US2550660A - Process for producing adherent coatings on stainless steel to facilitate drawing operations - Google Patents

Process for producing adherent coatings on stainless steel to facilitate drawing operations Download PDF

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Publication number
US2550660A
US2550660A US4793848A US2550660A US 2550660 A US2550660 A US 2550660A US 4793848 A US4793848 A US 4793848A US 2550660 A US2550660 A US 2550660A
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stainless
steel
coating
approximately
drawing
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Amundsen Paul
John A Henricks
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Parker Rust Proof Co
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Parker Rust Proof Co
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    • 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
    • C23C22/46Chemical 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 oxalates

Description

Patented May 1, 1951 PROCESS FOR PRODUCING ADHERENT COATINGS N STAINLESS STEEL TO FACILITATE DRAWING OPERATIONS Paul Amundsen, Detroit, Mich., and John A. Henricks, Lakewood, Ohio, assignors, by mesne assignments, to Parker Rust Proof Company, Detroit, Mich., a corporation of Michigan No Drawing. Application September 4, 1948, Serial No. 47,938

11 Claims. (01. 14s 's.24)

I The present invention relates to a novel process for producing adherent coatings on stainless steel to facilitate drawing operations. By the term :stainless steels we mean steels which.

contain elements such as chromium with or without nickel, to prevent tarnish of the metal on exposure. Working of such steels in' dies, particularly cold drawing in dies has been very difficult because of the nature of the surfaces of such stainless steels. a

I In cold drawing of carbon steels .it has been found that drawing operations are facilitated by providing an adherent phosphate coating on the, metal prior to the drawing operations. At-

tempts to produce a similar coating on stainless steel surfaces have not produced a coating hav ing satisfactory properties of adherence, which at the same time will facilitate the cold drawing of the stainless steel material and thus facilitate the working thereof in drawing dies.

It is therefore, an important object of the present invention to provide a novel process for producing an adherent coating on stainless steel by chemical means, the process being readily adapted for use on an economically feasible basis in commercial scale operations- It is a further object of the present invention to provide a novel process by which a chemically produced adherent coating is provided on stainless steel surfaces in a relatively short time, the produced coating being eifective to improve the drawing properties of the stainless steel thus facilitating its cold drawing in manufacturing operations, increasing the life of the drawing dies and equipment and permitting the making of deeper draws in a single operation than has heretofore been possible in stainless steel drawing operations,

Other objects of the invention will appear in the following description and appended claims.

Before explaining the present invention in detail,

certain conditions, very well suited for use in I forming coatings on stainless steels in view of their known reactions therewith. It has been suggested in German Patent 731,045 that oxalic acid .may be used with sulfides .or hydrogen sulfide (H28). .While: these solutions will 10.1fm

coatings on the lower stainless steel alloys, the reaction requires a long time at high temperature. cially the ones containing molybdenum, do not react to form any coating. As is known, hydrogen sulfide (HzS) is very poisonous and obnoxions and the difficulty in handling this material has made the process very impractical.

We have found that certain sulfur compounds which contain oxygen and. which yield sulfur dioxide (S02) and sulfur, can be used in the presence of oxalic acid and a soluble halide to form excellent coatings on stainless steel surfaces in a time interval of from about 2 to 10 minutes. Satisfactory compounds include thiosulfates, hydrosulfites, tetra-thionates and -'sul-" fites, together with alkali or ammonium halides such for example as sodium fluoride or bifluoride and/or sodium chloride.

' The term alkali in'the specification and appended claims is to include both the alkali metals and ammonium. The fluorides especially have proven to be effective and are preferred when high alloyed steels, containing molybdenum are to be coated.

Using such materials, a satisfactory coating is formed in 2 to 3 minutes at room temperature on 18-8 stainless steel. molybdenum the temperature may be raised to 14 0-l5 0 F. in which event the time interval may be lengthened to '7 minutes.

The produced coatings are unlike coatings previously produced. On visual inspection theyare dark gray in color. They are very adherent and form an ideal base for an additional conventional drawing compound or lubricant. For stainless steeltube drawing, a chlorinated wax emulsion has proven to be successful, whereas for stainless steel headlight rims, a simple soap solution such as sodium or potassium oleate in a dilute aqueous medium is satisfactory.

The concentration of the oxalic acid is not (Approx) 5% oxalic acid, dihydrate (Approx) 2% ammonium bi-fluoride (Approx) 0.2 %-0.5% sodiumthiosulfate Water to make Some higher stainless steel alloys, espe-' If the alloy contains oxalic acid sodium chloride (Approx;) 1 1% sodium ;bi-fluoride (Approx) 2% sodium thiosulfate Water to make 100% Such a solution is heated to reactive temperatures, usually within the rang'eof from approxi mately room temperature to approximately 190 F. and the properly cleaned stainlesssteel surfaces are immersed therein until a substantial coating is formed therein. This usually requires a time interval of from approximately 2 to approximately 10 minutes. The surfaces will be coated under these conditions and are then water rinsed and either dried or directly im.-' mersed in the drawing compound and subjected to the draw. In cleaning such surfaces they preferably are either alkali cleaned or pickled and water rinsed. I

'Ihe.- solution as described above is tested for strength with N/lO sodium hydroxide, using a 5 ml. sample and methyl orange and phenolphthalein respectively. Such a solution tests free acid 23, total acid 34.5, ratio 1:1.6. This acid ratio slowlytends to increase to 1:280 and even higher. If it gets above 1:2.4 the coating action becomes sluggish, and this can be remedied by removing'pa-rt ofthe sodium salts which crystallize out when-the solution is cold, or by adding hydrochloric acid (HCll or hydrofluoric acid (.I-IF) 1 -While we do not; at this time, fully understand .allof the reactions which occur in such a process, it-is our present belief that the soluble halide has an activator effect which overcomes the normal passivity of the stainless alloys and allows the coating-reactionto be carried out much more rapidly and at much lower temperatures than-in comparable processes in which the solublehalide is not used.

- We do know however, that the use of the above activators for oxalic acid, causes the precipitation of an extremely smooth and adherent film of sulfide to be deposited on the surface, over which the normal coating of ferrous and other metal oxalates is formed. The sulfide containing film isin itself a lubricant and the more adsorptive normal type of oxalate which is formed, is heavier and seems to serve as an ideal base for the'lubricant. It is possible to remove thetop layer of the coating by polishing the surface, and the darkthin film of metallic sulfide is clearly visible. y

i We consider the ftuiction of the sulfur compound used to be that of a hydrogen depolarizer since hydrogen evolution is minimized, although may be a' matter of conjecture. Under certain conditions these compounds may be considered reducing agents-but we believe that their action here is more of an oxidizing nature.

Asa class, we have found that the soluble halides are satisfactory activators and that of this group, thepresently preferred soluble halides comprise the" soluble alkali and ammonium salts of the fluorides-and chlorides.

I. Having thus described the invention, what we desired to secure by Letters Patent of the United States is: i

We claim:

1. In a process for-treating the surfaces of stainless steel to facilitate cold drawing byproducing an adherent coating thereon, the novel step of immersing the stainless steel in an (Approx) 5% (Approx) 2% 4 aqueous bath consisting essentially of oxalic acid, a sulfur compound containing oxygen which yields sulfur dioxide and sulfur under the conditions of the coating bath, and an activator consisting of a soluble alkali halide, fora time interval sufficient to form a substantial coating and at a reactive temperature withinthe range of from approximately room temperature to approximately F;

2; In a process for treating the surfaces of stainless steel to produce an adherent coating thereon as claimed in claim 1 and further characterized in that the oxygen containing sulfur compound is selected from the group consisting of thiosulfates', hydrosulfites, tetra-thionates and sulfites.

3. In a process for treating the surfaces of stainless steel to produce an adherent coating thereon as claimed in claim 1 and further characterized in that the soluble halide is selected from the group consisting of the soluble alkali andammonium salts of the chlorides o1 fluorides.

4. In a process for treating the surfaces of stainless steel to produce an adherent coating thereon as claimed in claim 3 and further char-- acterized in that the soluble halide is an alkali fluoride.

- 5. ma process for treating the surfaces of stainless steel to produce an adherent coating thereon as claimed in claim 3 and further characterized in that the oxygen containing compound is selected from the roup consisting of thios'ulfates, hydrosulfites, tetra-thionate's and sulfites.

6. A bath adapted to produce a coating on stainless steel surface and comprising an aqueous solution containing approximately 5% oxalic acid ('dihydrate), approximately 2% am-' monium bi-fluoride, 0.2% sodium thiosulfate and the balance water.

'7. A bath adapted to produce a coating on a stainless steel surface and comprising an aqueous solution containing approximately 5% o'xalic'aci'd- (dihydrate), 2% sodium chloride, 1% sodium bi-fluoride and 0.2% sodium thiosulfate and the balance water.

8. A bath adapted to produce a coating on stainless steel surfaces and comprising an aqueous solution containing approximately 5% oxalic acid (dihydrate), sodium thiosulfate in an amount ranging from approximately 0.2% to 0.5%, an activator selected from the group consisting of ammonium and sodiumbifiuoride in an amount of from approximately 1% to approximately 2%, and the balance water.

9; In a process for treating the surfaces of stainless steel to produce an adherent coating thereon the novel step of immersing the stainless steel in a bath containing approximately 5% oxalic acid (dihydrate), approximately 2% ammonium bi-fiuoride, 0.2% sodium thiosulfate and the balance water for a time interval sufficient to form a substantial coating .at a temperature within the range of from approximately room temperature to approximately 190 F.

v 10. In a process for treating the surfaces of stainless steel to produce an adherent coating thereon the novel step of immersing the stainless steel in a bath comprising approximately 5% in the range of from approximately room tern-' perature toapproximately 190 F.

11. In a process for treating the surfaces of REFERENCES CITED stainless Steel to produce an adherent coating The following references are of record in the thereon the novel step of immersing the stainfile of this patent: less steel in a bath containing approximately 5% oxalic acid (dihydrate), sodium thiosulfate in an 5 UNITED STATES PATENTS amount ranging from approximate1y1.-O.2% to Number Name Date 0.5%, an activator selected from. the group of 1,911,537 Tanrfer May 30, 1933 ammonium and sodium bifluoride in-an amount 3 of from approximately 1% to 2% and th e balance FOREIGN PATENTS water, for a time interval sufficient to foifm a subm Number o y Da gstantial coating at a temperature within the 554,280 Germany y 932 :range of from approximately room temperature 7 1,04 Germany Feb. 1, 1943 u to approximately 190 F.

PAUL AMUNDSEN. JOHN A. HENRICKS. 15

Claims (1)

1. IN A PROCESS FOR TREATING THE SURFACES OF STAINLESS STEEL TO FACILITATE COLD DRAWING BY PRODUCING AN ADHERENT COATING THEREON, THE NOVEL STEP OF IMMERSING THE STAINLESS STEEL IN AN AQUEOUS BATH CONSISTING ESSENTIALLY OF OXALIC ACID, A SULFUR COMPOUND CONTAINING OZYGEN WHICH YIELDS SULFUR DIOXIDE AND SULFUR UNDER THE CONDITIONS OF THE COATING BATH, AND AN ACTIVATOR CONSISTING OF A SOLUBLE ALKALI HALIDE, FOR A TIME INTERVAL SUFFICIENT TO FORM A SUBSTANTIAL COATING AND AT A REACTIVE TEMPERATURE WITHIN THE RANGE OF FROM APPROXIMATELY ROOM TEMPERATURE TO APPROXIMATELY 190* F.
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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2639245A (en) * 1950-01-12 1953-05-19 Parker Rust Proof Co Sulfide coating
US2715083A (en) * 1951-01-29 1955-08-09 Parker Rust Proof Co Method of applying sulfide coating on stainless steel and composition solution therefr
US2759862A (en) * 1952-03-11 1956-08-21 Devex Corp Coating compositions and method of treating ferrous surfaces therewith
DE961094C (en) * 1951-12-20 1957-04-04 Metallgesellschaft Ag A method for pre-treatment of alloy steel prior to cold deformation
US2809138A (en) * 1954-03-18 1957-10-08 Hoechst Ag Bath solution and a process of treating metal surfaces
US2836525A (en) * 1956-05-18 1958-05-27 American Chem Paint Co Method of and composition for coating zirconium
US2868680A (en) * 1952-03-03 1959-01-13 Devex Corp Method of pickling and coating stainless steel in the same bath
US2935431A (en) * 1953-06-11 1960-05-03 Ici Ltd Method of coating titanium
US2953487A (en) * 1959-03-12 1960-09-20 Amchem Prod Method, bath and composition for coating corrosion resistant alloys
DE1103109B (en) * 1954-05-28 1961-03-23 Metallgesellschaft Ag A method and solution for applying UEberzuegen on stainless metals
US3041215A (en) * 1955-02-07 1962-06-26 Parker Rust Proof Co Solutions and methods for forming protective coatings on titanium
US3082129A (en) * 1956-12-07 1963-03-19 Devex Corp Method of coating wires for drawing
US3130087A (en) * 1961-05-01 1964-04-21 Detrex Chem Ind Composition and method for coating stainless steel articles
US3879237A (en) * 1973-01-16 1975-04-22 Amchem Prod Coating compositions for stainless steels
US5272039A (en) * 1992-05-04 1993-12-21 Eastman Kodak Company Preparation of magnetic carrier particles
EP0882809A2 (en) * 1997-05-19 1998-12-09 Henkel Corporation Composition and process for preventing blistering during heat treating of aluminum alloys
US20020062866A1 (en) * 2000-11-29 2002-05-30 Sadao Sumiya Adjustment pipe for fuel injection valve, and press-fitting structure and press-fitting method for the same
DE102014220976A1 (en) 2013-10-17 2015-04-23 Chemetall Gmbh A process for the preparation of metallic shaped bodies for cold forming

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE554280C (en) * 1930-01-28 1932-07-07 Schoeller Bleckmann Stahlwerke A method for burnishing of articles made of stainless steel
US1911537A (en) * 1930-08-08 1933-05-30 Eobebt r
DE731045C (en) * 1939-07-15 1943-02-01 Ig Farbenindustrie Ag A method for generating Oberflaechenschichten on objects made of alloy, so-called Edelstaehlen for the pretreatment of non-cutting, z. For example, by pulling, to be deformed workpieces

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE554280C (en) * 1930-01-28 1932-07-07 Schoeller Bleckmann Stahlwerke A method for burnishing of articles made of stainless steel
US1911537A (en) * 1930-08-08 1933-05-30 Eobebt r
DE731045C (en) * 1939-07-15 1943-02-01 Ig Farbenindustrie Ag A method for generating Oberflaechenschichten on objects made of alloy, so-called Edelstaehlen for the pretreatment of non-cutting, z. For example, by pulling, to be deformed workpieces

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2639245A (en) * 1950-01-12 1953-05-19 Parker Rust Proof Co Sulfide coating
US2715083A (en) * 1951-01-29 1955-08-09 Parker Rust Proof Co Method of applying sulfide coating on stainless steel and composition solution therefr
DE961094C (en) * 1951-12-20 1957-04-04 Metallgesellschaft Ag A method for pre-treatment of alloy steel prior to cold deformation
US2868680A (en) * 1952-03-03 1959-01-13 Devex Corp Method of pickling and coating stainless steel in the same bath
US2759862A (en) * 1952-03-11 1956-08-21 Devex Corp Coating compositions and method of treating ferrous surfaces therewith
US2935431A (en) * 1953-06-11 1960-05-03 Ici Ltd Method of coating titanium
US2809138A (en) * 1954-03-18 1957-10-08 Hoechst Ag Bath solution and a process of treating metal surfaces
DE1103109B (en) * 1954-05-28 1961-03-23 Metallgesellschaft Ag A method and solution for applying UEberzuegen on stainless metals
US3041215A (en) * 1955-02-07 1962-06-26 Parker Rust Proof Co Solutions and methods for forming protective coatings on titanium
US2836525A (en) * 1956-05-18 1958-05-27 American Chem Paint Co Method of and composition for coating zirconium
US3082129A (en) * 1956-12-07 1963-03-19 Devex Corp Method of coating wires for drawing
US2953487A (en) * 1959-03-12 1960-09-20 Amchem Prod Method, bath and composition for coating corrosion resistant alloys
US3130087A (en) * 1961-05-01 1964-04-21 Detrex Chem Ind Composition and method for coating stainless steel articles
US3879237A (en) * 1973-01-16 1975-04-22 Amchem Prod Coating compositions for stainless steels
US5272039A (en) * 1992-05-04 1993-12-21 Eastman Kodak Company Preparation of magnetic carrier particles
EP0882809A2 (en) * 1997-05-19 1998-12-09 Henkel Corporation Composition and process for preventing blistering during heat treating of aluminum alloys
EP0882809A3 (en) * 1997-05-19 1999-08-25 Henkel Corporation Composition and process for preventing blistering during heat treating of aluminum alloys
US6013142A (en) * 1997-05-19 2000-01-11 Henkel Corporation Composition and process for preventing blistering during heat treating of aluminum alloys
US20020062866A1 (en) * 2000-11-29 2002-05-30 Sadao Sumiya Adjustment pipe for fuel injection valve, and press-fitting structure and press-fitting method for the same
US6834667B2 (en) * 2000-11-29 2004-12-28 Denso Corporation Adjustment pipe for fuel injection valve, and press-fitting structure and press-fitting method for the same
DE102014220976A1 (en) 2013-10-17 2015-04-23 Chemetall Gmbh A process for the preparation of metallic shaped bodies for cold forming

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