected from the group consisting of a primary brightener, a secondary brightener, and a secondary auxiliary brightener.
  • anionic class Of the four classes of organic surfactants i.e., anionic, cationic, nonionic or amphoteric, the type commonly used for the electrodeposition of Ni, Co, Fe, or alloys thereof and for functioning as anti-pitters is the anionic class.
  • the anionic class individual members commonly used may be exemplified by the following:
  • nickel-iron-containing, cobalt-iron-containing, and nickel-cobalt-iron-containing bath compositions which may be used in combination with effective amounts of about 0.0050.2 grams per liter of the primary brightener, with about 1.0-30 grams per liter of the secondary brightener, with about 05-10 grams per liter of the secondary auxiliary brightener, and with about 0.05-1 gram per liter of anti-pitting agent, described herein, are summarized below. Combinations of primary brighteners and of secondary brighteners may also be used with the total concentration of members of each class coming within the typical concentration limits stated.
  • hydroxy-sulfonate additive compounds of the invention may be prepared according to the following general reaction:
  • M is a cation having a valence of 1-2; preferably M is an alkali metal or alkaline earth metal cation or ammonium; k is an integer l-2 corresponding to the valence of M; and R is hydrogen or a monovalent aliphatic group of l-l6 carbon atoms.
  • Typical nickel-containing, cobalt-containing, and nickelcobalt-containing bath compositions also containing iron which may be used in combination with effective amounts of about 0.5-5 g/l of the hydroxy-sulfonate additive compounds and effective amounts of about 0.00SO.2 g/l of the primary brighteners, with about l.030 g/l of the secondary brightener, with about O.5l0 g/l of the secondary auxiliary brightener, and with about 0.05l g/l of anti-pitting agent, described herein are summarized below.
  • Boric acid should be present in an amount of from 15 grams per liter to 60 grams per liter.
  • Mannitol, sorbitol and dulcitol are optical isomers having the following formula: HOCH,(CHOH ,CH,0H
  • Mannitol, sorbitol, and dulcitol are used in single or combined concentration of grams per liter to 60 grams per liter. Their function in nickel, cobalt and iron alloys thereof plating baths have been disclosed in U.S. Pat. No. 3,804,726.
  • aqueous bath compositions for electrodeposition of cobalt with iron or nickel and iron alloys may contain effective amounts of iodide from widely varying sources. Ionic iodide compounds have been found to be most preferred since the addition of such compounds has been found to be convenient and inexpensive. Any water-soluble iodide having a bath-compatible cation associated therewith may be employed in amounts sufficient to provide enhanced cobalt-containing electro: deposits as compared to cobalt-containing electrode posits which may be obtainedvin the absence of iodide ion.
  • Typical iodide compounds include the alkali metal iodides, alkaline earth iodides, other inorganic watersoluble metal iodides, as well as organic or other suitable compounds which may provide ionizable iodide ions on addition to the bath.
  • iodide compounds include sodium iodide, potassium iodide, cesium iodide, lithium iodide, ammonium iodide, calcium iodide, magnesium iodide, nickel iodide, cobaltous iodide, etc.
  • Materials which are converted to iodide in the cobalt-containing electroplating bath or during the electrodeposition process may also be employed.
  • iodine may be added (such as in the form ofa solution in methanol) to the aqueous cobalt-containing bath composition to provide effective amounts of iodide anions by interaction with bath constituents such as cobaltous ions according to the invention herein.
  • Organic compounds which provide ionizable iodide ions may also be employed, but the use of such compounds is generally not preferred unless the organic moiety contributes some added effect which may be desirable for a particular cobalt or cobalt-alloy electroplating process.
  • any effective amount of iodide may be employed.
  • an effective amount as used herein is meant an amount of iodide which is sufficient to provide improved cobalt-containing electrodeposits from a cobalt-containing electroplating bath composition as compared to an identical cobalt-electroplating bath composition which is essentially free of iodide ions.
  • I, ion iodide
  • An iodide ion concentration of 0.1-5 g/l will generally be found sufficient. Higher amounts of iodide may be used, but in general-the use of excessive amounts of iodide does not produce further enhancement of the cobalt-containing electrodeposit and may only serve to increase costs.
  • Typical aqueous nickel-containing electroplating baths include the following wherein all concentrations are in grams per liter (g/l) unless otherwise indicated.
  • Salts to make up the bath are of the types generally used for nickel and cobalt plating i.e. the sulfates and chlorides, usually combinations thereof.
  • Ferrous iron 6 may be added as Ferrous Sulfate or Ferrous Chloride, or Ferrous Sulfamate, preferably the sulfate which is easily available at low cost and good degree of purity (as FeSO -7H O).
  • a typical sulfamate-type nickel plating bath which may be used in practice of this invention may include the following components:
  • a typical chloride-free sulfate-type nickel plating bath which may be used in practice of this invention may include the following components:
  • a typical chloride-free sulfamate-type nickel plating bath which may be used in practice of this invention may include the following components:
  • the pH of all of the foregoing illustrative aqueous iron-nickel-containing, cobalt-iron-containing and nickel-cobalt-iron-containing compositions may be maintained during plating at pH values of2.0 to 4.5 and preferably from 3.0 to 3.5.
  • the pH may normally tend to rise and may be adjusted with acids such as hydrochloric acid or sulfuric acid, etc.
  • Operating temperature ranges for the above baths may be about 30 to 70C. with temperatures within the range of 45 to 65C. preferred.
  • Agitation of the above baths during plating may consist of solution pumping, moving cathode rod, air agitation or combinations thereof.
  • Anodes used in the above baths may consist of the particular single metals being plated at the cathode such as iron and nickel, for plating nickel-iron, cobalt and iron, for plating cobalt-iron, or nickel, cobalt, and iron, for plating nickel-cobalt-iron alloys.
  • the anodes may consist of the separate metals involved suitably suspended in the bath as bars, strips or as small chunks in titanium baskets. In such cases the ratio of the separate metal anodes areas is adjusted to correspond to the particular cathode alloy composition desired.
  • anodes For plating binary or ternary alloys one may also use as anodes alloys of the metals involved in such a percent weight ratio of the separate metals as to correspond to the percent weight ratio of the same metals in the cathode alloy deposits desired. These two types of anode systems will generally result in a fairly constant bath metal ion concentration for the respective metals. If with fixed metal ratio alloy anodes there does occur some bath metal ion imbalance, occasional adjustments may be made by adding the appropriate corrective concentration of the individual metal salts. All anodes or anode baskets are usually suitably covered with cloth or plastic bags of desired porosity to minimize introduction into the bath of metal particles, anode slime, etc. which may migrate to the cathode either mechanically or electrophoretically to give roughness in cathode deposits.
  • Hull Cell tests were run under conditions described as follows and the deposits were examined along a line 2.54 cm from and parallel to the bottom edge of the Hull Cell panel.
  • a polished brass panel was scribed with a horizontal single pass of 2/0 grit emery to give a band width of about 1 cm. at a distance of about 2.5 cm. from the bottom of the panel. After cleaning the panel, including the use of a thin cyanide copper strike to assure excellent physical and chemical cleanliness, it was plated in a 267 ml. Hull Cell, at a 2 ampere cell current for 10 minutes, at a temperature of 50C. and using magnetic stirring.
  • a Watts Nickel bath was prepared having the following makeup composition:
  • nickel sulfate-300 g/l nickel chloride60 g/l boric acid-45 g/l The bath was given a high pH nickel carbonate treatment to precipitate heavy metal impurities, treated with 6 grams per liter of activated carbon and filtered after overnight digestion at 60C.
  • EXAMPLE I 250 ml. Watts Nickel 4 g/l Sodium Saccharinate 2.3 g/] Sodium Allyl Sulfonate 0.05 g/l Diethoxylated Butynediol 40 g/l FeSO .7H O (equivalent to 8.0 g/l Fe) 10 g/l Sodium Tartrate Dihydrate pH adjusted to 4.0
  • Erythorbic (Isoascorbic) Acid and readjusting pH to 4.0 thin, poorly leveled, hazy deposit from 0 to about 1.1 asd dull, iridescent from 1.1 to 4.0 asd, bright with fair leveling from 4.0 asd to high current density edge.
  • COBALT IRON PLATING CO ANODE USED A Cobalt Watts type solution was prepared having the following composition:
  • EXAMPLE VI 250 ml. of above stock solution 40 ml/l of 70% by wt. Sorbitol solution 80 g/l FeSO .7l-I O pH adjusted to 3.6.
  • Lustrous deposit from 0 to about 0.8 asd dull gray, brittle from 0.8 asd to high current density edge.
  • the deposit glossy semi-bright from 0 to about 0.2 asd non-uniform thin satiny white up to about 3.0 asd partially lustrous from 3 asd to high current density edge.
  • 20 g/l Sorbitol and readjusting pH to 4.0 deposit lustrous with scattered haze and ductile from 0 to about 8 asd dull gray, grainy, brittle from 8 asd to high current density edge.
  • EXAMPLE IX A bath having the following composition was prepared and purified by activated carbon treatment.
  • the deposit was non-uniformly very milky from to about 3.5 asd and lustrous from 3.5 asd to the high current density edge. The leveling was poor. On adding 1 g/l Sodium Formaldehyde Bisulfite the deposit was lustrous from 0 to 12 asd with poor leveling and a very slight rather uniform haze the ductility was excellent. On further adding 50 mg/l Diethoxylated Butynediol a brilliant, ductile, fairly well leveled deposit was obtained from 0 to 12 asd and the low current density coverage was fairly good. All the deposits of this Example were'made over a thin nickel strike deposit.
  • Temperature 60C. (maintained by immersing cell in a thermostatically controlled water bath).
  • Cathode brass strip (2.54 cm x 20.3 cm x 0.071 cm) buffed and polished on one side and immersed to a depth of about 17.8 cm horizontal bend 2.54 cm from bottom and the next 2.54 cm bent to give an internal angle on the polished side of cathode of about 45 polished side facing anode at an approximate distance of 10.2 cm and scribed vertically in center with a 1 cm wide band of a single pass of 2/0 grit emery paper scratches.
  • Example I Plating tests were first run on the bath of Example I also containing 0.125 g/l Sodium di-n-hexyl-sulfosuccinate and made up initially without Sodium Formaldehyde Bisulfite, using electrolytic nickel squares as anode in a bagged titanium anode basket, adding iron as 40 g/l FeSO .7I-I O and using air agitation at a temperature of C.
  • the first two deposits showed a definite haze in the recess of the bent cathode and at the solution line and this was completely eliminated after adding 1 g/l Sodium Formaldehyde Bisulfite to subsequently give brilliant, ductile, quite well leveled deposits overall.
  • Example XI Using the finally evolved bath composition of Example VIII a 4 liter life test was run on depositing a brilliant, leveled cobalt-iron alloy using essentially the conditions of Example X except that the anode metal was cobalt. Optimumly using moving cathode rod agitation to attain best deposit luster in extreme low cathode current density areas, bright, well-leveled, ductile cobaltiron deposits having tensile stress were obtained consistently. It was found, however, over an electrolysis period of several hundred ampere-hours that the average cobalt content was about 94% while the average iron content was only about 6 percent.
  • a process for the preparation of an electrodeposit which contains iron and at least .one metal selected from the group consisting of nickel and cobalt which comprises passing current from an-anode to a cathode through an aqueous acidic electroplating solution-containing an iron compound and at least one member selected from the group consisting of cobalt compounds and nickel compounds providing cobalt or nickel ions for electrodepositing alloys of iron with cobalt and/or nickel and containing in combination:
  • At least one member selected from the group of cooperating additives consisting of: a. 0.005 gram per liter to 0.2 gram per liter of primary brightener b. 1.0 gram per liter to 30 grams per liter of secondary brightener c. 0.5 gram per liter to 10 grams per liter of secondary auxiliary brightener d. 0.05 gram per liter to 1 gram per liter of anti-pitting agent; 2. 0.5 gram per liter to 5 grams per liter of an organic hydroxy-sulfonate compound of the formula:
  • M is a cation having a valence of 1-2; k is an integer l2 corresponding to the valence of M; and R is hydrogen or a monovalent aliphatic group of ll6 carbon atoms;
  • 1 at'leastonemember selected from the group of cooperating additives consisting of: a. 0.005 gram per liter to 0.2 gram per liter of primary brightener b. 1.0 gram per liter to 30 grams per liter of secondary brightener c. 0.5 gram per liter to 10 grams per liter of secondary auxiliary brightener i d. 0.05 gram per liter to 1 gram per liter of'anti-pitting agent; 2. 0.5 gram per liter to 5 grams per liter of an organic hydroxy-sulfonate compound of the formula:
  • M is a cation having a valence of 1-2; k is an integer l2 corresponding to the valence of M; and R is hydrogen or a monovalent aliphatic group of ll6 carbon atoms;
  • a process for the preparation of a cobalt-iron electrodeposit which comprises passing current from an anode to a cathode through an aqueous acidic plating solution containing 200 grams per liter to 500 grams per liter of cobalt sulfate, 45 grams per liter to grams per liter of cobalt chloride, 15 grams per liter to 60 grams per liter of boric acid, 0.5 gram per liter to 5 grams per liter of erythorbic acid, 0.5 gram per liter to 10 grams per liter of sodium formaldehyde bisulfite, 0.1 gram per liter to 5 grams per liter of potassium iodide, 1.0 gram per liter to 30 grams per liter of sodium saccharinate, 0.5 gram per liter to l0 grams per liter of sodium allyl sulfonate, 5 grams per liter to 60 grams per liter of ferrous sulfate, and 0.005 gram per liter to 0.2 gram per liter of diethoxyl
  • composition of claim 11 wherein said primary brightener is 1,4-di-(B-hydroxy ethoxy-2- butyne).
  • composition of claim 11 wherein said primary brightener is 1,4-di-(B-hydroxy propoxy-2- butyne).
  • composition of claim 11 wherein said organic hydroxy-sulfonate compound is sodium formaldehyde bisulfite.
  • composition of claim 11 wherein said hydroxy-carboxylate is sodium tartrate dihydrate.
  • composition of claim 11 wherein said hydroxy-carboxylate compound is malic acid.
  • composition of claim 11 wherein said hydroXy-carboxylate compound is sodium citrate dihydrate.
  • composition of claim 11 wherein said hydroxy-carboxylate compound is sodium glycolate.
  • composition of claim 11 wherein said hydroxy-carboxylate compound is sodium boroglucoheptonate.
  • composition as claimed in claim 11 wherein said nickel compounds are nickel sulfate and nickel chloride.
  • composition as claimed in claim 11 wherein said nickel compounds are nickel sulfamate and nickel chloride.
  • composition as claimed in claim 11 wherein said cobalt compounds are cobalt sulfate and cobalt chloride.
  • composition as claimed in claim 11 wherein said cobalt compounds are cobalt sulfamate and cobalt chloride.
  • composition as claimed in claim 11 wherein said ferrous compound is ferrous sulfate or ferrous chloride.
  • An aqueous acidic electroplating solution which contains 200 grams per liter to 500 grams per liter of cobalt sulfate, 45 grams per liter to grams per liter of cobalt chloride, 15 grams per liter to 60 grams per liter of boric acid, 10 grams per liter to 60 grams per liter of sorbitol, 0.5 gram per liter to 5 grams per liter of erythorbic acid, 0.5 gram per liter to 10 grams per liter of sodium formaldehyde bisulfite, 0.1 gram per liter to 5 grams per liter of potassium iodide, 1.0 grams per liter to 30 grams per liter of sodium saccharinate, 0.5 gram per liter to 10 grams per liter of sodium allyl sulfonate, 5 grams per liter to 60 grams per liter of ferrous sulfate, and 0.005 gram per liter to 0.2 gram per liter of diethoxylated butynediol.

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US498947A 1974-08-20 1974-08-20 Electrode position of alloys of nickel, cobalt or nickel and cobalt with iron and electrolytes therefor Expired - Lifetime US3922209A (en)

Priority Applications (14)

Application Number Priority Date Filing Date Title
US498947A US3922209A (en) 1974-08-20 1974-08-20 Electrode position of alloys of nickel, cobalt or nickel and cobalt with iron and electrolytes therefor
CA233,550A CA1058553A (en) 1974-08-20 1975-08-15 Electrodeposition of alloys of nickel, cobalt, or nickel and cobalt with iron
ZA00755278A ZA755278B (en) 1974-08-20 1975-08-18 Electrodeposition of alloys of nickel, cobalt or nickel and cobalt
BR7505302*A BR7505302A (pt) 1974-08-20 1975-08-19 Processo para eletrodeposicao de ligas de niquel cobalto ou niquel e cobalto com ferro e composicao de solucao aquosa de revestimento para o mesmo
CS755670A CS187487B2 (en) 1974-08-20 1975-08-19 Aqueous galvanic solution
AU84078/75A AU493939B2 (en) 1974-08-20 1975-08-19 Electrodeposition of alloys of nickel, cobalt, or nickel and cobalt with iron
GB3446775A GB1464483A (en) 1974-08-20 1975-08-19 Electrodeposition of alloys of nickel cobalt or nickel and cobalt with iron
SE7509245A SE416825B (sv) 1974-08-20 1975-08-19 Forfarande for elektrolytisk utfellning av legeringar av jern med kobolt och/eller nickel och medel for genomforande av forfarandet
ES440326A ES440326A1 (es) 1974-08-20 1975-08-19 Un procedimiento para la preparacion de un deposito electro-litico.
JP50101075A JPS599637B2 (ja) 1974-08-20 1975-08-20 ニツケル コバルトマタハ ニツケルト コバルトノテツゴウキンデンチヤクホウ
FR7525760A FR2282488A1 (fr) 1974-08-20 1975-08-20 Procede et composition pour l'electrodeposition d'alliages de nickel ou de cobalt, ou de nickel et de cobalt avec du fer
NL7509898A NL7509898A (nl) 1974-08-20 1975-08-20 Werkwijze voor het elektrolytisch platteren met legeringen van ijzer met nikkel en/of kobalt, voor het bereiden van een bad daarvoor, alsmede gevormde voortbrengsels, verkregen met behulp van deze werkwijze.
DE19752537065 DE2537065A1 (de) 1974-08-20 1975-08-20 Verfahren zur elektrolytischen abscheidung von legierungen von nickel, kobalt oder nickel und kobalt mit eisen
IT9519/75A IT1033839B (it) 1974-08-20 1975-08-20 Elettrodeposizione di leghe di nickel cobalto oppure di nickel e cobalto con ferro

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CA (1) CA1058553A (en(2012))
CS (1) CS187487B2 (en(2012))
DE (1) DE2537065A1 (en(2012))
ES (1) ES440326A1 (en(2012))
FR (1) FR2282488A1 (en(2012))
GB (1) GB1464483A (en(2012))
IT (1) IT1033839B (en(2012))
NL (1) NL7509898A (en(2012))
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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4014759A (en) * 1975-07-09 1977-03-29 M & T Chemicals Inc. Electroplating iron alloys containing nickel, cobalt or nickel and cobalt
US4053373A (en) * 1975-07-09 1977-10-11 M & T Chemicals Inc. Electroplating of nickel, cobalt, nickel-cobalt, nickel-iron, cobalt-iron and nickel-iron-cobalt deposits
FR2501241A1 (fr) * 1981-03-06 1982-09-10 Langbein Pfanhauser Werke Ag Bain de galvanoplastie pour deposer des alliages palladium-nickel, procede d'utilisation d'un tel bain
US4450051A (en) * 1981-01-13 1984-05-22 Omi International Corporation Bright nickel-iron alloy electroplating bath and process
EP0447044A1 (en) * 1990-02-23 1991-09-18 Eaton Corporation Magneto-elastic film and process
CN1038351C (zh) * 1992-11-16 1998-05-13 浙江省冶金研究所 聚氨酯磁性漆包圆铜线的制造工艺
WO2001027355A1 (de) * 1999-10-14 2001-04-19 Hille & Müller Gmbh & Co. Verfahren zur herstellung eines elektrolytisch beschichteten kaltbandes, vorzugsweise zur verwendung für die herstellung von batteriehülsen, sowie nach dem verfahren geferfigte batteriehülse
US6376063B1 (en) * 1998-06-15 2002-04-23 The Boeing Company Making particulates of controlled dimensions by electroplating
US20050029108A1 (en) * 2001-01-15 2005-02-10 Mitsuo Kawasaki Soft magnetic film having high saturation magnetic flux density, thin-film magnetic head using the same, and manufacturing method of the same
CN105132973A (zh) * 2015-09-22 2015-12-09 太原工业学院 一种环保型无氰电镀铜锌合金溶液及其电镀铜锌合金工艺
CN108130568A (zh) * 2018-02-06 2018-06-08 营口奥捷专用汽车制造有限公司 一种环保型代铬电镀液及配制方法

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US3697391A (en) * 1970-07-17 1972-10-10 M & T Chemicals Inc Electroplating processes and compositions
US3804726A (en) * 1973-04-23 1974-04-16 M & T Chemicals Inc Electroplating processes and compositions
US3806429A (en) * 1972-07-03 1974-04-23 Oxy Metal Finishing Corp Electrodeposition of bright nickel-iron deposits,electrolytes therefor and coating an article with a composite nickel-iron,chromium coating

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Publication number Priority date Publication date Assignee Title
US3697391A (en) * 1970-07-17 1972-10-10 M & T Chemicals Inc Electroplating processes and compositions
US3806429A (en) * 1972-07-03 1974-04-23 Oxy Metal Finishing Corp Electrodeposition of bright nickel-iron deposits,electrolytes therefor and coating an article with a composite nickel-iron,chromium coating
US3804726A (en) * 1973-04-23 1974-04-16 M & T Chemicals Inc Electroplating processes and compositions

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4053373A (en) * 1975-07-09 1977-10-11 M & T Chemicals Inc. Electroplating of nickel, cobalt, nickel-cobalt, nickel-iron, cobalt-iron and nickel-iron-cobalt deposits
US4014759A (en) * 1975-07-09 1977-03-29 M & T Chemicals Inc. Electroplating iron alloys containing nickel, cobalt or nickel and cobalt
US4450051A (en) * 1981-01-13 1984-05-22 Omi International Corporation Bright nickel-iron alloy electroplating bath and process
FR2501241A1 (fr) * 1981-03-06 1982-09-10 Langbein Pfanhauser Werke Ag Bain de galvanoplastie pour deposer des alliages palladium-nickel, procede d'utilisation d'un tel bain
EP0447044A1 (en) * 1990-02-23 1991-09-18 Eaton Corporation Magneto-elastic film and process
CN1038351C (zh) * 1992-11-16 1998-05-13 浙江省冶金研究所 聚氨酯磁性漆包圆铜线的制造工艺
US6699579B2 (en) 1998-06-15 2004-03-02 The Boeing Company Particulates of controlled dimension
US6376063B1 (en) * 1998-06-15 2002-04-23 The Boeing Company Making particulates of controlled dimensions by electroplating
WO2001027355A1 (de) * 1999-10-14 2001-04-19 Hille & Müller Gmbh & Co. Verfahren zur herstellung eines elektrolytisch beschichteten kaltbandes, vorzugsweise zur verwendung für die herstellung von batteriehülsen, sowie nach dem verfahren geferfigte batteriehülse
AU773366B2 (en) * 1999-10-14 2004-05-20 Hille & Muller Gmbh Method for producing an electrolytically coated cold band, preferably used for the manufacture of battery shells, and for battery shells manufactured according to this method
US6923897B1 (en) 1999-10-14 2005-08-02 Hille & Mueller Gmbh Method for producing electrolytically coated cold rolled strip, preferably for use in the production of battery sheaths, and battery sheath produced according to this method
US20050029108A1 (en) * 2001-01-15 2005-02-10 Mitsuo Kawasaki Soft magnetic film having high saturation magnetic flux density, thin-film magnetic head using the same, and manufacturing method of the same
US7396445B2 (en) * 2001-01-15 2008-07-08 Tdk Corporation Method of manufacturing a thin-film magnetic head using a soft magnetic film having high saturation magnetic flux density
CN105132973A (zh) * 2015-09-22 2015-12-09 太原工业学院 一种环保型无氰电镀铜锌合金溶液及其电镀铜锌合金工艺
CN108130568A (zh) * 2018-02-06 2018-06-08 营口奥捷专用汽车制造有限公司 一种环保型代铬电镀液及配制方法

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FR2282488A1 (fr) 1976-03-19
DE2537065C2 (en(2012)) 1989-07-13
ES440326A1 (es) 1977-03-01
DE2537065A1 (de) 1976-03-04
CS187487B2 (en) 1979-01-31
NL7509898A (nl) 1976-02-24
IT1033839B (it) 1979-08-10
JPS599637B2 (ja) 1984-03-03
BR7505302A (pt) 1976-08-03
FR2282488B1 (en(2012)) 1980-04-25
SE416825B (sv) 1981-02-09
SE7509245L (sv) 1976-02-23
JPS5166238A (en) 1976-06-08
ZA755278B (en) 1976-07-28
AU8407875A (en) 1977-02-24
GB1464483A (en) 1977-02-16
CA1058553A (en) 1979-07-17

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