CA1070637A - Electroplating process - Google Patents
Electroplating processInfo
- Publication number
- CA1070637A CA1070637A CA261,686A CA261686A CA1070637A CA 1070637 A CA1070637 A CA 1070637A CA 261686 A CA261686 A CA 261686A CA 1070637 A CA1070637 A CA 1070637A
- Authority
- CA
- Canada
- Prior art keywords
- nickel
- cobalt
- iron
- disulfide compound
- organic disulfide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
Abstract of the Disclosure - This invention relates to a process and composition for the preparation of an electrodeposit which contains; at least one metal selected from the group consisting of nickel and cobalt or; binary or ternary alloys of the metals selected from nickel, iron, and cobalt; which comprises passing current from an anode to a cathode through an aqueous acidic electroplating solution containing at least one member selected from nickel compounds and cobalt compounds and which may additionally contain iron compounds providing nickel, cobalt and iron ions for electro-depositing nickel, cobalt, nickel-cobalt alloys, nickel-iron alloys, cobalt-iron alloys or nickel-iron-cobalt alloys and containing an effective amount of at least one additive; the improvement comprising the presence of 10 micromoles per compound or salt thereof having the formula:
wherein R1 and R2 are independently selected from , and where n is an integer from 0 to 5, X1 is selected from -OH, -NH2, , and or salts thereof and X2, X3 and X4 are independently selected from -H, -OH, -NH2, , and simultaneously hydrogen; for a time period sufficient to form a metal electroplate upon said cathode.
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wherein R1 and R2 are independently selected from , and where n is an integer from 0 to 5, X1 is selected from -OH, -NH2, , and or salts thereof and X2, X3 and X4 are independently selected from -H, -OH, -NH2, , and simultaneously hydrogen; for a time period sufficient to form a metal electroplate upon said cathode.
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Description
IMPROVED ELECTROPLATING PROCESS
- Background of the Invention An important consideration in the commercial electro-plating of bright nickel at the present time and for the forseeable future is minimizing the cost of depositing nickel and conserving the nickel metal itself, which is not an unlimited resource, and often in short supply or available only at high cost. To conserve nickel and reduce costs a number of procedures have been tried by the nickel plating industry. One of the earliest approaches to the problem was to reduce the thickness of nickel deposited. However, in order to retain the degree of brightening and leveling to which the I nickel plating industry has grown accustomed, it is necessary to use more effective or "powerful" nickel brighteners or higher concentrations of nickel brighteners, so that a bright ~and well-leveled nickel deposit might be obtained with the thinner deposits. The more "powerful" nickel brighteners or ; high concentrations of brighteners, while capable of producing the desired brightening and leveling, may nevertheless cause I unacceptable side effects. The nickel deposits may be highly ~¦ ~ stressed, severely embrittled, less receptive to subsequent chromium deposits or exhibit hazes, reduced low current density covering power or "throw~ or striations and skip ¦ plate, i. areas ln which a deposit is not obtained.
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~ ~070637 Another method of saving nickel has been to substitute cobalt for some portion of the nickel, and thereby deposit nickel-cobalt alloys. Generally, cobalt is more expensive than nickel, but at times cobalt may be more readily available than nickel. If thinner deposits of nickel-cobalt alloys are then deposited in order to reduce costs, but higher concentra-tions of brighteners, or more "powerful" brighteners.are employed in the plating bath to retain the desired degree of . brightening and leveling, the same problems mentioned.previously with respect to nickel.plating may become manifest; that is, the deposits may be highly stressed, severely embrittled, . hazy, striated, etc.
More recently, electrodeposited alloys of nickel-iron, nickel-cobalt-iron or.cobalt-iron have begun to be used commercially as substitutes for.decorative nickel electro-. deposits in periods when nickel has been in short supply or : to reduce the cost of nickel electrodeposits by substituting relatively inexpensive iron for a portion of the more expensive nickel and/or cobalt. Electrodeposited alloys containing as much as 60% by weight iron (with.the remainder predomin-antly nickel and/or cobalt):are thus being used commercially : . in applications where formerly all nickel.electrodeposits were - .
considered necessary.
. Although in many respects, the electrodeposition of nickel-iron, cobalt-iron or nickel-cobalt-iron aIloys is very similar to the electrodeposition of nickel in that similar equipment, operating conditions and organic additives . .-
- Background of the Invention An important consideration in the commercial electro-plating of bright nickel at the present time and for the forseeable future is minimizing the cost of depositing nickel and conserving the nickel metal itself, which is not an unlimited resource, and often in short supply or available only at high cost. To conserve nickel and reduce costs a number of procedures have been tried by the nickel plating industry. One of the earliest approaches to the problem was to reduce the thickness of nickel deposited. However, in order to retain the degree of brightening and leveling to which the I nickel plating industry has grown accustomed, it is necessary to use more effective or "powerful" nickel brighteners or higher concentrations of nickel brighteners, so that a bright ~and well-leveled nickel deposit might be obtained with the thinner deposits. The more "powerful" nickel brighteners or ; high concentrations of brighteners, while capable of producing the desired brightening and leveling, may nevertheless cause I unacceptable side effects. The nickel deposits may be highly ~¦ ~ stressed, severely embrittled, less receptive to subsequent chromium deposits or exhibit hazes, reduced low current density covering power or "throw~ or striations and skip ¦ plate, i. areas ln which a deposit is not obtained.
:~ . ., , .
1~
,, . .
~ ~070637 Another method of saving nickel has been to substitute cobalt for some portion of the nickel, and thereby deposit nickel-cobalt alloys. Generally, cobalt is more expensive than nickel, but at times cobalt may be more readily available than nickel. If thinner deposits of nickel-cobalt alloys are then deposited in order to reduce costs, but higher concentra-tions of brighteners, or more "powerful" brighteners.are employed in the plating bath to retain the desired degree of . brightening and leveling, the same problems mentioned.previously with respect to nickel.plating may become manifest; that is, the deposits may be highly stressed, severely embrittled, . hazy, striated, etc.
More recently, electrodeposited alloys of nickel-iron, nickel-cobalt-iron or.cobalt-iron have begun to be used commercially as substitutes for.decorative nickel electro-. deposits in periods when nickel has been in short supply or : to reduce the cost of nickel electrodeposits by substituting relatively inexpensive iron for a portion of the more expensive nickel and/or cobalt. Electrodeposited alloys containing as much as 60% by weight iron (with.the remainder predomin-antly nickel and/or cobalt):are thus being used commercially : . in applications where formerly all nickel.electrodeposits were - .
considered necessary.
. Although in many respects, the electrodeposition of nickel-iron, cobalt-iron or nickel-cobalt-iron aIloys is very similar to the electrodeposition of nickel in that similar equipment, operating conditions and organic additives . .-
- 2 ~ I ~
1 1' 11 , . . ~
are employed; nevertheless, electroplating with iron containing alloys of nickel and/or cobalt presents some special problems.
For example, in order to maintain the desired ratio of nickel . or cobalt ions to iron.ions.in the electroplating solution, a portion.of the nickel or cobalt anodes are desirably replaced with iron anodes to provide ferrous ions to the plating solution as a replenishment for the iron plated out of the bath.
. These iron anodes should corrode evenly, smoothly and efficiently . to avoid anode polarization, as well as to preclude the sloughing off of particles of the iron anodes thereby clogging anode bags and filters or causing rough deposits. 5ince the introduction of undesirable foreign materials to a plating bath must always be guarded against, the iron anodes should be of high purity. Unfortunately, iron of suitable purity for use as anodes in an iron alloy bath may not corrode evenly .in the bath and can result in the aforementioned problems.
Another requirement in the electrodeposition of iron alloys of-nickel and/or cobalt is that the iron in the ~
electroplating solution should be predominantly in the ferrous state rather than the ferric.. At a pH of about 3.5, basic ferric salts precipitate and can clog the anode bags and filters and may produce rough electrodeposits.. It is, therefore, advantageous to prevent any ferric basic salts from precipitating.
. This ¢an be accomplished by the addition of suitable complexing, chelating, anti-oxidant or reducing agents to the iron containing ¦ electropla ng alloy bath ac taught by Koret~ky in U. S.
Il - 3 -1C~70637 Patent 3,354,059; Passal in U. S. Patent 3,804,726; or Clauss et al in U. S. Patent 3,806,429. While these complexing or chelating agents are necessary in order to provide a solution to the ferric iron problem, their use may result in several 5 undesirable side effects. They can cause a reduction in deposit leveling and can also produce striated, hazy or dull deposits which may further exhibit step plate or even skip plate, i.e., areas which are not plated, or else plated only very , thinly compared to other sections of the deposits.
Object fff the I-nvention It is an object of this invention to provide processes and compositions for depositing electrodeposits of nickel, cobalt, or binary or ternary alloys of the metals selected from nickel, cobalt and iron which possess a greater tolerance for high concentrations of brighteners. It is a further object of this invention to provide deposits of nickel, cobalt or binary or ternary alloys of the metals selected from nickel, cobalt and iron characterized by increased ductility, brightness, covering power, and leveling or scratch hiding ability. It is a further object of this invention to provide for more uniform corrosion or dissolution of iron anodes in iron containing alloy electroplating baths of nickel, cobalt or nickel and cobalt. Other objects of this invention will be apparent from the following detailed description of this invention.
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.~ ~070637 . Description of the Invention .
In accordance with certain of its aspects, this invention relates to.a process for the preparatian of an electrodeposit which contains at least one metal..selected from the group consisting of.nickel and cobalt and which may also contain iron, which comprises.passing current through an .. . aqueous, acidic plating solution containing at least one member .. selected from the group consisting of nickel compounds and . cobalt compounds, and.which may also contain iron compounds to provide nickel, cobalt and iron ions for electrodepositing nickel, cobalt, or binary or ternary alloys of nickel, cobalt and iron; the improvement.comprising the presence of.10 micro-moles per liter to 2000 micromoles per liter of an organic disulfide compound or salt thereof having the formula:
Rl-S-S-R2 .
wherein Rl and R2 are independently selected from ~:~ ~ Xl ~ X2, and -(CH2)n-CH 3 : where n is an integer from 0 to 5, Xl is selected from -OH, -NH2, -C~OH , and -C~'~NH or salts thereof and X2, X3 and X4 ~: are independently selected from -H, -OH, -NH2, -C$oH, and -C~NH or salts thereof, provided that X3 and X4 are not ¦ simultaneously hydrogen; for a time period sufficient to form a tal ele troplate upon sdid cathode.
_ 5 _ Il, I
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; 107~637 The baths of this invention may also contain an effective amount of at least one member selected fro~ the group consisting of:
(a). Class I brighteners ~ b) Class II brighteners (c) Anti-pitting or wetting agents ~ he term "Class I brighteners" as used herein, and as described in Modern Electroplatin~, Third Edition, F. Lowenheim, Editor, is meant to include aromatic sulfonates, sulfonamides, sulfonimides, sulfinates, etc., as well as aliphatic or aromatic-aliphatic olefinically or acetylenically unsal-urated sulfonates, sulfonamides, sulfonimides, etc.
. Specific examples of such plating additives are:
: (1) sodium o-sulfobenzimide . .
(2) disodium 1,5-naphthalene disulfonate
1 1' 11 , . . ~
are employed; nevertheless, electroplating with iron containing alloys of nickel and/or cobalt presents some special problems.
For example, in order to maintain the desired ratio of nickel . or cobalt ions to iron.ions.in the electroplating solution, a portion.of the nickel or cobalt anodes are desirably replaced with iron anodes to provide ferrous ions to the plating solution as a replenishment for the iron plated out of the bath.
. These iron anodes should corrode evenly, smoothly and efficiently . to avoid anode polarization, as well as to preclude the sloughing off of particles of the iron anodes thereby clogging anode bags and filters or causing rough deposits. 5ince the introduction of undesirable foreign materials to a plating bath must always be guarded against, the iron anodes should be of high purity. Unfortunately, iron of suitable purity for use as anodes in an iron alloy bath may not corrode evenly .in the bath and can result in the aforementioned problems.
Another requirement in the electrodeposition of iron alloys of-nickel and/or cobalt is that the iron in the ~
electroplating solution should be predominantly in the ferrous state rather than the ferric.. At a pH of about 3.5, basic ferric salts precipitate and can clog the anode bags and filters and may produce rough electrodeposits.. It is, therefore, advantageous to prevent any ferric basic salts from precipitating.
. This ¢an be accomplished by the addition of suitable complexing, chelating, anti-oxidant or reducing agents to the iron containing ¦ electropla ng alloy bath ac taught by Koret~ky in U. S.
Il - 3 -1C~70637 Patent 3,354,059; Passal in U. S. Patent 3,804,726; or Clauss et al in U. S. Patent 3,806,429. While these complexing or chelating agents are necessary in order to provide a solution to the ferric iron problem, their use may result in several 5 undesirable side effects. They can cause a reduction in deposit leveling and can also produce striated, hazy or dull deposits which may further exhibit step plate or even skip plate, i.e., areas which are not plated, or else plated only very , thinly compared to other sections of the deposits.
Object fff the I-nvention It is an object of this invention to provide processes and compositions for depositing electrodeposits of nickel, cobalt, or binary or ternary alloys of the metals selected from nickel, cobalt and iron which possess a greater tolerance for high concentrations of brighteners. It is a further object of this invention to provide deposits of nickel, cobalt or binary or ternary alloys of the metals selected from nickel, cobalt and iron characterized by increased ductility, brightness, covering power, and leveling or scratch hiding ability. It is a further object of this invention to provide for more uniform corrosion or dissolution of iron anodes in iron containing alloy electroplating baths of nickel, cobalt or nickel and cobalt. Other objects of this invention will be apparent from the following detailed description of this invention.
l I
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.~ ~070637 . Description of the Invention .
In accordance with certain of its aspects, this invention relates to.a process for the preparatian of an electrodeposit which contains at least one metal..selected from the group consisting of.nickel and cobalt and which may also contain iron, which comprises.passing current through an .. . aqueous, acidic plating solution containing at least one member .. selected from the group consisting of nickel compounds and . cobalt compounds, and.which may also contain iron compounds to provide nickel, cobalt and iron ions for electrodepositing nickel, cobalt, or binary or ternary alloys of nickel, cobalt and iron; the improvement.comprising the presence of.10 micro-moles per liter to 2000 micromoles per liter of an organic disulfide compound or salt thereof having the formula:
Rl-S-S-R2 .
wherein Rl and R2 are independently selected from ~:~ ~ Xl ~ X2, and -(CH2)n-CH 3 : where n is an integer from 0 to 5, Xl is selected from -OH, -NH2, -C~OH , and -C~'~NH or salts thereof and X2, X3 and X4 ~: are independently selected from -H, -OH, -NH2, -C$oH, and -C~NH or salts thereof, provided that X3 and X4 are not ¦ simultaneously hydrogen; for a time period sufficient to form a tal ele troplate upon sdid cathode.
_ 5 _ Il, I
.
; 107~637 The baths of this invention may also contain an effective amount of at least one member selected fro~ the group consisting of:
(a). Class I brighteners ~ b) Class II brighteners (c) Anti-pitting or wetting agents ~ he term "Class I brighteners" as used herein, and as described in Modern Electroplatin~, Third Edition, F. Lowenheim, Editor, is meant to include aromatic sulfonates, sulfonamides, sulfonimides, sulfinates, etc., as well as aliphatic or aromatic-aliphatic olefinically or acetylenically unsal-urated sulfonates, sulfonamides, sulfonimides, etc.
. Specific examples of such plating additives are:
: (1) sodium o-sulfobenzimide . .
(2) disodium 1,5-naphthalene disulfonate
(3) trisodium 1,3,6-naphthalene trisulfonate
(4) sodium benzene monosulfonate . (5) dibenzene sulfonimide (6) sodium benzene monosulfinate (7) sodium allyl sulfonate (8) sodium 3-chloro-2-butene-1-sulfonate (9) sodium ~-styrene sulfonate (10) sodium propargyl sulfonate (11) monoallyl sulfamide (12) diallyl sulfamide ~13) allyl sulfonamide Il I
.
Such plating additive compounds, which may be used I singly or in suitable combinations, are desirably employed ¦ in amounts ranging from about 0.5 to 10 grams per liter and l have one or more of the following functions:
.
Such plating additive compounds, which may be used I singly or in suitable combinations, are desirably employed ¦ in amounts ranging from about 0.5 to 10 grams per liter and l have one or more of the following functions:
5 ¦ (1) To obtain semi-lustrous deposits or to ¦ produce substantial gr~in-refinement over the usual dull, matte, grainy, non-relective deposits from additive free baths.
¦ (2) To act as ductilizing agents when used 10 ¦ in combination with other additives such as ¦ Class II brighteners.
¦ (3) To control internal stress of deposits, ¦ generally by making the stress desirably ¦ compressive.
15 ¦ t4) To introduce controlled sulfur contents ¦ into the electrodeposits to desirably affect ¦ chemical reactivity, potential differences ¦ in composite coating systems, etc. thereby ¦ decreasing corrosion, better protecting the 20 ¦ basis metal from corrosion, etc.
¦ t5) They may act to prevent or minimize pitting.
¦ t6) They may condition the cathode surface by ¦ catalytic poisoning, etc. so that the rates of ¦ consumption of cooperating additives (usually of the Class II brightener type) may be substantially reduced, making for better economy o peration and control.
_7_ The term "Class II brighteners~ as used herein, and as described in Modern Electroplating, Third Edition, F. Lowenheim, Editor, is meant to.include plating additive compounds such as reaction products of epoxides with alpha-hydroxy acetylenic alcohols such as diethoxylated.2-butyne-1, 4-diol.or dipropoxylated.2-butyne-1,4-diol, other a~etylenics, N-heterocyclics, active sulfur compounds, dye-stuffs, etc.
Specific examples of such plating additives are:
(1) 1,4-di-(~-hydroxyethoxy)-2-butyne (2) 1,4-d~ -hydroxy-y-chloropropoxy)-2-butyne ..
(3~ 1,4-di-(~ -epoxypropoxy)-2-butyne (4) 1,.4-di-(~-hydroxy-y-butenoxy)-2-butyne (5) 1,4-di-(2'-hydroxy-4'-oxa-6'-heptenoxy)-2-butyne
¦ (2) To act as ductilizing agents when used 10 ¦ in combination with other additives such as ¦ Class II brighteners.
¦ (3) To control internal stress of deposits, ¦ generally by making the stress desirably ¦ compressive.
15 ¦ t4) To introduce controlled sulfur contents ¦ into the electrodeposits to desirably affect ¦ chemical reactivity, potential differences ¦ in composite coating systems, etc. thereby ¦ decreasing corrosion, better protecting the 20 ¦ basis metal from corrosion, etc.
¦ t5) They may act to prevent or minimize pitting.
¦ t6) They may condition the cathode surface by ¦ catalytic poisoning, etc. so that the rates of ¦ consumption of cooperating additives (usually of the Class II brightener type) may be substantially reduced, making for better economy o peration and control.
_7_ The term "Class II brighteners~ as used herein, and as described in Modern Electroplating, Third Edition, F. Lowenheim, Editor, is meant to.include plating additive compounds such as reaction products of epoxides with alpha-hydroxy acetylenic alcohols such as diethoxylated.2-butyne-1, 4-diol.or dipropoxylated.2-butyne-1,4-diol, other a~etylenics, N-heterocyclics, active sulfur compounds, dye-stuffs, etc.
Specific examples of such plating additives are:
(1) 1,4-di-(~-hydroxyethoxy)-2-butyne (2) 1,4-d~ -hydroxy-y-chloropropoxy)-2-butyne ..
(3~ 1,4-di-(~ -epoxypropoxy)-2-butyne (4) 1,.4-di-(~-hydroxy-y-butenoxy)-2-butyne (5) 1,4-di-(2'-hydroxy-4'-oxa-6'-heptenoxy)-2-butyne
(6) N-(2,3-dichloro-2-propenyi)-pyridinium chloride . (7~ 2,4,6-trimethyl N-propargyl pyridinium bromide . . . (8) N-allylquinaldinium bromide (9) 2-butyne-1,4-diol (10) propargyl alcohol . (11) 2-methyl-3-butyn-2-ol (12) quinaldyl-N-propanesulfonic acid betaine . . ~13) quinaldine dimethyl sulfate (14) N-allylpyridinium bromide (15) isoquinaldyl-N-propanesulfonic acid betaine (16) isoquinaldine dimethyl sulfate (17) N-allylisoquinaldine bromide ( disullonated 1,4-di-(~-hydroxyethoxy)-2-butyne Il _~_ I
1(~70637 ~19) 1~ hydroxyethoxy)-2-propyne (20) 1-(~-hydroxypropoxy)-2-propyne (21) sulfonated 1-(~-hydroxyethoxy)-2-propyne (22) phenosafranin (23) fuchsin .
When used alone or in combination, desirably in amounts ranging from about 5 to 1000 milligrams per liter, a Class II brightener may produce no.visual ef-fect on the . electrodeposit, or may produce semi-lustrous, fine-grained :10 deposits. However, best results are obtained when Class II
brighteners are used with one or more Class I brighteners in order to provide optimum deposit luster, rate of brightening, leveling, bright plate current density range,. low current density coverage, etc.
~: I Ihe term "anti-pitting.or wetting agents" as used herein is meant to include a material which functions to . prevent or minimize gas pitting. An anti-pitting agent, when ::~ used alone or.in combination,.desirably in amounts ranging from about 0.05 to l gram.per liter, may also function to 9 : 20 .make.the baths more compatible with contaminants such.as oil, ~ qrease, etc. by their emulsifying, dispersing, solubilizing, :~: etc. action on such contaminants and thereby promote attaining of sounder deposits. Preferred anti-pitting agents may include sodium lauryl sulfate, sodium lauryl ether-sulfate 1~ and sodi -alky1~u1fosuccinates.
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1~706:~7 The nickel compounds, cobalt compounds and iron compounds employed to provide nickel, cobalt and iron ions for electrodepositing nickel, cobalt, or binary or ternary alloys of nickel, cobalt and iron, (such as nickel-cobalt, nickel-iron, cobalt-iron and nickel-cobalt-iron alloys) are typically added as the sulfate, chloride, sulfamate or fluoborate salts. The sulfate, chloride, sulfamate or fLuoborate salts of nickel or cobalt are employed in concer.-trations sufficient to provide nickel and/or cobalt ions in the electroplating solutions of this invention in concentrations ranging from about 10 to 150 grams per liter. The iron compounds, such as the sulfate, chloride, etc. when added to the nickel, cobalt, or nickel and cobalt containing electro-plating solutions of this invention, are employed in concen-trations sufficient to provide iron ions ranging in concen-tration from about 0.25 to 25 grams per liter. The ratio of nickel ions or cobalt ions or nickel and cobalt ions to iron ions may range from about 50 to 1 to about 5 to 1.
The iron ions in the electroplating solutions of this invention may also be introduced through the use of iron anodes, rather than through the addition of iron compounds.
Thus, for example, if some percentage of the total anode area -in a nickel electroplating bath is composed of ixon anodes, after some period of electrolysis enough iron will have been introduced into the bath by chemical or electrochemical dissolution of the iron anodes to provide the desired concen-tration of iron ions.
The nickel, cobalt, nickel-cobalt, nickel-iron, cobalt-iron and nickel-cobalt-iron electroplating baths of this invention additionally may contain from about 30 to 60 grams per liter, preferably about 45 grams per liter of boric S acid or other buffering agents to control the p~ (e.g. from about 2.5 to 5, preferably about 3 to 4) and to prevent high current density burning.
-When iron ions are present in the plating baths of -this invention, the inclusion of one or more iron complexing, chelating, anti-oxidizing, reducing, or other iron solubilizing agents such as citric, malic, glutaric, gluconic, ascorbic, isoascorbic, muconic, glutamic, glycollic, and aspartic acids or similar acids or their salts are desirable in the iron containing baths to solubilize iron ions. These iron complexing or solubilizing agents may range in concentration in the plating solution from about one gram per liter to about 100 grams per liter, depending, of course, on how much iron is present in the plating bath.
In order to prevent nburning" of high current density areas, provide for more even temperature control of the solution, and control the amount of iron in the iron containing alloy deposits, solution agitation may be employed. Air agitation.
mechanical stirring, pumping, cathode rod and other means of solution agitation are all satisfactory. Additionally, the bath may be operated without agitation.
, The operating temperature of the electroplating baths of this invention may range from about 45C to about 85C, preferably from about 50C to 70.
The average cathode current density may range from about 0.5 to 12 amperes per square decimeter, with 3 to 6 amperes per square decimeter.providing an.optimum range.
Typical aqueous nickel-containing electroplating baths (which may be used in combination with effective amounts of cooperating additives) include the following wherein all concentrations are in grams per liter (g/l) unless otherwise indicated:
TABLE I .
AQUEOUS NICKEL-CONTAINING ELECTROPLATING BATHS .
Minimum. Maximum Preferred Component:
NiS04.6H20 75 500 300 NiC12-6H2 20 100 60 pH (electrometric)3 . 5 4 When.ferrous sulfate (FeS04~7H20) is included in the foregoing bath the concentration is about 2.5 grams per liter to about 125 grams per liter. .
Typical sulfamate-type nickel plating baths which may be used in the practice.of this invention may include ¦ the follo~ ng components:
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'~ABLE'II
Minimum Maximum' Preferred Component:
Nickel Sulfamate 100 500 375 2 2 10 ~oo 60 H3B03 , 60 45 pH (Electrometric) 3 5 4 When ferrous sulate (FeS04-7H20) is included in . the foregoing bath the concentrati.on is about 2.5 grams per liter to about I25 grams per liter.
Typical chloride-free sulfate-type nickel plating . baths which may be used in the practice of this invention may include the following components:
~ABLE III
Minimum Maximum Preferred Component:
NiS04 6 2100 500 300 H3B03 30 ' 6Q 45 pH (Electrometric) 2.5 4 3-3.5 When ferrous sulfate (FeS04-7H20) is included in the foregoing baths the concentration is about 2.5 grams per liter to about 125 grams per liter.
Typical chloride-free sulfamate-type nickel plating baths which may be used in the practice of this invention may '.
include th following components:
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Ii . ' , : , ' ~ , ' , ~070637 ~
TABLE IV
Minimum Maximum ~referred Component:
Nickel sulfamate 200 500 350 H3BO3 30 . 60 45 pH (Electrometric) 2.5 4 3-3.5 When.ferrous sulfate (FeSO4-7H2O) is included in the foregoing baths the concentration.is about 2.5 grams per liter to about 125 grams per liter.
10 The following are aqueous cobalt-containing and cobalt-nickel-containing electroplating baths which may be used in the practice of this invention:
. ~A~LE V
-AQUEOUS COBALT-CONTAINING AND COBALT-NICKEL-15 ~ONTAINING ELECTROPLATIN~ BATHS
.(All concentrations in g/l unless otherwise noted) Minimum Maximum -Preferred : Cobalt bath :~ . CoSO4-?H2O 50 500 300 .Ccl2~6H2o 15 125 60 : Cobalt bath CoSO4 7H2O 100 .500 400 NaCl 15 60 30 _ 14 ~
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1~70637 . TAB:LE V (cont.) Minimum ~Maximum Prefer~ed High chloride cobalt bath . CoSO4-7H2O 75 350 225 CoC12-6H2O 50 350 225 Cobalt-nickel alioy bath NiC12 6H2 15 75 60 All-chloride cobalt bath CoCl 6H O 100 500 300 Sulfamate cobalt bath . Cobalt sulfamate 100 400 290 CoC12-6H2O 15 75 60 The pH in the typical formulations of Table V
may range from about 3 to 5 with 4 preferred.
When ferrous sulfate (FeSO4-7H2O) is included in the foregoing baths.the concentration is about 2.5 grams per liter to 125 grams per liter.
Typical nickel-iron containing electroplating baths which may be used in the practice of this invention may include ; the follow component~:
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. ', ll 1070637 ~A~LE VI
M~nimum Maximum Preferred Component:
NiSO4-6H2o 20 500 200 FeSO4-7H2O 1 125 40 ; H3BO3 30 60 45 pH (Electrometric) 2.5 5 3.5-4 With the inclusion of ferrous sulfate (FeSO4-7H2O) in the foregoing bath formulations it is desirable to additionally include one or more iron complexing, chelating or solubilizing agents ranging in concentration from about 1 gram per liter to about 100 grams per liter, depending, of course, on the actual iron concentration.
It will be apparent that the above baths may contain compounds in amounts falling outside the preferred minimum and maximum set forth, but.most satisfactory and economical . operation may normally be effected when the compounds are present : in the baths in the amounts indicated. A particular advantage of.the chlori.de-free baths of Tables III and.IV,-supra, is that . the deposits obtained may be substantially free of tensile :: stress and may permit high speed plating involving the use of "high speed" anodes. .
The pH of all of the foregoing illustrative aqueous nickel-containing, cobalt-containing, nickel-cobalt-containing, nickel-iron, cobalt-iron and nickel-cobalt-iron-containing compositions.may be maintained during plating at pH values of 2..5.to 5.0, and preferably from about 3.0 to 4Ø During bath operation, the pH may normally tend to rise and m~y be adjusted ~0 with acids such as hydrochloric acid, sulfuric acid, etc.
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~o70637 Anodes used in the above baths may consist of the particular single metal being plated at the cathode such as nickel or cobalt for plating nickel or cobalt respectively. For plating binary or ternary alloys such as nickel-cobalt, cobalt-S iron, nickel-iron or nickel-cobalt-iron, the anodes may consist of the separate metals involved suitable suspended in the bath as bars, strips or small chunks in titanium baskets. In such cases the ratio of the separate metal anode areas is adjusted to correspond to the particular cathode alloy composition ~esired. 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 concentra-tion for the respective metals. If with fixed metal ratio alloy anodes there does occur some bath ion imbalance, occasional adjustments may be made by adding the appropriate corrective concentration of the individual metal salts. All anodes are usually suitably covered with cloth or plastic bags o~ 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.
~he substrates on which the nickel-containing, cobalt-containing, nickel-cobalt-containing, nickel-iron-containing, cobalt-iron-containing or nicke]-cobalt-iron_ containing electrodeposits of this invention may be applied .~
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may be metal or metal alloys such as are commonly electro-deposited and used in the art of electroplating such as nickel, cobalt, nickel-cobalt, 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, tin and alloys thereof such as with lead, 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 cobalt, nickel, or iron containing electroplate applied on such substrates.
While nickel, cobalt, nickel-cobalt, nickel-iron, cobalt-iron or nickel-iron-cobalt electrodeposits can be obtained employing the various parameters described above, the brightness, leveling, ductility and covering power may not be sufficient or satisfactory for a particular application.
In addition, the deposit may be hazy or dull, and also exhibit striations ard step plate. These conditions may especially result after the addition of excessive replenishment amounts of Class II brighteners, or from the use of especially "powerful"
Class II brighteners. In the case of the iron-containing ~ plating baths which additionally contain iron solubilizing ; 25 agents, the solubilizing agents may also cause a loss of leveling and brightness, or may result in hazy, dull or striated deposits. I have discovered that the addition or inclusion of certain bath compatible disulfide compounds to an aqueous ' '~' .
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, ~ ~07()637 acidic nickel, cobalt, nickel-cobalt, nickel-iron, cobalt-iron or nickel-iron-cobalt electroplating bath will correct the aforementioned deficiencies. Additionally, the disulfide compounds of this invention permit the use of higher than normal concentrations of Class II brighteners, thus permitting higher rates of brightening and leveling without the undesirable striations, skip plate, brittleness, etc. normally expected under these conditions. In addition, in those electroplating baths employing iron anodes, the disulfide compounds of this invention also provide for improved iron anode corrosion or dissolution. These bath soluble disulfide compounds are exemplified by the following ~eneralized formula:
. Rl-S-S-R2 where Rl and R2 are independently selected from ~ Xl ~ X2 and ~(CH2)n~CH~
where n is an integer from 0 to 5, Xl is selected from -OH, 2' ~OH nd C-NH2 and X2~ X3 and X4 are independently 1 ted from -H, -OH, -NH2, -C~OH and C~NH2 that X3 and X4 are not simultaneously hydrogen. It will ; 20 be appreciated that quaternary salts of the amine groups or salts or esters of the carboxyli.c acid groups may also be ; successfully employed. ~'or example, the hydrochloride or hydrosulfate salts of the amine functions can improve the solubility of the parent compound, while the ammonium, lithium, potassium, sodium and similar salts of the carboxy acids with ¦ bath compatible cations may also be advantageously employed while the simple esters (e.g., methyl, ethyl, etc.) of the acids ¦ hydrolyze the plating bath to give the parent acid.
Il 19 ~070637 Typical or representative compounds which are characterized by the above generalized formula are listed but not limited to the following:
(CH2)2 S S (CH2)2-OH HCo~,C~CH2~S~S~CH2~C'~O
2,2'-dithiodiethanol 2,2'-dithiodiacetic acid ~C-(CH2)2-S-S-(CH2)2-C~oH HO,C (CH2)3 2 3 `OH
3,3'-dithiodiproprionic acid 4,4'-dithiodibutyric acid H2N- (CH2) 2-S-S- (CH2) 2-NH2 HoQ~c-cH-cH2-s-s-cH2-cH-c~o cystamine cystine ÇOOH ÇOOH
~ ~ --5-5-(~ 112N-~-5-5-~3_N~12 2,2'-dithiodibenzoic acid 4,4'-dithiodianiline ¦ ~ N ~ -S-S- ~ N ~ S s_ HOOC COOH
4,4'-dithiodipyridine 6,6'-dithiodinicotinic acid The above compounds or salts or esters thereof are additionally advantageous in that they are commercially available; and thus, : . complex, difficult or dangerous syntheses need not be carried out in ord to obtain these materi~1s.
11 1' i Il, , . . i ''' ,' ': ' ~ ~, ' .
The use of sulfide compounds of the type NC-(CH2)n-S-(CH2)n-CN
where n is an integer from 1 to 4 have been shown by DuRose in U. S. Patent No. 2,978,391 to be useful brighteners in nickel electroplating baths. However, it has been found that monosulfide compounds of this type are undesirable in a nickel-iron, cobalt-iron or nickel-iron-cobalt electroplating bath because even at concentrations as low as 0.005 g/l :hey severely embrittle the deposit, produce iridescent medium and low current density hazes, cause the deposit to be dark in color and also cause the plating solution to be extremely sensitive to agitation. The monosulfides as well as similar compounds containing the mercapto (-SH) group have also been found to cause exfoliation of nickel-iron, cobalt-iron and nickel-iron-cobalt deposits from the basis metal. The disulfide compounds of this invention, quite unexpectedly, produce just the opposite effects when added to nickel, cobalt, nickel-iron, cobalt-iron or nickel-iron-cobalt electroplating baths, i.e., they eliminate medium and low current density hazes, improve the deposit coverage or throwing power (that is, extend the low current density plating range), and increase the deposit ductility.
Clauss et al in U. S. Patent No. 3,795,591 claim the use of compounds containing d sulfide and a sulfonate group in the same molecule to extend the current density range of a nickel-iron electroplating bath. The sulfonate group is thought to play an essential role in making these ., 11 , . I
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1~70637 sulfide compounds useful additives, as indeed sulfonate groups have been found to be essential to bright nickel plating in general, (see Modern Electroplating, Third Edition, pp.297-306).
It was, therefore, most unexpected and surprising to find that .
the disulfide compounds of this invention, which additionally contain carboxylic acid, hydroxy, amine and amide groups function in such a superior dnd beneficial manner to the sulfides of the prior art and yet do not contain the sulfonic acid moiety which heretofore appears to have been an essential component of nickel, cobalt and nickel-iron alloy electroplating additives.
The disulfide compounds of this invention are unusual in that they do not act as brighteners per se in the same way as brighteners of the. first or second class and therefore should not be thought of as brighteners, but rather as addition ; agents whose function in the bath is to overcome haze, striation and skip plate. Finally, these materials promote improved corrosion of iron anodes and thereby reduce the propensity for clogged anode bags and filters and rough deposits.
~ 20 The disulfide compounds of this invention are :: employed in the electroplating baths of this invention at concentrations of from about 10 micromoles per liter to 2000 micromoles per liter and preferably from about 20 micromoles per liter to 1000 micromoles per liter. .
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Il 1070637 The following examples are presented as an illustration to provide those skilled in the art of eleatroplating a better understanding of the various embodiments and aspects of this invention. These examples should not be construed as limiting the scope of the invention in any way.
An aqueous nickel electroplating bath was prepared having the ~ollowing composition:
Composition in g/l NiS4-6H2 300 NiC12 6 2 60 Sodium 1,5-naphthalene 4 disulfonate l-~-hydroxyethoxy)-~-propyne 0.3 pH 3.7 Temperature 55C.
A polished brass panel was scribed with a horizontal single pass of 4/0 grit emery polishing paper to give a band about 1 cm wide at a distance of about 2.5 cm from and parallel to the bottom edge of the panel. The cleaned panel was then plated in a 267 ml Hull Cell, using the above solution, for 10 minutes at 2 amperes cell current, using magnetic stirring.
The resulting test panel was essentially devoid of deposit ~i.e., skip plate) in the current density range from zero to about 8.0 amperes per square decimeter (asd) except for a number of scattered "islands" of nickel averaging about 0.5 mm Il . . . I
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in diameter. From about 8.0 asd to the high current density edge of the panel, the deposit was bright but severely s~riated.
On adding 415 micromoles per liter (0.1 g/l) of cystine to the plating solution (added as a 25 g~l aqueous solution, prepared by dissolving L(-) Cystine in water with enough dilute sulfuric acid to give the quaternary sulfate salt, thereby incr~asing the solubility) and r~peating the plating test, the resulting nickel deposit was bright and covered the entire test panel. There were no areas of skip plate.
An aqueous cobalt electroplating bath was prepared havîng the following composition:
Composition in g/l CoSO4-7H2O 300 CoC12-6H2O 60 Sodium o-sulfobenzimide 3.6 1,4-di~-hydroxyethoxy~-2-butyne 0.1 pH 3.6 Temperature 55& .
A polished brass panel was scribed with a horizontal single pass of 4/0 grit emery polishing paper to give a band about 1 cm wide at a distance of about 2.5 cm from and parallel to the bottom edge of the panel. The cleaned panel was then plated in a 267 ml Hull Cell, using the above solution, 1~70637 for 10 minutes at 2 amperes cell current, using magnetic stirring.
The resulting cobalt deposit was bright to brilliant across the entire current density range of the test panel except that there was a dense irregular haze extending from the low current density edge of the panel up to about i.2 asd. In addition, the low current density coverage on the back of the test panel was quite limited and exhibited a sharp line of demarkation between plated and unplated areas.
~n adding 79 micromoles per liter (0.02 g/11 Of sodium 3,3'-dithiodiproprionate to the plating solution and repeating the plating test, a bright to brilliant deposit was again obtained, except that the dense haze noted above had been completely eliminated. The low current density coverage on the back of the test panel had been greatly extended and covered the entire rear of the test panel and the deposit shaded off gradually without a sharp cut-off.
An aqueous nickel electroplating bath was prepared having the following composition:
Composition in g/l NiS4-6H2 300 NiC12 6 2 60 Sodium benzenesulfonate - 8 Sodium allyl sulfonate 3.7 ; 1~ hydroxyethoxy)-2-propyne 0.1 Temperature 55C.
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10706-~
A polished brass panel was scribed with a horizontal single pass of 4/0 grit emery polishing paper to give a band about 1 cm wide at a distance of about 2.5 cm from and parallel to the bottom edge of the panel. The cleaned panel was then plated in a 267 ml Hull Cell, using the above solution, for 10 minutes at 2 amperes cell current, using magnetic stirring.
~he resulting nicke] deposit was briliant and lustrous, but exhibited severe striations and step plate across the entire current density range of the test panel. In addition, the low -¦
current density areas, from 0.05 to about 0.6 asd had areas of skip plate (i.e., no deposit), while the rear of the panel (away from the anode) was completely devoid of deposit.
On adding 137 micromoles per liter ~0.025 g/l) f 2,2'-dithiodiacetic acid to the plating solution and repeating the plating test, the resulting nickel deposit was brilliant, lustrous, well leveled and completely free of striations, step plate or skip plate. In addition, the rear of the test panel, representing an extremely low current density region, was completely covered with a sound nickel deposit.
¦ An aqueous nickel-cobalt electroplating bath was prepared having the following composition:
Composition in g/l NiS4-6H2 - 240 ~iCl2-6~l2 48 CoSO4 7H2O 60 CoC12-6H2O 12 , Il l Sodium benzenesulfonate 12.5 Sodium allyl sulfonate 4.6 ~1-(2,3-dichloro-2-propenyl)-pyridinium chloride 0.096 2-Methyl-3-butyn-2-ol 0.083 pH 2.5 Temperature 55 C.
~ he Hull Cell test procedure and conditions described in Example l were employed to obtain a nickel-cobalt alloy deposit from the above solution. The resulting deposit was dark, hazy and thin in the region from about 0.05 asd to about 0.6 asd. From 0.6 asd to the high current density edge of the test panel, the deposi~ was so severely stressed that the entire deposit was exfoliating from the basis metal. In addition, the back of the test panel, an area of extremely low current density, was practicaily devoid of a deposit.
On adding 1224 micromoles per liter (0,375 g/l) of 2,2'-dithiodibenzoic acid to the plating solution and repeating the plating test, the resulting nickel-cobalt alloy deposit was sound across the entire current density range of the test panel with no evidence of the stress and deposit exfoliation noted earlier. The back of the test panel was also covered with a deposit of ckel-cobalt.
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An aqueous nickel-cobalt electroplating bath was prepared having the following composition:
Composition in-g/l NiS4-6H2 240 S NiC12-6H2 48 CoS4-7H2 60 CoC12.6H20 12 Sodium o-sulfobenzimide 1.8 Sodium allyl sulfonate 4.6 N-(2,3-dichloro-2-propenyl)-pyridinium chloride 0.048 2-Methyl-3-butyn-2-ol 0.042 pH 3.6 Temperature 55C.
Using the Hull Cell test procedure and conditions described in Example 1, a nickel-cobalt alloy deposit was obtained from the above solution. The deposit was brilliant across the entire current density range of the test panel.
However, the deposit in the very low current density areas was rather thin and coverage on the back of the test panel was very poor, while the medium to high current density areas (i.e., about 2 asd and higher) were so highly tensile stressed that the de sit had a network of seress ~raokc.
l l i Il On adding 125 micromoles per liter (0.03 g/l) of Cystine to the above solution and repeating the plating test, a brilliant deposit was again obtained, except that the deposit was completely free of stress cracks and the low current density areas, such as the rear of the test panel, were well covered with a sound deposit of nickel-cobalt.
~XAMPLE 6 An aqueous nickel-iron ele-troplating bath was I prepared having the following composition:
Composition in g/1 NiS4-6H2 300 NiC12 6 2 60 FeSO4-7H2O 40 Sodium iso-ascorbate 8 Sodium o-sulfobenzimide 2 Sodium allyl sulfonate 3.7 1,4-di(~-hydroxyethoxy)-2-butyne0.2 pH 3.6 Temperature 55C.
A polished brass panel was scribed with a horizontal single pass of 4/0 grit emery polishing paper to give a band about 1 cm wide at a distance of about 2.5 cm from and parallel to the bottom edge of the panel. The cleaned panel was then plated in a 267 ml Hull Cell, using the above solution, for 10 minutes at 2 amperes cell current, using magnetic stirring.
107063q The resulting nickel-iron alloy electrodeposit was bright but rather thin and without leveling in the current density range below about 1.2 amperes per square decimeter (asd). The deposit in the region from about 1.2 to 5 asd was badly striated, exhibited step plate, poor leveling, and an iridescent haze, while from about 5 asd to the high current density edge of the ; test panel, the deposit was brilliant and lustrous with I excellent leveling.
On adding 83 micromoles per liter (0.02 g/l) of ~ystine to the plating solution (added as a 25 g/l aqueous solution, prepared by dissolving L(-) Cystine in water with enough dilute sulfuric acid to give the quaternary sulfate salt, thereby increasing the solubility) and repeating the plating test, the resulting nickel-iron alloy deposit was brilliant, lustrous and completely free of haze, s riations or step plate across the entire current density range of the test panel. In addition, the deposit exhibited good ductility and leveling as evidenced by the degree of obliteration or filling in of the emery scratches.
~ he test conditions and procedure described in Example 6 were repeated except that 89 micromoles per liter ~0.02 g/1) of cys,amine dihydxochloride were substituted for the cystine. The resulting nickel-iron alloy electrodeposit was essentially the same as obtained in Example 6 when using cystine, except that a sli~ht haze was present at the low current density edge of the test panel.
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` ~070~37 ¦EXAMPLE 8 The test conditions and procedure described in Example 6 were repeated except that 137 micromoles per liter (0.025 g/l) of 2,2'-dithiodiacetic acid were substituted for the cystine and only 0.1 g/l rather than 0.2 g/l of 1,4-di-(~-hydroxyethoxy)-2-butyne were employed. The resulting nickel-iron alloy deposit was uniformly brilliant, lustrous and free of any haze, striations, step plate, skip plate or thin areas across the entire current density range of the test panel.
In addition, the deposit was very ductile and exhibited good leveling.
¦EXAMPLE 9 An aqueous nickel-iron electroplating bath was prepared ha~ing the following composition:
Compositi-on in g/l NiS4-6H2 300 NiC12 6 2 60 ; Fe804-7H20 40 Sodium iso-ascorbate 8 Sodium o-sulfobenzimide 3.6 Sodium allyl sulfonate 3.7 1,4-di-(~-hydroxyethoxy)-2-butyne 0.1 - pH 3.8 ¦1 ~erpera re 55C.
_ 31 ~
Using the Hull Cell test conditions and procedure described in Example 6, a deposit was obtained from the above solution which was bright but hazy, thin and without leveling in the current density range below about 1.2 asd. The deposit in the region from about 1.2 to 5 asd was badly striated, exhibited step plate, poor leveling, and an iridescent haze, while from about 5 asd to the high current density edge of the test panel the deposit was brilliant and lustrous with excellent leveling.
10 On adding 81 micromoles per liter (0.0125 g/l) of 2,2'-dithiodiethanol to the plating solution and repeating the plating test, the resulting nickel-iron alloy deposit was brilliant and lustrous, free of any striations, step plate, skip plate, or thin areas across the entire current density range of the test panel. ~dditionally, the deposit possessed excellent ductility, fair leveling and exhibited a faint low current density haze.
The concentration of 1,4-di-~-hydroxyethoxy)-2-butyne was increased to 0.2 g/l and the above plating test repeated.
The resultin~; nickel-iron alloy electrodeposi~ was completely brilliant, lustrous and free of haze, striations, step plate, skip plate or thin areas across the entire current density range of the test panel. In addition,-the deposit exhibited good leveling, very good ductility and outstanding low current density coverage.
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_ 32 ~
., ,' . 1' Il, The concentration of tha 1,4-di-(~-hydroxyethoxy)-2-butyne was then increased to 0.4 g/l and the plating test again repeated. The results were essentially identical to the results using 0.2 g/l of 1,4-di-(~-hydroxyethoxy)-2-butyne except that the deposit was less ductile. These outstanding results were obtained in spite of the fact that an exceptionally high concentration of Class II brightener (namely 0.4 g/l of 1,4-di-(~-hydroxyethoxy)-2-butynP) was employed in the plating test, which normally would result in a completely unacceptable deposit.
The test conditions and procedure described in Example 6 were repeated using the bath composition of Example 9 except that 82 micromoles per liter (0.025 g/l) of 2,2'- ..
dithiodibenzoic acid (added as an aqueous solution of the sodium salt) were substituted for the 2,2'-dithiodiethanol.
The resulting nickel-iron alloy electrodeposit.was uniformly brilliant.and lustrous, completely free of any.haze, striation, . step plate or low current.density thinness or-skip plate, and .
exhibited good leveling and excellent duct.lity across the entire current density range of.the test panel.
The concentration of 1,4-di-(~-hydroxyethoxy)-2-butyne was increased to 0.2 g/l and the above plating test repeated. The resulting deposit was essentially identical to the one described above, except that the leveling was better while the ctility remained excellent.
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I 1, , 1070637 .
EXAMPLE ll An aqueous nickel-iron electroplating bath was prepared having the following composition:
Co~position in g/l NiS4-6H2 300 NiC12-6H2 60 FeSO4.7H2O 40 Sodiu;,l citrate dihydrate 49 Sodium o-sulfobenzimide 3.6 Sodium allyl sulfonate 3.7 1,4-di-(~-hydroxyethoxy)-2-butyne 0.2 pH 3.0 Temperature 55C.
Using the Hull Cell test conditions and procedure described in Example 6, a deposit was obtained from the above solution which was bright to brilliant from about 2 asd to the high current density edge of the panel. At a current density of less than about 2 asd there was an iridescent haze.
On adding 95 micromoles per liter (0.024 g/l) of sodium 3,3'-dithiodiproprionate to the plating solution and repeating the plating test, the resulting deposit was essentially ;
identical to the previous deposit except that the iridescent haze was no longer present. The over~ll deposit brightness, however, s diminished somewhat.
_ 34 _ The concentration of 1,4-di-(~-hydroxyethoxy)-2-butyne was increased to 0.6 g/l and the above plating test repeated.
The resulting deposit was bright to brilliant and completely haze-free across the entire current density range of the panel.
In spite of the extremely high concentration (i.e., 0.6 g/l) of Class II brightener (i.e., 1,4-di-(~-hydroxyethoxy)-2-butyne), the deposit was completely ductile and the low current density coverage was exceller,t; without any avidence OL thim~ess or skip plate.
An aqueous nickel-iron electroplating bath was prepared having the following composition:
Composition in g/l NiS4-6~2 300 lS NiC12 6H2 60 FeSO4.7H2O 40 Sodium citrate dihyrate 32 Sodium p-toluenesulfonate 4 -Sodium o-sulfobenzimide 0.4 Sodium allyl sulfonate 3.7 Sodium lauryl sulfate 0.125 l-(~-hydroxyethoxy)-2-propyne 0.05 25 ~¦ ~emperature 55C. I
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A polished brass panel was scribed with a horizontal single pass of 4/0 grit emery polishing paper to give a band about 1 cm wide at a distance of about 2.5 cm from.and parallel to the bottom edge of the panel. The cleaned panel was then plated in a 267 ml Hull Cell, using the above solution, for 10.minutes at 2 amperes cell current, using.magnetic stirring.
The resulting nickel-iron alloy electrodeposit had poor leveling, : was dull, hazy, severely striated and brittle across the entire . current density range of the test panel. In.addition the low current density range below about 0.6 asd was thin.
On adding 110 micromoles per liter .(0.02 g/l) of . 2,2'-dithiodiacetic acid to the plating solution and repeating the plating test, the resulting nickel-iron alloy deposit was bright to brilliant across.the entire current density range of the test panel. In addition,.the deposit was very ductile and free of the striations and dull haz~ observed before adding the 2,2'-dithiodiacetic acid.. The low current density . coverage was excellent and.the deposit was not thin.
1~ .EX~MPLE 13 An aqueous nickel-iron electr~plating bath was prepared having the composition listed in.Example 11.
Using the Hull Cell test conditions and procedure described in Example 6, a deposit.was ob~ained from the above solution.which was bright to brilliant from about 2 asd to the high current density edge of the panel. At a current density of less than about 2 asd there was an.iridescent haze.
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On adding.408 micromoles per liter (0.125 g/l) of 2,2'-dithiodibenæoic acid (added as an alcoholic solution) to the plating solution and repeating the plating test, the resulting deposit was again bright, but no longer had the irideiscent haze noted above.
EXAMPLE 14 . ...
An aqueous nickel-cobalt-iron electroplating bath was prepared having.the following composition:
. Composi~ion in g~l NiS04 6H2 255 NiC12 6H20 .. 51 CoSO4-7H2O 45 CoC12-6H20 9 FeSO4-7~2O 40 Sodium citrate dihydrate 20 . Sodium iso-ascorbate. 2 Sodium o-sulfobenzimide 3.6 Sodium allyl sulfonate .. 3.7 1,4-di~ hydroxyethoxy)-2-butyne 0.2 : pH . 3.. 7 Temperature 50C. ,;
The Hull Cell test procedure and conditions described in Example 1 were employed.to obtain a.nickel-cobalt-iron alloy deposit from.the.above solution..: .The resulting.deposit was bright across the entire current density range.of the test . panel. However, the deposit exhibited a dense blue-grey haze 1, -37_ 11 ~ It Il Il !
~070637 in the region from aboutØ8 asd to about 4 asd and a stirring pattern haze was evident in the region from about 4 asd to 10 asd. The deposit was also very brittle.
On adding 330 micromoles.per liter (0.06 g/l) of 2,2'-dithiodiacetic acid to the plating solution and repeating the plating test, the resulting nickel-cobalt-iron alloy deposit was bright as before,.except that the blue-grey haze and stirrina pattern noted above were no longer present. The deposit was.also significantly more ductile.
Although th.is invention has been.. i.llustrated by reference to specific embodiments, modifications thereof which are clearly within the scope of the invention will be apparent to those skilled in the art.
1(~70637 ~19) 1~ hydroxyethoxy)-2-propyne (20) 1-(~-hydroxypropoxy)-2-propyne (21) sulfonated 1-(~-hydroxyethoxy)-2-propyne (22) phenosafranin (23) fuchsin .
When used alone or in combination, desirably in amounts ranging from about 5 to 1000 milligrams per liter, a Class II brightener may produce no.visual ef-fect on the . electrodeposit, or may produce semi-lustrous, fine-grained :10 deposits. However, best results are obtained when Class II
brighteners are used with one or more Class I brighteners in order to provide optimum deposit luster, rate of brightening, leveling, bright plate current density range,. low current density coverage, etc.
~: I Ihe term "anti-pitting.or wetting agents" as used herein is meant to include a material which functions to . prevent or minimize gas pitting. An anti-pitting agent, when ::~ used alone or.in combination,.desirably in amounts ranging from about 0.05 to l gram.per liter, may also function to 9 : 20 .make.the baths more compatible with contaminants such.as oil, ~ qrease, etc. by their emulsifying, dispersing, solubilizing, :~: etc. action on such contaminants and thereby promote attaining of sounder deposits. Preferred anti-pitting agents may include sodium lauryl sulfate, sodium lauryl ether-sulfate 1~ and sodi -alky1~u1fosuccinates.
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1~706:~7 The nickel compounds, cobalt compounds and iron compounds employed to provide nickel, cobalt and iron ions for electrodepositing nickel, cobalt, or binary or ternary alloys of nickel, cobalt and iron, (such as nickel-cobalt, nickel-iron, cobalt-iron and nickel-cobalt-iron alloys) are typically added as the sulfate, chloride, sulfamate or fluoborate salts. The sulfate, chloride, sulfamate or fLuoborate salts of nickel or cobalt are employed in concer.-trations sufficient to provide nickel and/or cobalt ions in the electroplating solutions of this invention in concentrations ranging from about 10 to 150 grams per liter. The iron compounds, such as the sulfate, chloride, etc. when added to the nickel, cobalt, or nickel and cobalt containing electro-plating solutions of this invention, are employed in concen-trations sufficient to provide iron ions ranging in concen-tration from about 0.25 to 25 grams per liter. The ratio of nickel ions or cobalt ions or nickel and cobalt ions to iron ions may range from about 50 to 1 to about 5 to 1.
The iron ions in the electroplating solutions of this invention may also be introduced through the use of iron anodes, rather than through the addition of iron compounds.
Thus, for example, if some percentage of the total anode area -in a nickel electroplating bath is composed of ixon anodes, after some period of electrolysis enough iron will have been introduced into the bath by chemical or electrochemical dissolution of the iron anodes to provide the desired concen-tration of iron ions.
The nickel, cobalt, nickel-cobalt, nickel-iron, cobalt-iron and nickel-cobalt-iron electroplating baths of this invention additionally may contain from about 30 to 60 grams per liter, preferably about 45 grams per liter of boric S acid or other buffering agents to control the p~ (e.g. from about 2.5 to 5, preferably about 3 to 4) and to prevent high current density burning.
-When iron ions are present in the plating baths of -this invention, the inclusion of one or more iron complexing, chelating, anti-oxidizing, reducing, or other iron solubilizing agents such as citric, malic, glutaric, gluconic, ascorbic, isoascorbic, muconic, glutamic, glycollic, and aspartic acids or similar acids or their salts are desirable in the iron containing baths to solubilize iron ions. These iron complexing or solubilizing agents may range in concentration in the plating solution from about one gram per liter to about 100 grams per liter, depending, of course, on how much iron is present in the plating bath.
In order to prevent nburning" of high current density areas, provide for more even temperature control of the solution, and control the amount of iron in the iron containing alloy deposits, solution agitation may be employed. Air agitation.
mechanical stirring, pumping, cathode rod and other means of solution agitation are all satisfactory. Additionally, the bath may be operated without agitation.
, The operating temperature of the electroplating baths of this invention may range from about 45C to about 85C, preferably from about 50C to 70.
The average cathode current density may range from about 0.5 to 12 amperes per square decimeter, with 3 to 6 amperes per square decimeter.providing an.optimum range.
Typical aqueous nickel-containing electroplating baths (which may be used in combination with effective amounts of cooperating additives) include the following wherein all concentrations are in grams per liter (g/l) unless otherwise indicated:
TABLE I .
AQUEOUS NICKEL-CONTAINING ELECTROPLATING BATHS .
Minimum. Maximum Preferred Component:
NiS04.6H20 75 500 300 NiC12-6H2 20 100 60 pH (electrometric)3 . 5 4 When.ferrous sulfate (FeS04~7H20) is included in the foregoing bath the concentration is about 2.5 grams per liter to about 125 grams per liter. .
Typical sulfamate-type nickel plating baths which may be used in the practice.of this invention may include ¦ the follo~ ng components:
. I
. l I
'~ABLE'II
Minimum Maximum' Preferred Component:
Nickel Sulfamate 100 500 375 2 2 10 ~oo 60 H3B03 , 60 45 pH (Electrometric) 3 5 4 When ferrous sulate (FeS04-7H20) is included in . the foregoing bath the concentrati.on is about 2.5 grams per liter to about I25 grams per liter.
Typical chloride-free sulfate-type nickel plating . baths which may be used in the practice of this invention may include the following components:
~ABLE III
Minimum Maximum Preferred Component:
NiS04 6 2100 500 300 H3B03 30 ' 6Q 45 pH (Electrometric) 2.5 4 3-3.5 When ferrous sulfate (FeS04-7H20) is included in the foregoing baths the concentration is about 2.5 grams per liter to about 125 grams per liter.
Typical chloride-free sulfamate-type nickel plating baths which may be used in the practice of this invention may '.
include th following components:
., - 13 -I .. I
Ii . ' , : , ' ~ , ' , ~070637 ~
TABLE IV
Minimum Maximum ~referred Component:
Nickel sulfamate 200 500 350 H3BO3 30 . 60 45 pH (Electrometric) 2.5 4 3-3.5 When.ferrous sulfate (FeSO4-7H2O) is included in the foregoing baths the concentration.is about 2.5 grams per liter to about 125 grams per liter.
10 The following are aqueous cobalt-containing and cobalt-nickel-containing electroplating baths which may be used in the practice of this invention:
. ~A~LE V
-AQUEOUS COBALT-CONTAINING AND COBALT-NICKEL-15 ~ONTAINING ELECTROPLATIN~ BATHS
.(All concentrations in g/l unless otherwise noted) Minimum Maximum -Preferred : Cobalt bath :~ . CoSO4-?H2O 50 500 300 .Ccl2~6H2o 15 125 60 : Cobalt bath CoSO4 7H2O 100 .500 400 NaCl 15 60 30 _ 14 ~
. . I
I
.
1~70637 . TAB:LE V (cont.) Minimum ~Maximum Prefer~ed High chloride cobalt bath . CoSO4-7H2O 75 350 225 CoC12-6H2O 50 350 225 Cobalt-nickel alioy bath NiC12 6H2 15 75 60 All-chloride cobalt bath CoCl 6H O 100 500 300 Sulfamate cobalt bath . Cobalt sulfamate 100 400 290 CoC12-6H2O 15 75 60 The pH in the typical formulations of Table V
may range from about 3 to 5 with 4 preferred.
When ferrous sulfate (FeSO4-7H2O) is included in the foregoing baths.the concentration is about 2.5 grams per liter to 125 grams per liter.
Typical nickel-iron containing electroplating baths which may be used in the practice of this invention may include ; the follow component~:
. _ ]5 _ Il . , . , I
. ', ll 1070637 ~A~LE VI
M~nimum Maximum Preferred Component:
NiSO4-6H2o 20 500 200 FeSO4-7H2O 1 125 40 ; H3BO3 30 60 45 pH (Electrometric) 2.5 5 3.5-4 With the inclusion of ferrous sulfate (FeSO4-7H2O) in the foregoing bath formulations it is desirable to additionally include one or more iron complexing, chelating or solubilizing agents ranging in concentration from about 1 gram per liter to about 100 grams per liter, depending, of course, on the actual iron concentration.
It will be apparent that the above baths may contain compounds in amounts falling outside the preferred minimum and maximum set forth, but.most satisfactory and economical . operation may normally be effected when the compounds are present : in the baths in the amounts indicated. A particular advantage of.the chlori.de-free baths of Tables III and.IV,-supra, is that . the deposits obtained may be substantially free of tensile :: stress and may permit high speed plating involving the use of "high speed" anodes. .
The pH of all of the foregoing illustrative aqueous nickel-containing, cobalt-containing, nickel-cobalt-containing, nickel-iron, cobalt-iron and nickel-cobalt-iron-containing compositions.may be maintained during plating at pH values of 2..5.to 5.0, and preferably from about 3.0 to 4Ø During bath operation, the pH may normally tend to rise and m~y be adjusted ~0 with acids such as hydrochloric acid, sulfuric acid, etc.
. l I - 16 - l ll ~.. , . I . , . I
: .
: .
~o70637 Anodes used in the above baths may consist of the particular single metal being plated at the cathode such as nickel or cobalt for plating nickel or cobalt respectively. For plating binary or ternary alloys such as nickel-cobalt, cobalt-S iron, nickel-iron or nickel-cobalt-iron, the anodes may consist of the separate metals involved suitable suspended in the bath as bars, strips or small chunks in titanium baskets. In such cases the ratio of the separate metal anode areas is adjusted to correspond to the particular cathode alloy composition ~esired. 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 concentra-tion for the respective metals. If with fixed metal ratio alloy anodes there does occur some bath ion imbalance, occasional adjustments may be made by adding the appropriate corrective concentration of the individual metal salts. All anodes are usually suitably covered with cloth or plastic bags o~ 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.
~he substrates on which the nickel-containing, cobalt-containing, nickel-cobalt-containing, nickel-iron-containing, cobalt-iron-containing or nicke]-cobalt-iron_ containing electrodeposits of this invention may be applied .~
_ 17 .. .
I
may be metal or metal alloys such as are commonly electro-deposited and used in the art of electroplating such as nickel, cobalt, nickel-cobalt, 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, tin and alloys thereof such as with lead, 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 cobalt, nickel, or iron containing electroplate applied on such substrates.
While nickel, cobalt, nickel-cobalt, nickel-iron, cobalt-iron or nickel-iron-cobalt electrodeposits can be obtained employing the various parameters described above, the brightness, leveling, ductility and covering power may not be sufficient or satisfactory for a particular application.
In addition, the deposit may be hazy or dull, and also exhibit striations ard step plate. These conditions may especially result after the addition of excessive replenishment amounts of Class II brighteners, or from the use of especially "powerful"
Class II brighteners. In the case of the iron-containing ~ plating baths which additionally contain iron solubilizing ; 25 agents, the solubilizing agents may also cause a loss of leveling and brightness, or may result in hazy, dull or striated deposits. I have discovered that the addition or inclusion of certain bath compatible disulfide compounds to an aqueous ' '~' .
, ~ - 18 - I I
,. , 1 ,.
, ~ ~07()637 acidic nickel, cobalt, nickel-cobalt, nickel-iron, cobalt-iron or nickel-iron-cobalt electroplating bath will correct the aforementioned deficiencies. Additionally, the disulfide compounds of this invention permit the use of higher than normal concentrations of Class II brighteners, thus permitting higher rates of brightening and leveling without the undesirable striations, skip plate, brittleness, etc. normally expected under these conditions. In addition, in those electroplating baths employing iron anodes, the disulfide compounds of this invention also provide for improved iron anode corrosion or dissolution. These bath soluble disulfide compounds are exemplified by the following ~eneralized formula:
. Rl-S-S-R2 where Rl and R2 are independently selected from ~ Xl ~ X2 and ~(CH2)n~CH~
where n is an integer from 0 to 5, Xl is selected from -OH, 2' ~OH nd C-NH2 and X2~ X3 and X4 are independently 1 ted from -H, -OH, -NH2, -C~OH and C~NH2 that X3 and X4 are not simultaneously hydrogen. It will ; 20 be appreciated that quaternary salts of the amine groups or salts or esters of the carboxyli.c acid groups may also be ; successfully employed. ~'or example, the hydrochloride or hydrosulfate salts of the amine functions can improve the solubility of the parent compound, while the ammonium, lithium, potassium, sodium and similar salts of the carboxy acids with ¦ bath compatible cations may also be advantageously employed while the simple esters (e.g., methyl, ethyl, etc.) of the acids ¦ hydrolyze the plating bath to give the parent acid.
Il 19 ~070637 Typical or representative compounds which are characterized by the above generalized formula are listed but not limited to the following:
(CH2)2 S S (CH2)2-OH HCo~,C~CH2~S~S~CH2~C'~O
2,2'-dithiodiethanol 2,2'-dithiodiacetic acid ~C-(CH2)2-S-S-(CH2)2-C~oH HO,C (CH2)3 2 3 `OH
3,3'-dithiodiproprionic acid 4,4'-dithiodibutyric acid H2N- (CH2) 2-S-S- (CH2) 2-NH2 HoQ~c-cH-cH2-s-s-cH2-cH-c~o cystamine cystine ÇOOH ÇOOH
~ ~ --5-5-(~ 112N-~-5-5-~3_N~12 2,2'-dithiodibenzoic acid 4,4'-dithiodianiline ¦ ~ N ~ -S-S- ~ N ~ S s_ HOOC COOH
4,4'-dithiodipyridine 6,6'-dithiodinicotinic acid The above compounds or salts or esters thereof are additionally advantageous in that they are commercially available; and thus, : . complex, difficult or dangerous syntheses need not be carried out in ord to obtain these materi~1s.
11 1' i Il, , . . i ''' ,' ': ' ~ ~, ' .
The use of sulfide compounds of the type NC-(CH2)n-S-(CH2)n-CN
where n is an integer from 1 to 4 have been shown by DuRose in U. S. Patent No. 2,978,391 to be useful brighteners in nickel electroplating baths. However, it has been found that monosulfide compounds of this type are undesirable in a nickel-iron, cobalt-iron or nickel-iron-cobalt electroplating bath because even at concentrations as low as 0.005 g/l :hey severely embrittle the deposit, produce iridescent medium and low current density hazes, cause the deposit to be dark in color and also cause the plating solution to be extremely sensitive to agitation. The monosulfides as well as similar compounds containing the mercapto (-SH) group have also been found to cause exfoliation of nickel-iron, cobalt-iron and nickel-iron-cobalt deposits from the basis metal. The disulfide compounds of this invention, quite unexpectedly, produce just the opposite effects when added to nickel, cobalt, nickel-iron, cobalt-iron or nickel-iron-cobalt electroplating baths, i.e., they eliminate medium and low current density hazes, improve the deposit coverage or throwing power (that is, extend the low current density plating range), and increase the deposit ductility.
Clauss et al in U. S. Patent No. 3,795,591 claim the use of compounds containing d sulfide and a sulfonate group in the same molecule to extend the current density range of a nickel-iron electroplating bath. The sulfonate group is thought to play an essential role in making these ., 11 , . I
.
1~70637 sulfide compounds useful additives, as indeed sulfonate groups have been found to be essential to bright nickel plating in general, (see Modern Electroplating, Third Edition, pp.297-306).
It was, therefore, most unexpected and surprising to find that .
the disulfide compounds of this invention, which additionally contain carboxylic acid, hydroxy, amine and amide groups function in such a superior dnd beneficial manner to the sulfides of the prior art and yet do not contain the sulfonic acid moiety which heretofore appears to have been an essential component of nickel, cobalt and nickel-iron alloy electroplating additives.
The disulfide compounds of this invention are unusual in that they do not act as brighteners per se in the same way as brighteners of the. first or second class and therefore should not be thought of as brighteners, but rather as addition ; agents whose function in the bath is to overcome haze, striation and skip plate. Finally, these materials promote improved corrosion of iron anodes and thereby reduce the propensity for clogged anode bags and filters and rough deposits.
~ 20 The disulfide compounds of this invention are :: employed in the electroplating baths of this invention at concentrations of from about 10 micromoles per liter to 2000 micromoles per liter and preferably from about 20 micromoles per liter to 1000 micromoles per liter. .
.
Il 1070637 The following examples are presented as an illustration to provide those skilled in the art of eleatroplating a better understanding of the various embodiments and aspects of this invention. These examples should not be construed as limiting the scope of the invention in any way.
An aqueous nickel electroplating bath was prepared having the ~ollowing composition:
Composition in g/l NiS4-6H2 300 NiC12 6 2 60 Sodium 1,5-naphthalene 4 disulfonate l-~-hydroxyethoxy)-~-propyne 0.3 pH 3.7 Temperature 55C.
A polished brass panel was scribed with a horizontal single pass of 4/0 grit emery polishing paper to give a band about 1 cm wide at a distance of about 2.5 cm from and parallel to the bottom edge of the panel. The cleaned panel was then plated in a 267 ml Hull Cell, using the above solution, for 10 minutes at 2 amperes cell current, using magnetic stirring.
The resulting test panel was essentially devoid of deposit ~i.e., skip plate) in the current density range from zero to about 8.0 amperes per square decimeter (asd) except for a number of scattered "islands" of nickel averaging about 0.5 mm Il . . . I
.
. .
in diameter. From about 8.0 asd to the high current density edge of the panel, the deposit was bright but severely s~riated.
On adding 415 micromoles per liter (0.1 g/l) of cystine to the plating solution (added as a 25 g~l aqueous solution, prepared by dissolving L(-) Cystine in water with enough dilute sulfuric acid to give the quaternary sulfate salt, thereby incr~asing the solubility) and r~peating the plating test, the resulting nickel deposit was bright and covered the entire test panel. There were no areas of skip plate.
An aqueous cobalt electroplating bath was prepared havîng the following composition:
Composition in g/l CoSO4-7H2O 300 CoC12-6H2O 60 Sodium o-sulfobenzimide 3.6 1,4-di~-hydroxyethoxy~-2-butyne 0.1 pH 3.6 Temperature 55& .
A polished brass panel was scribed with a horizontal single pass of 4/0 grit emery polishing paper to give a band about 1 cm wide at a distance of about 2.5 cm from and parallel to the bottom edge of the panel. The cleaned panel was then plated in a 267 ml Hull Cell, using the above solution, 1~70637 for 10 minutes at 2 amperes cell current, using magnetic stirring.
The resulting cobalt deposit was bright to brilliant across the entire current density range of the test panel except that there was a dense irregular haze extending from the low current density edge of the panel up to about i.2 asd. In addition, the low current density coverage on the back of the test panel was quite limited and exhibited a sharp line of demarkation between plated and unplated areas.
~n adding 79 micromoles per liter (0.02 g/11 Of sodium 3,3'-dithiodiproprionate to the plating solution and repeating the plating test, a bright to brilliant deposit was again obtained, except that the dense haze noted above had been completely eliminated. The low current density coverage on the back of the test panel had been greatly extended and covered the entire rear of the test panel and the deposit shaded off gradually without a sharp cut-off.
An aqueous nickel electroplating bath was prepared having the following composition:
Composition in g/l NiS4-6H2 300 NiC12 6 2 60 Sodium benzenesulfonate - 8 Sodium allyl sulfonate 3.7 ; 1~ hydroxyethoxy)-2-propyne 0.1 Temperature 55C.
.
ll -25- l ll I , . . I
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10706-~
A polished brass panel was scribed with a horizontal single pass of 4/0 grit emery polishing paper to give a band about 1 cm wide at a distance of about 2.5 cm from and parallel to the bottom edge of the panel. The cleaned panel was then plated in a 267 ml Hull Cell, using the above solution, for 10 minutes at 2 amperes cell current, using magnetic stirring.
~he resulting nicke] deposit was briliant and lustrous, but exhibited severe striations and step plate across the entire current density range of the test panel. In addition, the low -¦
current density areas, from 0.05 to about 0.6 asd had areas of skip plate (i.e., no deposit), while the rear of the panel (away from the anode) was completely devoid of deposit.
On adding 137 micromoles per liter ~0.025 g/l) f 2,2'-dithiodiacetic acid to the plating solution and repeating the plating test, the resulting nickel deposit was brilliant, lustrous, well leveled and completely free of striations, step plate or skip plate. In addition, the rear of the test panel, representing an extremely low current density region, was completely covered with a sound nickel deposit.
¦ An aqueous nickel-cobalt electroplating bath was prepared having the following composition:
Composition in g/l NiS4-6H2 - 240 ~iCl2-6~l2 48 CoSO4 7H2O 60 CoC12-6H2O 12 , Il l Sodium benzenesulfonate 12.5 Sodium allyl sulfonate 4.6 ~1-(2,3-dichloro-2-propenyl)-pyridinium chloride 0.096 2-Methyl-3-butyn-2-ol 0.083 pH 2.5 Temperature 55 C.
~ he Hull Cell test procedure and conditions described in Example l were employed to obtain a nickel-cobalt alloy deposit from the above solution. The resulting deposit was dark, hazy and thin in the region from about 0.05 asd to about 0.6 asd. From 0.6 asd to the high current density edge of the test panel, the deposi~ was so severely stressed that the entire deposit was exfoliating from the basis metal. In addition, the back of the test panel, an area of extremely low current density, was practicaily devoid of a deposit.
On adding 1224 micromoles per liter (0,375 g/l) of 2,2'-dithiodibenzoic acid to the plating solution and repeating the plating test, the resulting nickel-cobalt alloy deposit was sound across the entire current density range of the test panel with no evidence of the stress and deposit exfoliation noted earlier. The back of the test panel was also covered with a deposit of ckel-cobalt.
~ I
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:
An aqueous nickel-cobalt electroplating bath was prepared having the following composition:
Composition in-g/l NiS4-6H2 240 S NiC12-6H2 48 CoS4-7H2 60 CoC12.6H20 12 Sodium o-sulfobenzimide 1.8 Sodium allyl sulfonate 4.6 N-(2,3-dichloro-2-propenyl)-pyridinium chloride 0.048 2-Methyl-3-butyn-2-ol 0.042 pH 3.6 Temperature 55C.
Using the Hull Cell test procedure and conditions described in Example 1, a nickel-cobalt alloy deposit was obtained from the above solution. The deposit was brilliant across the entire current density range of the test panel.
However, the deposit in the very low current density areas was rather thin and coverage on the back of the test panel was very poor, while the medium to high current density areas (i.e., about 2 asd and higher) were so highly tensile stressed that the de sit had a network of seress ~raokc.
l l i Il On adding 125 micromoles per liter (0.03 g/l) of Cystine to the above solution and repeating the plating test, a brilliant deposit was again obtained, except that the deposit was completely free of stress cracks and the low current density areas, such as the rear of the test panel, were well covered with a sound deposit of nickel-cobalt.
~XAMPLE 6 An aqueous nickel-iron ele-troplating bath was I prepared having the following composition:
Composition in g/1 NiS4-6H2 300 NiC12 6 2 60 FeSO4-7H2O 40 Sodium iso-ascorbate 8 Sodium o-sulfobenzimide 2 Sodium allyl sulfonate 3.7 1,4-di(~-hydroxyethoxy)-2-butyne0.2 pH 3.6 Temperature 55C.
A polished brass panel was scribed with a horizontal single pass of 4/0 grit emery polishing paper to give a band about 1 cm wide at a distance of about 2.5 cm from and parallel to the bottom edge of the panel. The cleaned panel was then plated in a 267 ml Hull Cell, using the above solution, for 10 minutes at 2 amperes cell current, using magnetic stirring.
107063q The resulting nickel-iron alloy electrodeposit was bright but rather thin and without leveling in the current density range below about 1.2 amperes per square decimeter (asd). The deposit in the region from about 1.2 to 5 asd was badly striated, exhibited step plate, poor leveling, and an iridescent haze, while from about 5 asd to the high current density edge of the ; test panel, the deposit was brilliant and lustrous with I excellent leveling.
On adding 83 micromoles per liter (0.02 g/l) of ~ystine to the plating solution (added as a 25 g/l aqueous solution, prepared by dissolving L(-) Cystine in water with enough dilute sulfuric acid to give the quaternary sulfate salt, thereby increasing the solubility) and repeating the plating test, the resulting nickel-iron alloy deposit was brilliant, lustrous and completely free of haze, s riations or step plate across the entire current density range of the test panel. In addition, the deposit exhibited good ductility and leveling as evidenced by the degree of obliteration or filling in of the emery scratches.
~ he test conditions and procedure described in Example 6 were repeated except that 89 micromoles per liter ~0.02 g/1) of cys,amine dihydxochloride were substituted for the cystine. The resulting nickel-iron alloy electrodeposit was essentially the same as obtained in Example 6 when using cystine, except that a sli~ht haze was present at the low current density edge of the test panel.
. .. ~, . .
_ 30 ~ I I
!
~i I
` ~070~37 ¦EXAMPLE 8 The test conditions and procedure described in Example 6 were repeated except that 137 micromoles per liter (0.025 g/l) of 2,2'-dithiodiacetic acid were substituted for the cystine and only 0.1 g/l rather than 0.2 g/l of 1,4-di-(~-hydroxyethoxy)-2-butyne were employed. The resulting nickel-iron alloy deposit was uniformly brilliant, lustrous and free of any haze, striations, step plate, skip plate or thin areas across the entire current density range of the test panel.
In addition, the deposit was very ductile and exhibited good leveling.
¦EXAMPLE 9 An aqueous nickel-iron electroplating bath was prepared ha~ing the following composition:
Compositi-on in g/l NiS4-6H2 300 NiC12 6 2 60 ; Fe804-7H20 40 Sodium iso-ascorbate 8 Sodium o-sulfobenzimide 3.6 Sodium allyl sulfonate 3.7 1,4-di-(~-hydroxyethoxy)-2-butyne 0.1 - pH 3.8 ¦1 ~erpera re 55C.
_ 31 ~
Using the Hull Cell test conditions and procedure described in Example 6, a deposit was obtained from the above solution which was bright but hazy, thin and without leveling in the current density range below about 1.2 asd. The deposit in the region from about 1.2 to 5 asd was badly striated, exhibited step plate, poor leveling, and an iridescent haze, while from about 5 asd to the high current density edge of the test panel the deposit was brilliant and lustrous with excellent leveling.
10 On adding 81 micromoles per liter (0.0125 g/l) of 2,2'-dithiodiethanol to the plating solution and repeating the plating test, the resulting nickel-iron alloy deposit was brilliant and lustrous, free of any striations, step plate, skip plate, or thin areas across the entire current density range of the test panel. ~dditionally, the deposit possessed excellent ductility, fair leveling and exhibited a faint low current density haze.
The concentration of 1,4-di-~-hydroxyethoxy)-2-butyne was increased to 0.2 g/l and the above plating test repeated.
The resultin~; nickel-iron alloy electrodeposi~ was completely brilliant, lustrous and free of haze, striations, step plate, skip plate or thin areas across the entire current density range of the test panel. In addition,-the deposit exhibited good leveling, very good ductility and outstanding low current density coverage.
.
_ 32 ~
., ,' . 1' Il, The concentration of tha 1,4-di-(~-hydroxyethoxy)-2-butyne was then increased to 0.4 g/l and the plating test again repeated. The results were essentially identical to the results using 0.2 g/l of 1,4-di-(~-hydroxyethoxy)-2-butyne except that the deposit was less ductile. These outstanding results were obtained in spite of the fact that an exceptionally high concentration of Class II brightener (namely 0.4 g/l of 1,4-di-(~-hydroxyethoxy)-2-butynP) was employed in the plating test, which normally would result in a completely unacceptable deposit.
The test conditions and procedure described in Example 6 were repeated using the bath composition of Example 9 except that 82 micromoles per liter (0.025 g/l) of 2,2'- ..
dithiodibenzoic acid (added as an aqueous solution of the sodium salt) were substituted for the 2,2'-dithiodiethanol.
The resulting nickel-iron alloy electrodeposit.was uniformly brilliant.and lustrous, completely free of any.haze, striation, . step plate or low current.density thinness or-skip plate, and .
exhibited good leveling and excellent duct.lity across the entire current density range of.the test panel.
The concentration of 1,4-di-(~-hydroxyethoxy)-2-butyne was increased to 0.2 g/l and the above plating test repeated. The resulting deposit was essentially identical to the one described above, except that the leveling was better while the ctility remained excellent.
_ 33 I
I 1, , 1070637 .
EXAMPLE ll An aqueous nickel-iron electroplating bath was prepared having the following composition:
Co~position in g/l NiS4-6H2 300 NiC12-6H2 60 FeSO4.7H2O 40 Sodiu;,l citrate dihydrate 49 Sodium o-sulfobenzimide 3.6 Sodium allyl sulfonate 3.7 1,4-di-(~-hydroxyethoxy)-2-butyne 0.2 pH 3.0 Temperature 55C.
Using the Hull Cell test conditions and procedure described in Example 6, a deposit was obtained from the above solution which was bright to brilliant from about 2 asd to the high current density edge of the panel. At a current density of less than about 2 asd there was an iridescent haze.
On adding 95 micromoles per liter (0.024 g/l) of sodium 3,3'-dithiodiproprionate to the plating solution and repeating the plating test, the resulting deposit was essentially ;
identical to the previous deposit except that the iridescent haze was no longer present. The over~ll deposit brightness, however, s diminished somewhat.
_ 34 _ The concentration of 1,4-di-(~-hydroxyethoxy)-2-butyne was increased to 0.6 g/l and the above plating test repeated.
The resulting deposit was bright to brilliant and completely haze-free across the entire current density range of the panel.
In spite of the extremely high concentration (i.e., 0.6 g/l) of Class II brightener (i.e., 1,4-di-(~-hydroxyethoxy)-2-butyne), the deposit was completely ductile and the low current density coverage was exceller,t; without any avidence OL thim~ess or skip plate.
An aqueous nickel-iron electroplating bath was prepared having the following composition:
Composition in g/l NiS4-6~2 300 lS NiC12 6H2 60 FeSO4.7H2O 40 Sodium citrate dihyrate 32 Sodium p-toluenesulfonate 4 -Sodium o-sulfobenzimide 0.4 Sodium allyl sulfonate 3.7 Sodium lauryl sulfate 0.125 l-(~-hydroxyethoxy)-2-propyne 0.05 25 ~¦ ~emperature 55C. I
~, ~\
:
A polished brass panel was scribed with a horizontal single pass of 4/0 grit emery polishing paper to give a band about 1 cm wide at a distance of about 2.5 cm from.and parallel to the bottom edge of the panel. The cleaned panel was then plated in a 267 ml Hull Cell, using the above solution, for 10.minutes at 2 amperes cell current, using.magnetic stirring.
The resulting nickel-iron alloy electrodeposit had poor leveling, : was dull, hazy, severely striated and brittle across the entire . current density range of the test panel. In.addition the low current density range below about 0.6 asd was thin.
On adding 110 micromoles per liter .(0.02 g/l) of . 2,2'-dithiodiacetic acid to the plating solution and repeating the plating test, the resulting nickel-iron alloy deposit was bright to brilliant across.the entire current density range of the test panel. In addition,.the deposit was very ductile and free of the striations and dull haz~ observed before adding the 2,2'-dithiodiacetic acid.. The low current density . coverage was excellent and.the deposit was not thin.
1~ .EX~MPLE 13 An aqueous nickel-iron electr~plating bath was prepared having the composition listed in.Example 11.
Using the Hull Cell test conditions and procedure described in Example 6, a deposit.was ob~ained from the above solution.which was bright to brilliant from about 2 asd to the high current density edge of the panel. At a current density of less than about 2 asd there was an.iridescent haze.
: _ 36 ~
Il . ' I
On adding.408 micromoles per liter (0.125 g/l) of 2,2'-dithiodibenæoic acid (added as an alcoholic solution) to the plating solution and repeating the plating test, the resulting deposit was again bright, but no longer had the irideiscent haze noted above.
EXAMPLE 14 . ...
An aqueous nickel-cobalt-iron electroplating bath was prepared having.the following composition:
. Composi~ion in g~l NiS04 6H2 255 NiC12 6H20 .. 51 CoSO4-7H2O 45 CoC12-6H20 9 FeSO4-7~2O 40 Sodium citrate dihydrate 20 . Sodium iso-ascorbate. 2 Sodium o-sulfobenzimide 3.6 Sodium allyl sulfonate .. 3.7 1,4-di~ hydroxyethoxy)-2-butyne 0.2 : pH . 3.. 7 Temperature 50C. ,;
The Hull Cell test procedure and conditions described in Example 1 were employed.to obtain a.nickel-cobalt-iron alloy deposit from.the.above solution..: .The resulting.deposit was bright across the entire current density range.of the test . panel. However, the deposit exhibited a dense blue-grey haze 1, -37_ 11 ~ It Il Il !
~070637 in the region from aboutØ8 asd to about 4 asd and a stirring pattern haze was evident in the region from about 4 asd to 10 asd. The deposit was also very brittle.
On adding 330 micromoles.per liter (0.06 g/l) of 2,2'-dithiodiacetic acid to the plating solution and repeating the plating test, the resulting nickel-cobalt-iron alloy deposit was bright as before,.except that the blue-grey haze and stirrina pattern noted above were no longer present. The deposit was.also significantly more ductile.
Although th.is invention has been.. i.llustrated by reference to specific embodiments, modifications thereof which are clearly within the scope of the invention will be apparent to those skilled in the art.
Claims (22)
1. In a process for the preparation of an electrodeposit which contains; at least one metal selected from the group consisting of nickel and cobalt or; binary or ternary alloys of the metals selected from nickel, iron, and cobalt; which comprises passing current from an anode to a cathode through an aqueous acidic electroplating solution containing at least one member selected from nickel compounds and cobalt compounds or compounds providing nickel, cobalt and iron ions for electrodepositing nickel, cobalt, nickel-cobalt alloys, nickel-iron alloys, cobalt-iron alloys or nickel-iron-cobalt alloys and containing an effective amount of at least one additive; the improvement comprising the presence of 10 micromoles per liter to 2000 micromoles per liter of an organic disulfide compound or salt thereof having the formula:
wherein R1 and R2 are each independently selected from , and where n is an integer from 0 to 5, X1 is selected from -OH, -NH2, and or salts thereof and X2, X3 and X4 are each independently selected from -H, -OH, -NH2, , and or salts thereof, provided that X3 and X4 are not simultaneously hydrogen; for a time period sufficient to form a metal electroplate upon said cathode.
wherein R1 and R2 are each independently selected from , and where n is an integer from 0 to 5, X1 is selected from -OH, -NH2, and or salts thereof and X2, X3 and X4 are each independently selected from -H, -OH, -NH2, , and or salts thereof, provided that X3 and X4 are not simultaneously hydrogen; for a time period sufficient to form a metal electroplate upon said cathode.
2. The process of Claim 1 wherein said organic disulfide compound is 2,2'-dithiodiethanol.
3. The process of Claim 1 wherein said organic disulfide compound is 2,2'-dithiodiacetic acid.
4. The process of Claim 1 wherein said organic disulfide compound is 3,3'-dithiodiproprionic acid.
5. The process of Claim 1 wherein said organic disulfide compound is 4,4'-dithiodibutyric acid.
6. The process of Claim 1 wherein said organic disulfide compound is cystamine.
7. The process of Claim 1 wherein said organic disulfide compound is cystine.
8. The process of Claim 1 wherein said organic disulfide compound is 2,2'-dithiodibenzoic acid.
9. The process of Claim 1 wherein said organic disulfide compound is 4,4'-dithiodianiline.
10. The process of Claim 1 wherein said organic disulfide compound is 4,4'-dithiodipyridine.
11. The process of Claim 1 wherein said organic disulfide compound is 6,6'-dithiodinicotinic acid.
12. In a composition for the preparation of an electrodeposit which contains; at least one metal selected from the group consisting of nickel and cobalt or; binary or ternary alloys of the metals selected from nickel, iron, and cobalt; which comprises an aqueous acidic electroplating solution containing at least one member selected from nickel compounds and cobalt compounds or compounds providing nickel, cobalt and iron ions for electrodepositing nickel, cobalt, nickel-cobalt alloys, nickel-iron alloys,. cobalt-iron alloys or nickel-iron-cobalt alloys and containing an effective amount of at least one additive; the improvement comprising the presence of 10 micromoles per liter to 2000 micromoles per liter of an organic disulfide compound or salt thereof having the formula:
wherein R1 and R2 are each independently selected from , and where n is an integer from 0 to 5, X1 is selected from -OH, -NH2, and or salts thereof and X2, X3 and X4 are each independently selected from -H, -OH, -NH2, and or salts thereof, provided that X3 and X4 are not simultaneously hydrogen.
wherein R1 and R2 are each independently selected from , and where n is an integer from 0 to 5, X1 is selected from -OH, -NH2, and or salts thereof and X2, X3 and X4 are each independently selected from -H, -OH, -NH2, and or salts thereof, provided that X3 and X4 are not simultaneously hydrogen.
13. The composition of Claim 12 wherein said organic disulfide compound is 2,2'-dithiodiethanol.
14. The composition of Claim 12 wherein said organic disulfide compound is 2,2'-dithiodiacetic acid.
15. The composition of Claim 12 wherein said organic disulfide compound is 3,3'-dithiodiproprionic acid.
16. The composition of Claim 12 wherein said organic disulfide compound is 4,4'-dithiodibutyric acid.
17. The composition of Claim 12 wherein said organic disulfide compound is cystamine.
18. The composition of Claim 12 wherein said organic disulfide compound is cystine.
19. The composition of Claim 12 wherein said organic disulfide compound is 2,2'-dithiodibenzoic acid.
20. The composition of Claim 12 wherein said organic disulfide compound is 4,4'-dithiodianiline.
21. The composition of Claim 12 wherein said organic disulfide compound is 4,4'-dithiodipyridine.
22. The composition of Claim 12 wherein said organic disulfide compound is 6,6'-dithiodinicotinic acid.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US61519575A | 1975-09-22 | 1975-09-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1070637A true CA1070637A (en) | 1980-01-29 |
Family
ID=24464400
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA261,686A Expired CA1070637A (en) | 1975-09-22 | 1976-09-21 | Electroplating process |
Country Status (17)
| Country | Link |
|---|---|
| JP (1) | JPS5248526A (en) |
| AU (1) | AU498234B2 (en) |
| BE (1) | BE846465A (en) |
| BR (1) | BR7606259A (en) |
| CA (1) | CA1070637A (en) |
| CH (1) | CH626122A5 (en) |
| CS (1) | CS189788B2 (en) |
| DE (1) | DE2642666A1 (en) |
| DK (1) | DK424876A (en) |
| ES (1) | ES451714A1 (en) |
| FR (1) | FR2324762A1 (en) |
| GB (1) | GB1510079A (en) |
| MX (1) | MX143051A (en) |
| NL (1) | NL7610541A (en) |
| NO (1) | NO147995C (en) |
| SE (1) | SE7610517L (en) |
| ZA (1) | ZA765638B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2614312B1 (en) * | 1987-04-24 | 1990-03-09 | Elf Aquitaine | WATER SOLUBLE ADDITIVES WITH EXTREME PRESSURE EFFECT FOR AQUEOUS FUNCTIONAL FLUIDS, FUNCTIONAL FLUIDS AND CONCENTRATED AQUEOUS COMPOSITIONS CONTAINING SAID ADDITIVES. |
| DE3726518A1 (en) * | 1987-08-10 | 1989-03-09 | Hille & Mueller | COLD BAND WITH ELECTROLYTICALLY APPLIED NICKEL COATING HIGH DIFFUSION DEPTH AND METHOD FOR THE PRODUCTION OF COLD BELT |
| DE3909811A1 (en) * | 1989-03-24 | 1990-09-27 | Lpw Chemie Gmbh | Use of at least one organic sulphinic acid and/or at least one alkali metal salt of an organic sulphinic acid as an agent ... |
| DE19949549A1 (en) * | 1999-10-14 | 2001-04-26 | Hille & Mueller Gmbh & Co | Electrolytically coated cold strip, preferably for use in the production of battery sleeves and processes for coating the same |
| TWI758252B (en) | 2015-06-30 | 2022-03-21 | 美商麥克達米德恩索龍股份有限公司 | Cobalt filling of interconnects in microelectronics |
| US11035048B2 (en) | 2017-07-05 | 2021-06-15 | Macdermid Enthone Inc. | Cobalt filling of interconnects |
| WO2022169694A1 (en) * | 2021-02-03 | 2022-08-11 | Octet Scientific, Inc. | Electrolyte additives for zinc batteries |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB920922A (en) * | 1959-11-26 | 1963-03-13 | Canning & Co Ltd W | Nickel plating solutions |
| US3682788A (en) * | 1970-07-28 | 1972-08-08 | M & T Chemicals Inc | Copper electroplating |
| US3857765A (en) * | 1973-09-20 | 1974-12-31 | Metalux Corp | Purification of nickel and cobalt electroplating solutions |
-
1976
- 1976-09-21 DK DK424876A patent/DK424876A/en not_active Application Discontinuation
- 1976-09-21 ES ES451714A patent/ES451714A1/en not_active Expired
- 1976-09-21 CA CA261,686A patent/CA1070637A/en not_active Expired
- 1976-09-21 BR BR7606259A patent/BR7606259A/en unknown
- 1976-09-21 ZA ZA765638A patent/ZA765638B/en unknown
- 1976-09-22 GB GB39278/76A patent/GB1510079A/en not_active Expired
- 1976-09-22 NO NO763257A patent/NO147995C/en unknown
- 1976-09-22 MX MX166373A patent/MX143051A/en unknown
- 1976-09-22 JP JP51114320A patent/JPS5248526A/en active Pending
- 1976-09-22 FR FR7628454A patent/FR2324762A1/en active Granted
- 1976-09-22 CS CS766142A patent/CS189788B2/en unknown
- 1976-09-22 NL NL7610541A patent/NL7610541A/en not_active Application Discontinuation
- 1976-09-22 SE SE7610517A patent/SE7610517L/en unknown
- 1976-09-22 DE DE19762642666 patent/DE2642666A1/en not_active Withdrawn
- 1976-09-22 AU AU18007/76A patent/AU498234B2/en not_active Expired
- 1976-09-22 BE BE170843A patent/BE846465A/en not_active IP Right Cessation
- 1976-09-22 CH CH1201876A patent/CH626122A5/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| CS189788B2 (en) | 1979-04-30 |
| MX143051A (en) | 1981-03-02 |
| FR2324762A1 (en) | 1977-04-15 |
| BR7606259A (en) | 1977-06-21 |
| SE7610517L (en) | 1977-03-23 |
| ES451714A1 (en) | 1977-09-01 |
| CH626122A5 (en) | 1981-10-30 |
| AU1800776A (en) | 1978-04-06 |
| FR2324762B1 (en) | 1980-11-07 |
| NO147995C (en) | 1983-07-20 |
| AU498234B2 (en) | 1979-02-22 |
| BE846465A (en) | 1977-01-17 |
| ZA765638B (en) | 1977-08-31 |
| NO763257L (en) | 1977-03-23 |
| NL7610541A (en) | 1977-03-24 |
| NO147995B (en) | 1983-04-11 |
| GB1510079A (en) | 1978-05-10 |
| DK424876A (en) | 1977-03-23 |
| JPS5248526A (en) | 1977-04-18 |
| DE2642666A1 (en) | 1977-03-24 |
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