US3374156A - Electro-depositing stainless steel coatings on metal surfaces - Google Patents

Electro-depositing stainless steel coatings on metal surfaces Download PDF

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Publication number
US3374156A
US3374156A US457215A US45721565A US3374156A US 3374156 A US3374156 A US 3374156A US 457215 A US457215 A US 457215A US 45721565 A US45721565 A US 45721565A US 3374156 A US3374156 A US 3374156A
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US
United States
Prior art keywords
hydrazine
stainless steel
electro
liter
coatings
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
US457215A
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English (en)
Inventor
Schiffman Louis
Machu Willibald
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.)
Henkel Corp
Original Assignee
Amchem Products 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 Amchem Products Inc filed Critical Amchem Products Inc
Priority to US457215A priority Critical patent/US3374156A/en
Priority to GB18357/66A priority patent/GB1149011A/en
Priority to DEA52288A priority patent/DE1242968B/de
Priority to SE6181/66A priority patent/SE313960B/xx
Priority to BE680978D priority patent/BE680978A/xx
Priority to FR62155A priority patent/FR1504490A/fr
Application granted granted Critical
Publication of US3374156A publication Critical patent/US3374156A/en
Assigned to AMCHEM PRODUCTS, INC. A CORP. OF DEL. reassignment AMCHEM PRODUCTS, INC. A CORP. OF DEL. MERGER (SEE DOCUMENT FOR DETAILS). Assignors: AMCHEM PRODUCTS, INC. (MERGED INTO), HHC, INC. (CHANGED TO)
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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

Definitions

  • the coatings formed by the process of the patent do-not' display all of the desirable properties of stain less steel coatings formed in'other ways.
  • the stainless steel coating formed in accordance with the patent is relatively thin and, for reasons which are not fully understood, does not exhibit the degree of corrosion resistance characteristic of thicker layers of stainless steel, such as those which may be rolled onto metal surfaces.
  • corrosion resistance is .oneof the many desirable properties of stainless steels and the failure of electro-deposited coatings of the patent to exhibit all of the characteristic good qualities of stainless steels generally has been a puzzling drawback to the full exploitation of the breakthrough represented by the teachings of U.S. Patent 3,093,556.
  • chemical passivating treatments and heat treatments of the kind used in the plating art do not materially improve the corrosion resistance of electro-plated stainless steel coatings.
  • the process yields stainless steel alloy coatings in which the chromium content is from about 8.2% to about 217.1%, the nickel from about 3.6% to about 33% and iron the balance of the coating. Within the above ranges, the iron content is always predominant-- 1y greater than either chromium or nickel and is at least 58.5%.
  • the plating bath should contain at least 0.2 mol/liter of each of the three ions to be deposited, although the upper concentration limit is not as vital and may be as high as saturation for each ion.
  • Sulfate and chloride salts, including hydrated salts, may be used to supply the metal ions.
  • Urea in amounts between about 1.0 and 4.0 mols/liter is another component of the bath.
  • plated coatings having compositions of the kind usually referred toas stainless steel it has been found that in order to obtain plated coatings having compositions of the kind usually referred toas stainless steel,
  • the pH of the plating bath be maintained between about 1.5 and 3.5.
  • the pH can be adjusted by addition of free acid or base to the bath.
  • the other plating bath operating variables which are of importance are current density and operating temperature.
  • the current density may be varied between about 0.645 to 2.148 amps per square inch and variations in the current density will cause changes in the relative proportions of the three metals forming the coating. In general, an increase in current-density tends to cause an increase in the chromium concentration in the alloy and a decrease in the nickel.
  • the operating temperature should be held between about 30" and C. Theop'erating-temperature, like the current density, alfects the relative proportions of the metals in the plated alloys. In.
  • boricacid is a desirable optional ingredient in .the plating baths since it appears to have the elfect of smoothing the coating and making it more homogeneous.
  • concentration of boric acid should be between about 0.2 and 0.6 mol/liter.
  • Various other subsidiary ingredients can be included, such as pyridine, which acts as a brightening agent.
  • Another subsidiary ingredient, not specifically mentioned in Patent 3,093,556 is citric acid. Its use in the present invention is optional, but if it is used, it tends to smooth out the coat-,
  • the amount of hydrazine used should be from about 0.3 gram/liter to about 3.0 grams/ liter, calculated as N H when the coating baths and their operating conditions in other respects follow the teachings of U.S. Patent 3,093,556 outlined above.
  • the concentration limits just given are imposed by practical considerations. Thus, it hasbeen found that if the concentration of the hydrazine falls below about 0.3 m'ol/liter, the improvement in corrosion resistance obtained is so small. that itvis of no. .practical valuecwhen the concentration of hy-,1
  • the corrosion resistance is optimized if the hydrazine content is at least about l 1.8 'g./l.
  • the hydrazine concentration held between about 1.8 and 3.0
  • any hydrazine which is soluble in the plating baths, and which does not cause the precipitation of the other components of the plating bath is suitable.
  • hydrazine as used herein is meant to denote a class of-compounds, rather than a single compound.
  • Typical hydrazines which work in accordance with the invention are: hydrazine (N H methyl hydrazine, dimethyl hydrazine, phenyl hydrazine, hydrazine sulfate, and hydrazine chloride.
  • the base metals which can be coated in accordance with the processes of this invention include the group consisting of iron, nickel, zinc, and alloys of each wherein the particular metal constitutes the principal ingredient of the alloy.
  • the improved corrosion resistance of coatings formed in accordance with the invention is obtained for coatings on all of these base metals, and the nature of the base metal has substantially no effect on the corrosion resistance properties.
  • the hydrazines are bases and will thus tend to raise somewhat the pH of plating baths in which they are included. However, it is still preferred that the pH be maintained between about 1.5 and 3.5, as taught by the aforementioned patent. Final adjustment of the pH is desirably accomplished by addition of acid or base to the bath.
  • the stock solution was used to form plating baths for a series of tests in which stainless steel coatings were electro-plated on steel panels. Some of the panels were coated in a bath containing the stock solution, without modification, and others were plated in a bath containing stock solution to which hydrazine had been added. In this way, the effect of the use of hydrazine on the corrosion resistance properties of the coatings was isolated and observed.
  • the plated panels were iven the same post treatment as were the panels in the previous series of examples.
  • the dried panels were then subjected to the ASTM salt fog cabinet test until failure.
  • the failure times were as follows:
  • the method of electro-depositing a stainless steel alloy coating consisting of chromium, nickel and iron on a metal surface comprising using the metal to be coated as a cathode in a plating bath consisting essent-ially of an aqueous solution of from 0.2 mol/liter to saturation of a salt of each of the metals in the alloy to be deposited, said salt being selected from the class cons-isting of sulfate salts and chloride salts of each of said metals, from 1 to 4 mols/liter of urea, at least 0.3 gram per liter of a soluble hydrazine, calculated as N H with the balance water; maintaining the temperature of the bath at from 30 C. to 80 C., and the pH at from 1.5 to 3.5, and passing an electric current of from 0.645 to 2.148 amps/in. therethrough between an anode and the said cathode.
  • hydrazine is selected from the class consisting of hydrazine (N 'H methyl hydrazine, dimethyl hydrazine, phenyl hydrazine, hydrazine sulfate, and hydrazine chloride.

Landscapes

  • 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)
US457215A 1965-05-19 1965-05-19 Electro-depositing stainless steel coatings on metal surfaces Expired - Lifetime US3374156A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US457215A US3374156A (en) 1965-05-19 1965-05-19 Electro-depositing stainless steel coatings on metal surfaces
GB18357/66A GB1149011A (en) 1965-05-19 1966-04-27 Improvements in or relating to the electro-deposition of stainless steel coatings onthe surfaces of metals
DEA52288A DE1242968B (de) 1965-05-19 1966-04-27 Bad und Verfahren zum galvanischen Abscheiden von rostfreien Stahlueberzuegen
SE6181/66A SE313960B (enrdf_load_html_response) 1965-05-19 1966-05-05
BE680978D BE680978A (enrdf_load_html_response) 1965-05-19 1966-05-13
FR62155A FR1504490A (fr) 1965-05-19 1966-05-18 Solution et procédé pour le dépôt électrolytique d'alliages dits aciers inoxydables sur des surfaces métalliques

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US457215A US3374156A (en) 1965-05-19 1965-05-19 Electro-depositing stainless steel coatings on metal surfaces

Publications (1)

Publication Number Publication Date
US3374156A true US3374156A (en) 1968-03-19

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US457215A Expired - Lifetime US3374156A (en) 1965-05-19 1965-05-19 Electro-depositing stainless steel coatings on metal surfaces

Country Status (6)

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US (1) US3374156A (enrdf_load_html_response)
BE (1) BE680978A (enrdf_load_html_response)
DE (1) DE1242968B (enrdf_load_html_response)
FR (1) FR1504490A (enrdf_load_html_response)
GB (1) GB1149011A (enrdf_load_html_response)
SE (1) SE313960B (enrdf_load_html_response)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4990225A (en) * 1989-04-28 1991-02-05 Matsushita Electric Industrial Co., Ltd. Method of manufacturing high magnetic flux density electrodeposited quaternary alloy thin film
US20030178314A1 (en) * 2002-03-21 2003-09-25 United States Steel Corporation Stainless steel electrolytic coating
CN104711645A (zh) * 2015-01-28 2015-06-17 南通新源特种纤维有限公司 一种电镀铬溶液
CN105112959A (zh) * 2015-09-21 2015-12-02 无锡清杨机械制造有限公司 一种Cr-Ni合金电镀液及电镀方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3093556A (en) * 1961-06-13 1963-06-11 Amchem S A Electro-depositing stainless steel coatings on metal surfaces

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3093556A (en) * 1961-06-13 1963-06-11 Amchem S A Electro-depositing stainless steel coatings on metal surfaces

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4990225A (en) * 1989-04-28 1991-02-05 Matsushita Electric Industrial Co., Ltd. Method of manufacturing high magnetic flux density electrodeposited quaternary alloy thin film
US20030178314A1 (en) * 2002-03-21 2003-09-25 United States Steel Corporation Stainless steel electrolytic coating
CN104711645A (zh) * 2015-01-28 2015-06-17 南通新源特种纤维有限公司 一种电镀铬溶液
CN104711645B (zh) * 2015-01-28 2017-04-26 南通新源特种纤维有限公司 一种电镀铬溶液
CN105112959A (zh) * 2015-09-21 2015-12-02 无锡清杨机械制造有限公司 一种Cr-Ni合金电镀液及电镀方法

Also Published As

Publication number Publication date
BE680978A (enrdf_load_html_response) 1966-10-17
GB1149011A (en) 1969-04-16
DE1242968B (de) 1967-06-22
SE313960B (enrdf_load_html_response) 1969-08-25
FR1504490A (fr) 1967-12-08

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AS Assignment

Owner name: AMCHEM PRODUCTS, INC. A CORP. OF DEL.

Free format text: MERGER;ASSIGNORS:AMCHEM PRODUCTS, INC. (MERGED INTO);HHC, INC. (CHANGED TO);REEL/FRAME:004102/0461

Effective date: 19810320