US3755117A - Coating stainless steels - Google Patents

Coating stainless steels Download PDF

Info

Publication number
US3755117A
US3755117A US00114357A US3755117DA US3755117A US 3755117 A US3755117 A US 3755117A US 00114357 A US00114357 A US 00114357A US 3755117D A US3755117D A US 3755117DA US 3755117 A US3755117 A US 3755117A
Authority
US
United States
Prior art keywords
stainless steel
treatment
bath
chromic acid
sulfuric acid
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
US00114357A
Other languages
English (en)
Inventor
A Hart
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.)
Huntington Alloys Corp
Original Assignee
International Nickel Co Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by International Nickel Co Inc filed Critical International Nickel Co Inc
Application granted granted Critical
Publication of US3755117A publication Critical patent/US3755117A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/38Chromatising
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/24Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F17/00Multi-step processes for surface treatment of metallic material involving at least one process provided for in class C23 and at least one process covered by subclass C21D or C22F or class C25

Definitions

  • the stainless steel is immersed inan aqueous solution of chromic acid which also contains sulphuric acid and," in the latter of these patents, also containing manganous sulfate.
  • the coloring bath may contain CrO in an amount between 50 and 1,000 g/l. (grams per liter) of water, and canbe further acidified with sulfuric acid in amounts up to 600 g/l.
  • a preferred ratio of the weights of Cr(), to sul-' fate ion added as sulfuric acid is from' about 100:1 to about 1:1, although in'some cases the ratiocan extend to 1:2.
  • the bath temperature should be in the range from about room temperature up to about 100C., e.g.,
  • a so-called terminal gold color can be. produced by immersion in the above-described solutions, e.g., a chromic acidsulfuric acid bath at a temperature of 65 to 75C. containing 520 g/l. to 580 g/l. of CrO, and a Cro -sulfate ion ratio of from 3:1 to 7 :1, which color is not changed by increasing the period of immersion. It is possible, however, to obtain. blue to red colored films from such terminal gold film by heat treating in air at a temperature of from 300 to 7000C.,
  • the corrosion resistance of stainless steel is well known but nevertheless susceptible of improvement.
  • Our main object in the invention is to improve this resistance.
  • Another object is to improve the resistance of colored stainless steel to both corrosion and abrasion.
  • a film is produced on the surface of stainless steel by treatment with an aqueous solution of chromic acid with or without other constitubred and uncolored (that is-to say, natural colored) steels are rendered more resistant to corrosion by the application of the'cathodic treatment and the resistance to abrasion of colored steels is muchimproved.
  • Coloring may preferablybe achieved by'immersing the-stainless steel in a hot aqueous solution containing chromicand sulphuric acids, thecomposition and temperature range being as follows:
  • the cathodic treatment of the film-bearing stainless steel is most advantageously carried out in an electrolyte containing 250 g/l. CrO, and 2.5 g/l. sulfuric acid at a temperature of 40C.
  • the most advantageous current density is from 2.4 to 4.8 amp/dm.
  • the period of treatment will then normally be from 4 to 15 minutes, e.g., from 7 to 10 minutes.
  • the concentration of CrO is at least 25 gll.,' preferably from 100 to 750 g/l.
  • sulfuric acid is broadly 0.1 to 100 g/l'., preferablyfrom l to 10 g/L
  • the temperature may vary from 10 to about 100C., e.g., from 20 to C.
  • the current density may be in the range 0.3 to 30 ampldm., preferably 0.6 to 10 amp/dm., e.g., from about 1 to 5 amp/dm.
  • Both the coloring and hardening treatments can be carried out in lead-lined tanks heated by steam jackets, of the type used for conventional chromium plating. It is desirable to stir the coloring solution gently so as to maintain uniformity of temperature throughout it, but not to agitate either solution.
  • the resistance to corrosion can be tested by the CASS test described in BS 4601/1970, Appendedix G, and various test panels have been subjected to this test.
  • Panels of an l 8/8 chromium-nickel stainless steel polished to a mirror finish were colored blue by immersion in an aqueous solution containing 300 g/l. of CrO and 550 g/l. of sulfuric acid at 70C for 8 minutes. The blue films thus formed were removed from some of these after from 2 to 4 rubs.
  • the other panels were then given cathodic hardening treatment in aqueous solutions containing various amounts of chromic acid under various conditions of temperature, time of exposure and current density. The color of the test panels was virtually unaffected by this treatment.
  • the colored and hardened panels were then rubbed, the tests being stopped after 200 rubs. The results are shown in Table 3 below in which 200+ means that the coating had not failed at this stage.
  • mechanically abraded steel surfaces preferably are employed to obtain an even color.
  • the treated material can be bent, deep drawn and rigidized without cracking the film or reducing the color intensity of the deformed areas.
  • the colored and hardened material has been bent through 90 without cracking or flaking the colored films orreducing the color intensity at the bent portion. Further, the material has been deep drawn to form a cup 35 mm. in diameter by 20 mm. deep without damaging the colored film. Colored and hardened panels have also been rigidized, by deforming them in a diamond pattern without cracking the film or reducing its color intensity.
  • a process for improving the corrosion resistance of stainless steel and the abrasion resistance of an immersion coating thereon which comprises forming a coating on the steel surface by immersion in chromic acid and then electrolytically treating the coated stainless steel as a cathode in a chromic acid bath for 21 period of time not of sufficient duration to produce a visible chromium deposit on the surface, but of sufficient duration to harden the immersion coating.
  • a process according to claim 1 wherein said electrolytic treatment comprises immersing the coated stainless steel as a cathode in a bath containing from about 25 to about 750 g/l. of chromic acid and 0.1 to 100 g/l. of sulfuric acid, maintaining the bath temperature from about 10 to about 100C., and passing current through the bath at a current density of from about 0.6 to about 10 A/dm for a period of at least one-half minute.
  • the concentration of chromic acid is at least l00 g/l.
  • the concentration of sulfuric acid is about 1 to 10 g/L
  • the bath temperature is in the range from about 20 to about 80C.
  • the current density is from about 1 to about 5 A/dm
  • the time of treatment is from about 2 to about 30 minutes.
  • the immersion coating is produced by immersion in an aqueous solution containing about 200 to about 400 g/l. chromic acid, about 350 to about 700 g/l. sulfuric acid, at atemperature of about 65 to about 80C. for a time of at least about 5 minutes.
  • said aqueous solution contains about 300 g/l. chromic acid, about 550 g/l sulfuric acid and is used at a temperature of about C.
  • a process according to claim 1 wherein the immersion coating is produced in an aqueous solution containing 50 to 1 ,000 g/l. chromic acid, up to 600 g/l. sulfuric acid and up to 50 g/l. manganous sulfate.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Electroplating Methods And Accessories (AREA)
US00114357A 1970-05-26 1971-02-10 Coating stainless steels Expired - Lifetime US3755117A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB2521570 1970-05-26
GB124571 1971-01-11

Publications (1)

Publication Number Publication Date
US3755117A true US3755117A (en) 1973-08-28

Family

ID=26236586

Family Applications (2)

Application Number Title Priority Date Filing Date
US00114357A Expired - Lifetime US3755117A (en) 1970-05-26 1971-02-10 Coating stainless steels
US00252459A Expired - Lifetime US3766023A (en) 1970-05-26 1972-05-11 Coloring stainless steels

Family Applications After (1)

Application Number Title Priority Date Filing Date
US00252459A Expired - Lifetime US3766023A (en) 1970-05-26 1972-05-11 Coloring stainless steels

Country Status (13)

Country Link
US (2) US3755117A (de)
JP (1) JPS5331817B1 (de)
AT (1) AT304986B (de)
BE (1) BE767691A (de)
CA (2) CA1009605A (de)
CH (1) CH525287A (de)
DK (1) DK135855B (de)
ES (1) ES391488A1 (de)
FR (1) FR2090295B1 (de)
GB (1) GB1305636A (de)
NL (1) NL149556B (de)
NO (1) NO130239B (de)
SE (1) SE382079B (de)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4071416A (en) * 1976-02-13 1978-01-31 The International Nickel Company, Inc. Treatment of chromium-containing iron alloys
US4756874A (en) * 1986-12-22 1988-07-12 General Electric Company Minimization of radioactive material deposition in water-cooled nuclear reactors
US4915799A (en) * 1986-02-21 1990-04-10 Kinki Yakuhin Industrial Co., Ltd. Electrolytic coloring method for chromium alloy
US8801539B2 (en) * 2008-09-30 2014-08-12 Taylor Made Golf Company, Inc. Method of applying decorative layers to a steel shaft

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU8386982A (en) * 1981-06-01 1982-12-09 Wiggin Alloys Ltd. Increasing absorptance of porous film on cr containing iron alloy
US20050266130A1 (en) * 2004-05-28 2005-12-01 Henry Aoki Method for solidification and storing of components extracted from plant, animal, or mineral matter and extract components extracted from held plant, animal, or mineral matter
US20050287222A1 (en) * 2004-06-24 2005-12-29 Henry Aoki Method for producing water containing extracted ingredients from plant, animal, or mineral matter
EP1995355A1 (de) * 2006-10-24 2008-11-26 Wolf-Dieter Franz Graustichige Chromoberfläche
JP5030560B2 (ja) * 2006-11-29 2012-09-19 クリナップ株式会社 ミラーキャビネット
CN106435585B (zh) * 2016-08-16 2019-07-12 深圳市诚达科技股份有限公司 一种不锈钢件的表面cts抗腐蚀处理方法

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1827204A (en) * 1927-10-18 1931-10-13 Western Electric Co Method of protecting metal surfaces
US1827247A (en) * 1927-10-18 1931-10-13 Western Electric Co Method of protecting metal surfaces
US1946151A (en) * 1931-06-20 1934-02-06 Aluminum Co Of America Protecting aluminum from corrosion
US2172353A (en) * 1938-11-23 1939-09-12 Allegheny Ludlum Steel Coloration of stainless steel
US2219554A (en) * 1938-11-23 1940-10-29 Allegheny Ludlum Steel Coloration of stainless steel
US2283171A (en) * 1938-06-30 1942-05-19 Allegheny Ludlum Steel Colored steel
CA448565A (en) * 1948-05-18 The Coloron Corporation Electroplating
US3081238A (en) * 1958-09-03 1963-03-12 Quaker Chem Corp Electrolytic treatment of metal surfaces
US3210220A (en) * 1962-07-30 1965-10-05 Norman E Clegg Process for coating stainless steel
GB1097197A (en) * 1965-11-05 1967-12-29 Int Nickel Ltd Colouring nickel-containing stainless steel
GB1187785A (en) * 1966-03-26 1970-04-15 Fuji Iron & Steel Co Ltd Chromate-Coated Chromium Plated Steels and Two-Step processes for the preparation thereof by Electrolytic Treatment

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3535213A (en) * 1967-12-20 1970-10-20 Yawata Seitetsu Kk Method of surface-treating metals

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA448565A (en) * 1948-05-18 The Coloron Corporation Electroplating
US1827204A (en) * 1927-10-18 1931-10-13 Western Electric Co Method of protecting metal surfaces
US1827247A (en) * 1927-10-18 1931-10-13 Western Electric Co Method of protecting metal surfaces
US1946151A (en) * 1931-06-20 1934-02-06 Aluminum Co Of America Protecting aluminum from corrosion
US2283171A (en) * 1938-06-30 1942-05-19 Allegheny Ludlum Steel Colored steel
US2172353A (en) * 1938-11-23 1939-09-12 Allegheny Ludlum Steel Coloration of stainless steel
US2219554A (en) * 1938-11-23 1940-10-29 Allegheny Ludlum Steel Coloration of stainless steel
US3081238A (en) * 1958-09-03 1963-03-12 Quaker Chem Corp Electrolytic treatment of metal surfaces
US3210220A (en) * 1962-07-30 1965-10-05 Norman E Clegg Process for coating stainless steel
GB1097197A (en) * 1965-11-05 1967-12-29 Int Nickel Ltd Colouring nickel-containing stainless steel
GB1187785A (en) * 1966-03-26 1970-04-15 Fuji Iron & Steel Co Ltd Chromate-Coated Chromium Plated Steels and Two-Step processes for the preparation thereof by Electrolytic Treatment

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Stainless Steel Fabrication by Allegheny Ludlum Steel Corp., 1959 pp. 346 and 347. *
The Corrosion Handbook edited by H. H. Uhlig, John Wiley & Sons (1948), pp. 22 and 23. *
Theory of Corrosion and Protection of Metals by N. D. Tomashov, The MacMillan Co. (1966), page 327. *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4071416A (en) * 1976-02-13 1978-01-31 The International Nickel Company, Inc. Treatment of chromium-containing iron alloys
US4915799A (en) * 1986-02-21 1990-04-10 Kinki Yakuhin Industrial Co., Ltd. Electrolytic coloring method for chromium alloy
US4756874A (en) * 1986-12-22 1988-07-12 General Electric Company Minimization of radioactive material deposition in water-cooled nuclear reactors
US8801539B2 (en) * 2008-09-30 2014-08-12 Taylor Made Golf Company, Inc. Method of applying decorative layers to a steel shaft

Also Published As

Publication number Publication date
NL7107126A (de) 1971-11-30
CA1009605A (en) 1977-05-03
DE2126129A1 (de) 1971-12-09
DK135855C (de) 1977-11-28
ES391488A1 (es) 1973-06-16
US3766023A (en) 1973-10-16
CH525287A (fr) 1972-07-15
CA1008401A (en) 1977-04-12
SE382079B (sv) 1976-01-12
NO130239B (de) 1974-07-29
GB1305636A (de) 1973-02-07
DE2126129B2 (de) 1976-08-05
BE767691A (fr) 1971-11-26
FR2090295B1 (de) 1975-01-17
DK135855B (da) 1977-07-04
JPS5331817B1 (de) 1978-09-05
FR2090295A1 (de) 1972-01-14
NL149556B (nl) 1976-05-17
AT304986B (de) 1973-02-12

Similar Documents

Publication Publication Date Title
US3928157A (en) Cathodic treatment of chromium-plated surfaces
US2231373A (en) Coating of articles of aluminum or aluminum alloys
US3755117A (en) Coating stainless steels
CH380483A (de) Verfahren zur Erzeugung von Oxydüberzügen auf Aluminium oder dessen Legierungen
US3592747A (en) Method of forming a decorative and protective coating on a surface
US5104463A (en) Blackening process for stainless steels
US3284321A (en) Manufacture of aluminum articles with anodized surfaces presenting multicolor effects
US3099610A (en) Method of multi-coloring anodized aluminum
US3839163A (en) Process for forming on an aluminum surface a colored design
US4024039A (en) Coloring methods for aluminum and aluminum alloys
US2512563A (en) Method of electrolytically coating magnesium and its alloys
US2888391A (en) Process for coating metal
US2499231A (en) Method of producing surface conversion coatings on zinc
US2022798A (en) Manufacture of coated aluminum articles
US2407809A (en) Treatment of oxide coated aluminum articles
US4115212A (en) Electrolytic coloring process for non anodized aluminum and its alloys
JPS6213563A (ja) ステンレス鋼の着色処理方法
GB2053972A (en) Electrolytic colouring of anodized aluminium
GB2242201A (en) Colouring anodized aluminium
US4071416A (en) Treatment of chromium-containing iron alloys
JPS581094A (ja) マグネシウム材表面に着色保護皮膜を形成する方法
JPS59226197A (ja) アルミニウム合金の模様付け表面処理方法
US1946150A (en) Coating of aluminum
US4000053A (en) Method for treatment of aluminum substrate
US2450508A (en) Tin plate treatment