US3753872A - Method of and bath for producing microcrack chromium coatings - Google Patents

Method of and bath for producing microcrack chromium coatings Download PDF

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Publication number
US3753872A
US3753872A US00216724A US3753872DA US3753872A US 3753872 A US3753872 A US 3753872A US 00216724 A US00216724 A US 00216724A US 3753872D A US3753872D A US 3753872DA US 3753872 A US3753872 A US 3753872A
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United States
Prior art keywords
nickel
acid
chromium
bath
coating
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
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US00216724A
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English (en)
Inventor
M Koehl
R Ludwig
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Langbein Pfanhauser Werke AG
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Langbein Pfanhauser Werke AG
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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
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/625—Discontinuous layers, e.g. microcracked layers

Definitions

  • a microcrack chromium coating is applied by electroplating it upon a coating of nickel, cobalt, nickel-cobalt, nickel-iron or iron-cobalt previously electrodeposited upon a substrate, e.g. of steel, from an electroplating bath containing 5 g./liter to the limit of solubility of at least one aromatic mono-, dior polycarboxylic acid anhydride or salt.
  • the aromatic carboxylic acid is benzoic acid, phthalic acid or phenylacetic acid and is present in an amount of 5 g./liter to 70 g./liter or the limit of solubility whichever is less, the electroplatinng is carried out at a temperature of 35 to 70 C. and the current density of 3 to a./dm.
  • microcrack chromium coating has the advantage of excellent corrosion-protection characteristics and these characteristics are enhanced when it is formed as the final layer in a corrosion-resistant system consisting of copper-nickel-chromium or nickel-chromium upon steel or iron bodies and upon pressure-cast zinc.
  • the copper and nickel coatings may be deposited from a combined electrolyte or from individual electrolytic baths.
  • the chromium layer is applied to a bright-nickel electrodeposited coating and is found to have relatively high internal stress and relatively low elongation-to-break valves.
  • An electrolyte must be used which provides high dispersion if the optimal plating-thickness distribution is to be reached.
  • the chromium coating is then electroplated with a final chromium coating from a second chromium-plating bath.
  • the quality of such electrodeposited layers often leaves much to be desired and they have low bonding-strength tolerance to mechanical distortion.
  • Similar chromium coatings which are rendered microporous by incorporating nonconductive particles in the underlying nickel coating, have similar disadvantages.
  • the nickel coating is not a high-internal-stress layer (a stress of the order of 980 N/mm. being common) while the elongation-to-break or failure load is about 0.5 and, therefore, relatively high.
  • the anticorrosion character of such nickel coatings tested in accordance with German Industrial Standards DIN 50,958 without kaolin or in accordance with ASTM standard B380, against a saturated calomel electrode in a Corrodkote solvents, revealed a potential of the layer of 300 to 500 mv. which is unsatisfactory.
  • a further disadvantage of this latter system is that high current densities during electrodeposition result in clouding of the deposit, especially when the substrate is exposed to the plating conditions for a long period.
  • the principal object of the present invention is to provide an improved electroplating bath for the electrodeposition of an intermediate nickel layer upon a substrate such that the subsequent chromium deposit Will have a high and uniform microcrack character.
  • Yet another object of the invention is to provide an improved method of applying corrosion-resistant coatings to metallic substrates.
  • the invention resides in the provision of an electrolyte or electroplating bath for the formation of the intermediate layer, which contains nickel, cobalt, nickel-and-cobalt, nickel-and-iron or iron-and-cobalt ions, the usual ammonium and chloride ions common in nickel and cobalt-plating baths and the customary additives thereto together with at least one aromatic mono-, dior polycarboxylic acid or a salt thereof (or the anhydride thereof which is converted to salt or free acid upon addition).
  • the intervening coating is a nickel layer deposited from a nickel electroplating bath of conventional composition except for inclusion of at least 5 grams per liter (g./l.) of the aromatic carboxylic acid which can be present in amounts up to the limit of solubility thereof in the aqueous electroplating bath.
  • the aromatic carboxylic acid is benzoic acid, phthalic acid or phenylacetic acid and in the case of phthalic acid may be of the auto-, meta-, or paraform.
  • the aromatic carboxylic acid is present in an amount between 5 to 70 g./l. or the limit of solubility whichever is less. More preferably, the aromatic carboxylic acid is present in an amount between 20 to 60 g./l.
  • the nickel-plating bath (or the cobalt-containing plating bath as the case may be) will contain the ususal substances employed in the deposition of the respective coatings. Reference is made in this respect to the Encyclopedia of Electrochemistry, Reinhard Publishing Corporation, New York, 1964.
  • the metal ions are present in an amount ranging from 30 to 100 g./l. and will be nickel and cobalt and combinations thereof with one another or with iron, the metal ions being introduced into an aqueous bath in the form of the sulfate, sulfamate, chloride, fluorborate, fluoride and/or acetate.
  • the bath further should contain 10 to 150 g./l.
  • chloride introduced in the form of nickel, cobalt, iron, ammonium, magnesium or alkali-metal (lithium, sodium, potassium) chloride. 10 to 100 g. of ammonium ion may also be present and, if desired, boric acid in conventional quantities.
  • the chromium coating is applied in accordance with the conventional technique described above. It is found that the system of the invention can operate at high current densities without significant clouding of the intermediate layer, that in all cases Within the temperature range of the present invention there is a volatilization of liquid from the bath so that replenishing chemicals can be added without increasing the volume, that the intermediate coating has an internal stress above 1960 N/mm. and an elongation to break of less than 0.1%.
  • the potential of the intervening layer measured against a saturated calomel electrode in accordance with DIN 5 0,95 8 and ASTM B380 as described above is between -100 and l50 mv., and thus is not disadvantageous from the point of view of corrosion protection.
  • Electrodeposition was carried out for a period of three minutes at a pH of 3.0 to 3.9, a temperature of 40 to 50 C. and a current density of 5 to 10 a../drn. against the nickel electrode.
  • the unclouded nickel layer was washed and coated with chromium in an aqueous bath containing 300 g./liter chromic acid, 2.5 g./1iter sulfuric acid and 1-3 g./liter aluminum silicofluoride.
  • the chromium plating was carried out at a temperature of 30 C. and a current density of 6 a. ldm.
  • the nickel coating was found to have an internal stress value of 1960 N/mm? and a potential of -100 mv. measured as described above.
  • the elongation at break was about 0.09% and the chromium coating had a crack count of 300-850 cracks per cm. uniformly distributed over the electroplated region.
  • the chromium-plating step is carried out using a bright-chromium plating bath under cold conditions as described in the aforementioned publications at a temperature of 25 to 35 C. and a current density of 3 to 12 a./dm.
  • a method of coating a metal substrate to restrict corrosion thereof comprising applying a first metallic layer to said substrate by electroplating nickel, cobalt or a combination thereof, or a combination of either with iron onto said substrate from a aqueous acidic electroplating bath containing the respective metal ions, ammonium ion and chloride ion together with 20 to 60 g./l. of phthalic acid and thereafter electrodepositing a chromium layer upon said first layer to produce a microcrack coating.
  • An aqueous acidic electroplating bath containing essentially 30 to g./l. of nickel or cobalt ion individually or in combination, or in combination either with iron ion, 10 to g./1. chloride ion, 1 to 100 g./liter ammonium ion and 20 g./1. to 60 g./l. of phthalic acid.

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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)
US00216724A 1971-01-11 1972-01-10 Method of and bath for producing microcrack chromium coatings Expired - Lifetime US3753872A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE2100971A DE2100971B2 (de) 1971-01-11 1971-01-11 Verfahren und Bad zur Erzeugung mikrorissiger Chromschichten über Zwischenschichten

Publications (1)

Publication Number Publication Date
US3753872A true US3753872A (en) 1973-08-21

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ID=5795549

Family Applications (1)

Application Number Title Priority Date Filing Date
US00216724A Expired - Lifetime US3753872A (en) 1971-01-11 1972-01-10 Method of and bath for producing microcrack chromium coatings

Country Status (6)

Country Link
US (1) US3753872A (enExample)
DE (1) DE2100971B2 (enExample)
FR (1) FR2123246B1 (enExample)
GB (1) GB1371172A (enExample)
IT (1) IT946426B (enExample)
SE (1) SE401209B (enExample)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3901773A (en) * 1972-08-01 1975-08-26 Langbein Pfanhauser Werke Ag Method of making microcrack chromium coatings
US5871641A (en) * 1996-05-30 1999-02-16 H-Tech, Inc. Fluid filter with pleated septum
US20060096868A1 (en) * 2004-11-10 2006-05-11 Siona Bunce Nickel electroplating bath designed to replace monovalent copper strike solutions
US20120157297A1 (en) * 2010-12-16 2012-06-21 Nguyen Thien Duyen Thi Catalysts and methods of preparation of catalyst
US9315736B2 (en) 2010-12-16 2016-04-19 Energia Technologies, Inc. Methods of fuel production
US11377748B2 (en) * 2017-11-20 2022-07-05 Basf Se Composition for cobalt electroplating comprising leveling agent
US12098473B2 (en) * 2018-12-21 2024-09-24 Basf Se Composition for cobalt plating comprising additive for void-free submicron feature filling

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3471271A (en) * 1965-08-16 1969-10-07 Udylite Corp Electrodeposition of a micro-cracked corrosion resistant nickel-chromium plate

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3901773A (en) * 1972-08-01 1975-08-26 Langbein Pfanhauser Werke Ag Method of making microcrack chromium coatings
US5871641A (en) * 1996-05-30 1999-02-16 H-Tech, Inc. Fluid filter with pleated septum
US20060096868A1 (en) * 2004-11-10 2006-05-11 Siona Bunce Nickel electroplating bath designed to replace monovalent copper strike solutions
WO2006052310A3 (en) * 2004-11-10 2006-12-21 Macdermid Inc Nickel electroplating bath designed to replace monovalent copper strike solutions
US20120157297A1 (en) * 2010-12-16 2012-06-21 Nguyen Thien Duyen Thi Catalysts and methods of preparation of catalyst
US20120157299A1 (en) * 2010-12-16 2012-06-21 Nguyen Thien Duyen Thi Method of making a catalyst
US8507400B2 (en) * 2010-12-16 2013-08-13 Energia Technologies, Inc. Method of making a catalyst
US8524629B2 (en) * 2010-12-16 2013-09-03 Energia Technologies, Inc. Catalysts
US8597599B2 (en) 2010-12-16 2013-12-03 Energia Technologies, Inc. Systems for fuel production
US9315736B2 (en) 2010-12-16 2016-04-19 Energia Technologies, Inc. Methods of fuel production
US11377748B2 (en) * 2017-11-20 2022-07-05 Basf Se Composition for cobalt electroplating comprising leveling agent
US20220298664A1 (en) * 2017-11-20 2022-09-22 Basf Se Composition for Cobalt Electroplating Comprising Leveling Agent
US12098473B2 (en) * 2018-12-21 2024-09-24 Basf Se Composition for cobalt plating comprising additive for void-free submicron feature filling

Also Published As

Publication number Publication date
GB1371172A (en) 1974-10-23
SE401209B (sv) 1978-04-24
IT946426B (it) 1973-05-21
FR2123246B1 (enExample) 1974-06-21
DE2100971A1 (de) 1972-07-13
FR2123246A1 (enExample) 1972-09-08
DE2100971B2 (de) 1975-04-17

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