EP0452471B1 - Schutz von bleienthaltenden anoden während der elektrobeschichtung mit chrom - Google Patents

Schutz von bleienthaltenden anoden während der elektrobeschichtung mit chrom Download PDF

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Publication number
EP0452471B1
EP0452471B1 EP90917257A EP90917257A EP0452471B1 EP 0452471 B1 EP0452471 B1 EP 0452471B1 EP 90917257 A EP90917257 A EP 90917257A EP 90917257 A EP90917257 A EP 90917257A EP 0452471 B1 EP0452471 B1 EP 0452471B1
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EP
European Patent Office
Prior art keywords
acid
use according
plating
chromium
anode
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 - Lifetime
Application number
EP90917257A
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English (en)
French (fr)
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EP0452471A1 (de
EP0452471A4 (en
Inventor
Kenneth Russ Newby
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Atotech Deutschland GmbH and Co KG
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Atotech USA LLC
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Application filed by Atotech USA LLC filed Critical Atotech USA LLC
Publication of EP0452471A1 publication Critical patent/EP0452471A1/de
Publication of EP0452471A4 publication Critical patent/EP0452471A4/en
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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
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/12—Process control or regulation
    • C25D21/14—Controlled addition of electrolyte components
    • 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
    • C25D3/04—Electroplating: Baths therefor from solutions of chromium

Definitions

  • This invention is in the field of protecting lead anodes from corrosion during metal-electroplating processes. More particularly, this invention provides a process and composition for electroplating chromium, using lead or lead-containing anodes under conditions which produce adherent, bright chromium deposits at high efficiencies, where cathodic low-current-density etching is substantially reduced in comparison with existing high-efficiency catalyst systems.
  • U.S.-A- 4,588,481 specifies a variety of sulfonic acids, including methane-sulfonic acid (MSA), ethane-sulfonic acid (ESA), methanedisulfonic acid (MDSA) and 1,2-ethanedisulfonic acid (EDSA).
  • MSA methane-sulfonic acid
  • ESA ethane-sulfonic acid
  • MDSA methanedisulfonic acid
  • EDSA 1,2-ethanedisulfonic acid
  • MSA has become the agent of choice in a number of commercial embodiments for chromium plating which have appeared in the marketplace, even though severe scale buildup and anodic corrosion are encountered.
  • Conventional plating processes or “conventional baths” are herein defined as those which are conducted with a plating bath consisting of chromic acid and sulfate ion as the essential ingredients, the sulfate ion generally being provided by sulfuric acid or sodium sulfate, although those are not limiting sources, the requirement being solely that a soluble sulfate be provided. It has been found that as a lead anode is used repeatedly in functional chromium electroplating with baths containing MSA, the anode disintegrates at a faster rate than in conventional baths, and it must therefore be replaced much sooner than the anode in an analogous conventional bath.
  • lead anode is intended to define plating-bath anodes formed of lead or lead alloys commonly containing varying percentages of tin or antimony, either alone or in combination with other metals. Such materials are well known to those skilled in the art, and as such form no part of this invention.
  • MSA and ESA have been generically identified as useful additives in plating baths for functional chromium-plating processes.
  • the relevant references have indicated the problem of severe anodic corrosion when chromium is functionally electroplated for an extended period of time with lead anodes in plating baths containing MSA, the industry standard.
  • those references fail to suggest or disclose any particular means for an economical solution to the problem without sacrificing cost or process efficiency, or the other advantages obtained using baths containing MSA.
  • the present invention provides the use of an alkylpolysulphonic acid, halogenated alkylpolysulphonic acid, or salt thereof as a sulphonic additive, in order to keep down the extent of corrosion of a lead anode,
  • a functional chromium deposit is electroplated onto a basis-metal cathode at a current density of at least 30 A/dm 2 and temperature of from 45°C to 70°C using the lead anode in a plating bath free of anode corrosion-inhibiting amounts of bismuth, arsenic or antimony ions and containing chromic acid and sulphate ion and said sulphonic additive, which is an alkylsulphonic acid, halogenated alkylsulphonic acid or salt thereof having from one to three carbon atoms and giving a cathode efficiency of at least 20%.
  • a composition for securing chromium electroplated from an etch-free, high-efficiency, plating bath onto a basis-metal cathode with a lead anode in the substantial absence of corrosion-causing amounts of monosulfonic acids comprises chromic acid and sulfate ion in amounts sufficient to obtain the desired deposit of chromium, and at least one alkylpolysulfonic acid, halogenated alkylpolysulfonic acid, or salt thereof, which acid or salt contains from one to three carbon atoms.
  • the process comprises contacting a basis-metal cathode and a lead anode with a plating bath consisting essentially of chromic acid and sulfate ion in amounts sufficient to obtain a useful deposit of chromium, and at least one alkylpolysulfonic acid, halogenated alkylpolysulfonic acid, or salt thereof, which acid or salt contains from one to three carbon atoms, and electrodepositing chromium at a cathode efficiency of at least 20%, at a current density of from about 11 to about 230 as.d., and at a plating temperature of about 45 to about 70°C for a time sufficient to obtain a bright, adherent chromium deposit.
  • a plating bath consisting essentially of chromic acid and sulfate ion in amounts sufficient to obtain a useful deposit of chromium, and at least one alkylpolysulfonic acid, halogenated alkylpolysulfonic acid, or
  • the benefits of the present invention may be realized by the use in the plating bath of at least one material selected from the group consisting of alkylpolysulfonic acids containing from one to about carbon atoms, halogenated alkylpolysulfonic acids, and salts of such acids and halogenated acids, which acids or salts contain from one to three carbon atoms.
  • Halogenated acids are those containing fluorine, chlorine, bromine or iodine bound to a carbon atom; fluorine- and chlorine-substituted derivatives are preferred.
  • acids and salts include MDSA, mono- and dichloro-methanedisulfonic acid, 1,1-ethanedisulfonic acid, and monochloro- or 1,2-dichloroethanedisulfonic acid and their salts, provided that there is no precipitation of chromium or sulfate moieties caused by the addition of the salt.
  • Preferred cations are chosen from alkali metals. Particularly preferred are sodium and potassium salts.
  • the alkylpolysulfonic acids or salts have the formula where a and b are independently from 0 to 2, n is from 1 to 3, m and y are independently from 1 to 3, provided that the total number of sulfonic groups in the molecule is not less than 2, X is halogen or oxygen, R is unsubstituted lower alkyl or substituted lower alkyl, where the substituents on R are halogen or oxygen, and where hydrogen occupies any positions otherwise unaccounted for, i.e., to satisfy unfilled valences of carbon or oxygen.
  • the salts can be formed by the replacement of the labile hydrogen of the sulfonic group by a metal, such as, e.g., sodium, potassium, or the like.
  • the alkylpolysulfonic acids contain at least two sulfonic acid groups connected to carbon, and any one carbon atom can have up to three sulfonic acids groups attached thereto.
  • the polysulfonic acids or salts thereof are incorporated into a functional chromium-plating bath in substantially catalytic amounts. Depending upon plating conditions, that amount has been determined to be usually from about 0.25 to about 40 grams per liter (g/l), and preferably from about 1 to about 12 g/l, of the alkylpolysulfonic acid, halogenated alkylpoly-sulfonic acid or salt thereof. Particularly preferred amounts range from about 2 to about 8 g/l. In a preferred embodiment, the alkylpolysulfonic acid is MDSA.
  • Excessive corrosion is that amount of corrosion perceptibly in excess of the corrosion observed in conventional plating processes.
  • Extended use is the amount of use of a lead anode in a conventional system which leads to detectable corrosion of that anode.
  • the present invention enables a functional chromium electroplating bath which is useful to produce bright, adherent chromium deposits at high efficiencies, but which substantially avoids the excessive anode corrosion which is characteristic of industrial baths containing MSA.
  • Useful chromic acid amounts range from about 100 to about 450 g/l, preferred ranges being from about 200 to about 300 g/l.
  • Sulfate ion is incorporated in amounts ranging from about 1 to about 5 g/l, and preferably ranging from about 1.5 to about 3.5 g/l.
  • the electroplating baths may include other ingredients which do not substantially affect process efficiency, chromium adherence or brightness in a negative manner.
  • Such additives may be incorporated to improve handling of the baths, such as, e.g., fume suppressants, brightening agents and the like.
  • current density is from about 50 to about 100 A/dm 2 .
  • Plating temperature is of from 45 to 70°C. Plating efficiencies of at least 20% are achieved, with values of from about 22 to about 28% being typical under the described most-preferred conditions.
  • the functional electroplating system includes a lead anode, a cathode generally comprising a work-piece for plating, and the chromium electroplating bath as described above.
  • Typical cathode items include crankshafts, piston rings and the like.
  • typical anode materials include substantially pure lead, but are more generally alloys containing lead in combination with tin, antimony, tellurium and a variety of other metals, either singly or in combination.
  • a term such as "Pb-7%Sn" is a tin-lead composition being primarily lead, and having about 7% tin by weight as the alloying metal. In such compositions, there may further be minor amounts of other materials present.
  • Extended bath usage was simulated by plating at 60°C at an anode current density of 0.5 A/dm 2 for 30 minutes, followed by 30 minutes of non-plating. This process was conducted for about eight hours and the power turned off overnight, during which time the bath was allowed to cool. These steps were repeated for a period of several weeks; the anodes were occasionally removed, dried, weighed and then re-inserted into the bath. The results are given in Table I.
  • bath (c) containing MDSA as set forth herein for use in the process of this invention, anode corrosion remains substantially at the level of a conventional chromium-plating bath (a), whereas bath (b), with MSA as the plating-improvement medium, leads to corrosion at a substantially higher rate.
  • bath (b) there was evidence of serious interfacial attack on the anode
  • the conventional bath (a) and inventive bath (c) the appearance of the anode was substantially unaffected by the plating process.
  • the quality of the deposit obtained with the invention was at least as good as, and possibly somewhat harder than, the plating achieved with either the conventional commercial plating bath or that containing MSA.
  • a replenishment composition for a chromium-plating bath having chromic acid and at least one alkylpolysulfonic acid, halogenated alkylpolysulfonic acid or salt thereof in amounts from about 1 to about 40 g per kilogram (kg) of CrO 3 , and preferably from about 2 to about 25 g per kg, of replenishment composition.
  • This composition can be either a solid mixture or a solution.
  • the chromium can be present as the oxide, the acid or a salt, and that the amount of chromium is calculated and expressed for convenience as CrO 3 , irrespective of the exact nature of the chromium-containing material present.

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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)
  • Automation & Control Theory (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Paints Or Removers (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Claims (11)

  1. Verwendung einer Alkylpolysulfonsäure, einer halogenierten Alkylpolysulfonsäure oder eines Salzes davon als Sulfonadditiv, um das Ausmaß der Korrosion einer Bleianode niedrig zu halten, bei einem Verfahren, bei dem eine funktionelle Chromabscheidung auf eine Grundmetallkathode bei einer Stromdichte von mindestens 30 A/dm2 und einer Temperatur von 45°C bis 70°C unter Verwendung einer Bleianode in einem Plattierungsbad, das frei ist von Anodenkorrosions-inhibierenden Mengen an Wismut-, Arsen- oder Antimonionen und Chromsäure und Sulfationen und das Sulfonadditiv enthält, welches eine Alkylsulfonsäure, eine halogenierte Alkylsulfonsäure oder ein Salz davon mit 1 bis 3 Kohlenstoffatomen ist, elektroplattiert wird, und wobei eine Kathodenausbeute von mindestens 20% erhalten wird.
  2. Verwendung nach Anspruch 1, dadurch gekennzeichnet, daß das Sulfonadditiv ausgewählt wird aus
    Methandisulfonsäure,
    Monochlorethan-1,2-disulfonsäure,
    Dichlorethan-1,2-disulfonsäure,
    1,1-Ethandisulfonsäure,
    Monochlormethandisulfonsäure,
    Dichlormethandisulfonsäure und
    den Salzen davon.
  3. Verwendung nach Anspruch 2, dadurch gekennzeichnet, daß das Sulfonadditiv Methandisulfonsäure oder ein Salz davon ist.
  4. Verwendung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das Salz ein Alkalimetallsalz ist.
  5. Verwendung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Menge an Sulfonsäureadditiv von 0,5 bis 20 g/l beträgt.
  6. Verwendung nach Anspruch 5, dadurch gekennzeichnet, daß die Menge an Sulfonsäureadditiv von 1 bis 12 g/l beträgt.
  7. Verwendung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Temperatur von 50°C bis 60°C beträgt.
  8. Verwendung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Stromdichte von 30 bis 100 A/dm2 beträgt.
  9. Verwendung nach Anspruch 8, dadurch gekennzeichnet, daß die Stromdichte 45 bis 90 A/dm2 beträgt.
  10. Verwendung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Menge an Chromsäure in dem Plattierungsbad von 100 bis 450 g/l beträgt.
  11. Verwendung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Menge an Sulfat in dem Plattierungsbad von 1 bis 5 g/l beträgt.
EP90917257A 1989-11-06 1990-11-06 Schutz von bleienthaltenden anoden während der elektrobeschichtung mit chrom Expired - Lifetime EP0452471B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US43196389A 1989-11-06 1989-11-06
US431963 1989-11-06
PCT/US1990/006422 WO1991006693A1 (en) 1989-11-06 1990-11-06 Protection of lead-containing anodes during chromium electroplating

Publications (3)

Publication Number Publication Date
EP0452471A1 EP0452471A1 (de) 1991-10-23
EP0452471A4 EP0452471A4 (en) 1993-11-18
EP0452471B1 true EP0452471B1 (de) 1997-03-12

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Application Number Title Priority Date Filing Date
EP90917257A Expired - Lifetime EP0452471B1 (de) 1989-11-06 1990-11-06 Schutz von bleienthaltenden anoden während der elektrobeschichtung mit chrom

Country Status (9)

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EP (1) EP0452471B1 (de)
JP (1) JPH04502786A (de)
AT (1) ATE150100T1 (de)
AU (1) AU638512B2 (de)
BR (1) BR9006995A (de)
CA (1) CA2054201C (de)
DE (1) DE69030176T2 (de)
SG (1) SG52702A1 (de)
WO (1) WO1991006693A1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2792770A1 (de) 2013-04-17 2014-10-22 ATOTECH Deutschland GmbH Funktionelle Chromschicht mit verbesserter Korrosionsbeständigkeit

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5192515A (en) * 1990-09-20 1993-03-09 Molecular Technology Corporation Reduction of nitrogen oxide and carbon monoxide in effluent gases
DE102006042076A1 (de) * 2006-09-05 2008-03-20 Goldschmidt Tib Gmbh Ein neues Additiv für Chromelektrolyte

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3402554A1 (de) * 1984-01-26 1985-08-08 LPW-Chemie GmbH, 4040 Neuss Abscheidung von hartchrom auf einer metallegierung aus einem waessrigen, chromsaeure und schwefelsaeure enthaltenden elektrolyten
US4588481A (en) * 1985-03-26 1986-05-13 M&T Chemicals Inc. Chromium plating bath for producing non-iridescent, adherent, bright chromium deposits at high efficiencies and substantially free of cathodic low current density etching
US4786378A (en) * 1987-09-01 1988-11-22 M&T Chemicals Inc. Chromium electroplating baths having reduced weight loss of lead and lead alloy anodes
US4810337A (en) * 1988-04-12 1989-03-07 M&T Chemicals Inc. Method of treating a chromium electroplating bath which contains an alkyl sulfonic acid to prevent heavy lead dioxide scale build-up on lead or lead alloy anodes used therein

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2792770A1 (de) 2013-04-17 2014-10-22 ATOTECH Deutschland GmbH Funktionelle Chromschicht mit verbesserter Korrosionsbeständigkeit
WO2014170037A1 (en) 2013-04-17 2014-10-23 Atotech Deutschland Gmbh Functional chromium layer with improved corrosion resistance

Also Published As

Publication number Publication date
AU638512B2 (en) 1993-07-01
EP0452471A1 (de) 1991-10-23
BR9006995A (pt) 1991-10-22
AU6756990A (en) 1991-05-31
CA2054201A1 (en) 1991-05-07
CA2054201C (en) 2000-04-11
SG52702A1 (en) 1998-09-28
WO1991006693A1 (en) 1991-05-16
ATE150100T1 (de) 1997-03-15
DE69030176T2 (de) 1997-07-10
JPH04502786A (ja) 1992-05-21
DE69030176D1 (de) 1997-04-17
EP0452471A4 (en) 1993-11-18

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