US2800421A - Composition and method for coating stainless metals - Google Patents

Composition and method for coating stainless metals Download PDF

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Publication number
US2800421A
US2800421A US433282A US43328254A US2800421A US 2800421 A US2800421 A US 2800421A US 433282 A US433282 A US 433282A US 43328254 A US43328254 A US 43328254A US 2800421 A US2800421 A US 2800421A
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US
United States
Prior art keywords
bath
coating
oxalic acid
stainless
metals
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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US433282A
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English (en)
Inventor
Edwin W Goodspeed
Gaillard W Dell
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.)
Parker Rust Proof Co
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Parker Rust Proof Co
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
Priority to NL94192D priority Critical patent/NL94192C/xx
Priority to NL197493D priority patent/NL197493A/xx
Application filed by Parker Rust Proof Co filed Critical Parker Rust Proof Co
Priority to US433282A priority patent/US2800421A/en
Priority to FR1131540D priority patent/FR1131540A/fr
Priority to DEM27148A priority patent/DE1103109B/de
Priority to CH333944D priority patent/CH333944A/fr
Priority to GB15622/55A priority patent/GB769779A/en
Application granted granted Critical
Publication of US2800421A publication Critical patent/US2800421A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING 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
    • C23C22/00—Chemical 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
    • C23C22/05—Chemical 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
    • C23C22/06—Chemical 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
    • C23C22/46—Chemical 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

Definitions

  • the present invention relates tothe treating of stainless metals to produce adherent protective coatings thereon to facilitate drawing, forming or other working operations. More particularly, the invention relates to the application of oxalate-type coatings to stainless metals selected from the class consisting of iron, chromium, nickel and alloys of at least any two of these metals.
  • adherent phosphate coatings facilitate the cold working of carbon steels and protect the metal, and that adherent oxalate coatings do the same for the so-called stainless steels.
  • Satisfactory oxalate coatings on stainless steel have been produced but the known methods have not been entirely satisfactory because of' noxious odors, bath instability, uneconomical consumption of oxalic acid and erratic coating action on certain types of stainless steels.
  • accelerators, activators and oxidizing agents are required in order to increase the rate of attack of the oxalic acid on the relatively passive stainless steel.
  • oxalic acid is sensitive to certain of these additives, especially to oxidizing agents.
  • oxidizing agents such as sodiumchlorate, hydrogen peroxide and others react so readily with oxalic acid as to require slow continuous or periodic addition of the oxidizing agent to maintain satisfactory bath life.
  • stainless metals the stainless or corrosion-resistant metals selected from the class consisting of iron, chromium, nickel and alloys of at least any two of these metals.
  • iron in itself is not corrosion-resistant, when combined with either or both chromium and nickel, the resulting alloys are notably so.
  • Chromium and nickel in the essentially pure state are quite corrosion-resistant, when combined they are more so, and when both are combined in even minor proportions with major proportions of iron they form the well-known corrosion-resistant stainles steels.
  • alloying elements such as manganese, tantalum, columbium, titanium, molybdenum, silicon, vanadium, phosphorus and others.
  • austenitic, martensitic and ferritic stainless steels contain a major proportion of iron, from 16 to 26% chromium and from 6 to 22% nickel, with the total of the alloying elements being at least 23%.
  • the martensitic steels contain 4 to 18% chromium, and nickel, if present, not more than 2 or 3%.
  • the ferritic stainless steels differ slightly in composition from the martensitic, usually containing greater amounts of chromium, no nickel and a relatively greater variety and higher proportions of other alloying elements.
  • Another type of corrosion-resistant or stainless alloy which may be coated by this method is the nickel-chromium alloys high in nickel and low in iron, such as Inconel X.
  • Other alloys containing major proportions of nickel, minor proportions of chromium and little or no iron are usually resistant to corrosion and are used for making clad steel sheets. Particularly good results are obtained with the method of this invention when applied to the stainless steels. Best results are obtained with the austenitic stainless steels.
  • halide ion includes chloride ion, bromide ion, fluoride ion and iodide ion.
  • the halide ion may be introduced in the form of any soluble hydrohalic acid, or soluble salt thereof, the cation of which does not form complexes or insoluble or sparinglysoluble compounds by reaction with the oxalic acid.
  • a preferred activator is a compound selected from the class consisting of the water-soluble alkali-metal and ammonium chlorides, bromides, fluorides, silicofluorides, borofluorides and thiocyanates.
  • the chloride and thiocyanate ions are most preferred as activating ions in this invention.
  • organic nitro compounds having the requisite solubility in the solutions of this invention can be utilized as the oxidizing agent in this invention.
  • organic nitro compounds may have a greater solubility in oxalic acid than in plain water, and vice versa.
  • the organic nitro compound should have a solubility in the oxalic acid solutions of this invention which will enable the use of an amount having the ability to increase the attack of the solution on the metal.
  • Illustrative compounds which may be utilized include nitromethane, nitroethane, 1,1 dinitroethane, 1 nitropropane, nitrochloropropane, 2 nitroethanol, glycerol mononitrate, glycerol 1,3 dinitrate, phenylnitromethane, 2,4 dinitrophenylacetic acid, nitrobenzene, o-nitrobenzaldehyde, nitrotoluene, m dinitrobenzene, m nitrochlorobenzene, 0-, mand p-nitrophenol, 2,4-dinitro- 1- naphthol, l-nitro- Z-naphthol, 8-nitro Z-naphthol, picric acid, picramic acid, m-nitrobenzoic acid, 2,4-dinitrobenzoic acid, p-nitroaniline, m-nitrobenzene sodium sulfonate, o-nitrobenzene potassium sulfonate, pnitro
  • Preferred compounds are selected from the class consisting of the soluble sodium, potassium and ammonium salts of the nitrobenzene sulfonic acids; the nitrophenols; and nitroguanidine. Because of their greater solubility and satisfactory stability the sodium, potassium and ammonuim salts ofthe nitrobenzene sulfonic acids are most preferred. As indicated above, mixtures of one or more of the above and other organic nitro compounds may be used.
  • concentration of the various substances in the bath may vary somewhat within limits.
  • concentration of the oxalic acid is not critical for extremely strong solutions have given good coatings.
  • An effective range of concentration is from 2% to approximately 30%, although it is preferred to maintain the bath between 7 and 25%, with about 20% being most preferred.
  • the concentration of the halide ion and a thiocyanate ion may vary quite widely. Good adherent coatings of satisfactory weight are obtained with as little as 1% halide ion or thiocyanate ion and equally' good coatings have been obtained from oxalate solutions saturated with these ions. An efiective range of concentration is from about 2% to about 20%, with about 10% being most preferred. In this case also, mixtures of one or more halide ions and mixtures of one or more halide ions with thiocyanate ion may also be used.
  • the concentration of the organic nitro compound is, however, fairly critical because certain minimum amounts are required for the production of hard, adherent coatings at satisfactory speed.
  • the minimum concentration varies with the activity of 'the particular organic nitro compound and, of course, to some extent-with the concentration of oxalic acid and halide ion present.
  • m nitrobenzene sodium sulfonate (Sitol) in a concentration of 0.0007% gives only a slight trace of coating, 0.04% a heavy trace, 0.07% a fair coating but not entirely uniform' and 0.1% a complete, uniform and adherent coating.
  • the bath of the invention is made simply by dissolving the oxalic acid in water, the halide salt added and finally the organic-nitro compound, followed by' stirring until all ingredients are dissolved. Since both oxalic acid and many ofv the nitro compounds are more soluble in'warm or hot Water than in the cold, the solution of these compounds is sometimes. facilitated by warming the bath, for example to l-195 F., and-then cooling, if necessary, before use. The order of adding the ingredientsis'not critical since the latter do not. reactto-any appreciable extent.
  • the method of the. invention is carried outby first cleaning the stainless steel by any conventional method such as Wiping, spraying or immersing in a solvent such as mineral spirits, alkali cleaning bath, or an acid pickling bath, followed by a rinsing with clear water and then contacting or immersing the metal in the oxalic acid bath for the required time.
  • the period of immersion will vary, of course, depending on the efiiciency of the cleaning treatment, on'the strength of the bath, and on the temperature of the bath. With the lower concentrations specified above as much as 10 minutes will be required for a satisfactory coating. With the preferred concentrations 1 to 7 minutes will usually sutfice.
  • the temperature of the bath may vary from room temperature F.) to about 190 F. At temperatures below about F., the time required for the production of a satisfactory coating will be beyond best commercial practice. Temperatures beyond 175 F. do not result in appreciable increases in coating speed and moreover require excessive heat input. It is preferred, therefore, to operate the process at coating temperatures between 115 F. and 175 F. Temperatures of to 170 F. are most preferred.
  • Example 1 Inone series of examples, a stock solution was utilized containing the following ingredients:
  • Oxalie Acidt 20 Sodium Chloride 15 Organic Nitro Compouu Variable.
  • the strong inorganic oxidizing agents i. e. nitrate, nitrite and chlorate did. not produce a sufficiently heavy or adherent coat for metal deformation operations.
  • oxidizing agents sodium m-nitrobenzene sulfonate,, nitroguanidine and picric acid were employed.
  • the concentration of sodium m-nitrobenzene sulfonate was varied from 0.04%, 0.07%, 0.1%, 2% and saturation (about 30%).
  • the concentration of nitroguanidine employed was varied by increments of 0.003% up to 0.03% and again at saturation (less than 4%).
  • the concentration of picric acid employed was varied from 0.003, 0.010, 0.027% and saturation (less than 4%). In every case, type 302 stainless steel was immersed for 5 minutes at 170 F.
  • Example 2 A solution containing 20% oxalic acid, 15% sodium thiocyanate and 2% picric acid was utilized to coat type 302 stainless steel. A panel of this steel was immersed in the solution for five minutes at 170 F. A very good quality, uniform and adherent coating on the metal was obtained.
  • the proportions and concentrations used herein are percent weight/ volume. In other words, the density of the solution is taken is unity.
  • a process for treating the surface of stainless metals selected from the class consisting of iron, chromium, nickel and alloys of at least any two of these metals which comprises the step of contacting a surface of the metal with an aqueous bath consisting essentially of water, oxalic acid, at least one activating ion selected from the class consisting of halide ions and thiocyanate ions, and an organic compound which contains the nitro group in an amount sufficient to increase the ability of said bath to form a coating on said surface, for a time suflicient to form an adherent protective coating thereon and at a temperature within the range from approximately room temperature to approximately 190 F.
  • the source of the activating ion is a compound selected from the group consisting of the water-soluble alkali and ammonium chlorides, bromides, iodides, fluorides, silicofluorides, borofluorides and thiocyanates, and the stainless metal is a stainless steel.
  • the organic nitro compound is selected from the class consisting of the soluble sodium, potassium and ammonium salts of nitrobenzene sulfonic acids; nitroguanidine; and the nitro-phenols and the stainless metal as an austenitic stainless steel.
  • the novel step of immersing the stainless steel in an aqueous bath consisting essentially of water, oxalic acid, alkali metal chloride and a minimum of about 0.1% of picric acid, at a coating temperature and for a time sufiicient to form an adherent protective coating thereon.
  • the novel step of immersing the stainless steel in an aqueous bath consisting essentially of water, oxalic acid, alkali metal chloride, and a minimum of about 0.1% of nitroguanidine, at a coating temperature and for a time sufiicient to deposit an adherent protective coating thereon.
  • a solution for coating the surface of stainless steel consisting essentially of water, oxalic acid, an activating compound selected from the class consisting of watersoluble alkali-metal and ammonium chlorides, bromides, iodides, fluorides, silicofluorides, borofluorides and thiocyanates, and at least about 0.1% of a compound selected from the class consisting of the soluble sodium, potassium and ammonium salts of the nitrobenzene sulfonic acids; nitroguanidine; and the nitrophenols.
  • a solution for coating the surface of stainless steel consisting of water, oxalic acid, sodium chloride and at least 0.07% of m-nitrobenzene sodium sulfonate,
  • a solution for coating the surfaces of stainless steel consisting of water, oxalic acid, sodium chloride and at least 0.03% of nitroguanidine.
  • a solution for coating the surface of stainless steel consisting of water, oxalic acid, sodium chloride and at least 0.03% of picric acid.
  • An aqueous bath for coating the surface of stainless metals selected from the class consisting of iron, chromium, nickel and alloys of at least any two of these metals consisting essentially of water, oxalic acid, at least one activating compound selected from the class consisting of water-soluble alkali metal and ammonium chlorides, bromides, iodides, fluorides, silicofluorides, borofluorides and thiocyanates, and at least one organic compound which contains a nitro group in an amount of at least about 0.1%.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US433282A 1954-05-28 1954-05-28 Composition and method for coating stainless metals Expired - Lifetime US2800421A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
NL94192D NL94192C (enrdf_load_stackoverflow) 1954-05-28
NL197493D NL197493A (enrdf_load_stackoverflow) 1954-05-28
US433282A US2800421A (en) 1954-05-28 1954-05-28 Composition and method for coating stainless metals
FR1131540D FR1131540A (fr) 1954-05-28 1955-05-16 Composition et procédé de revêtement des aciers inoxydables
DEM27148A DE1103109B (de) 1954-05-28 1955-05-18 Verfahren und Loesung zum Aufbringen von UEberzuegen auf rostfreien Metallen
CH333944D CH333944A (fr) 1954-05-28 1955-05-20 Procédé de revêtement des métaux inoxydables et solution pour la mise en oeuvre de ce procédé
GB15622/55A GB769779A (en) 1954-05-28 1955-05-31 Improvements relating to the formation of oxalate coatings on metal surfaces

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US433282A US2800421A (en) 1954-05-28 1954-05-28 Composition and method for coating stainless metals

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US2800421A true US2800421A (en) 1957-07-23

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US433282A Expired - Lifetime US2800421A (en) 1954-05-28 1954-05-28 Composition and method for coating stainless metals

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US (1) US2800421A (enrdf_load_stackoverflow)
CH (1) CH333944A (enrdf_load_stackoverflow)
DE (1) DE1103109B (enrdf_load_stackoverflow)
FR (1) FR1131540A (enrdf_load_stackoverflow)
GB (1) GB769779A (enrdf_load_stackoverflow)
NL (2) NL94192C (enrdf_load_stackoverflow)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1243943B (de) * 1961-06-01 1967-07-06 Rca Corp Verfahren zur Stabilisierung oder Steuerung der Oberflaecheneigenschaften eines kristallinen Halbleiterplaettchens
US3459604A (en) * 1966-04-18 1969-08-05 Hooker Chemical Corp Metal surface coating methods
US4194929A (en) * 1978-09-08 1980-03-25 The United States Of America As Represented By The Secretary Of The Army Technique for passivating stainless steel
US4906327A (en) * 1989-05-04 1990-03-06 Rem Chemicals, Inc. Method and composition for refinement of metal surfaces
USRE34272E (en) * 1989-05-04 1993-06-08 Rem Chemicals, Inc. Method and composition for refinement of metal surfaces
US5795661A (en) * 1996-07-10 1998-08-18 Bethlehem Steel Corporation Zinc coated steel sheet and strip having improved formability and surface quality and method thereof

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2129837B (en) * 1982-11-01 1986-02-05 Pyrene Chemical Services Ltd Process for forming oxalate coating on metal surfaces

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2431728A (en) * 1942-04-29 1947-12-02 Despo Mfg Co Ltd Treatment of ferrous metals to improve resistance to rusting
GB675024A (en) * 1949-08-26 1952-07-02 Parker Rust Proof Co The production of oxalate coatings on metals

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE742340C (de) * 1933-07-15 1943-12-11 Ig Farbenindustrie Ag Verfahren zur Erzeugung rostschuetzender Phosphatschichten auf Metallen
BE432557A (enrdf_load_stackoverflow) * 1938-02-04
BE439289A (enrdf_load_stackoverflow) * 1939-07-15
US2609308A (en) * 1947-11-22 1952-09-02 Parker Rust Proof Co Method and material for producing coatings on metal
US2550660A (en) * 1948-09-04 1951-05-01 Parker Rust Proof Co Process for producing adherent coatings on stainless steel to facilitate drawing operations
US2577887A (en) * 1949-02-12 1951-12-11 Parker Rust Proof Co Activation of oxalate metal coating compositions
BE506526A (enrdf_load_stackoverflow) * 1950-10-19
DE882639C (de) * 1951-06-26 1953-07-09 Metallgesellschaft Ag Verfahren zum Aufbringen von UEberzuegen auf Metallen
DE887138C (de) * 1951-08-12 1953-08-20 Parker Rust Proof Company Verfahren zur Herstellung von festhaftenden UEberzuegen auf rostfreiem Stahl zur Erleichterung von Ziehvorgaengen

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2431728A (en) * 1942-04-29 1947-12-02 Despo Mfg Co Ltd Treatment of ferrous metals to improve resistance to rusting
GB675024A (en) * 1949-08-26 1952-07-02 Parker Rust Proof Co The production of oxalate coatings on metals

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1243943B (de) * 1961-06-01 1967-07-06 Rca Corp Verfahren zur Stabilisierung oder Steuerung der Oberflaecheneigenschaften eines kristallinen Halbleiterplaettchens
US3459604A (en) * 1966-04-18 1969-08-05 Hooker Chemical Corp Metal surface coating methods
US4194929A (en) * 1978-09-08 1980-03-25 The United States Of America As Represented By The Secretary Of The Army Technique for passivating stainless steel
US4906327A (en) * 1989-05-04 1990-03-06 Rem Chemicals, Inc. Method and composition for refinement of metal surfaces
EP0395815A1 (en) * 1989-05-04 1990-11-07 Rem Chemicals, Inc. Method and composition for refinement of metal surfaces
AU607637B2 (en) * 1989-05-04 1991-03-07 Rem Chemicals, Inc. Method and composition for refinement of metal surfaces
USRE34272E (en) * 1989-05-04 1993-06-08 Rem Chemicals, Inc. Method and composition for refinement of metal surfaces
JPH0753917B2 (ja) 1989-05-04 1995-06-07 レム ケミカルズ インコーポレーテッド 金属表面仕上げ用組成物および仕上げ方法
US5795661A (en) * 1996-07-10 1998-08-18 Bethlehem Steel Corporation Zinc coated steel sheet and strip having improved formability and surface quality and method thereof

Also Published As

Publication number Publication date
NL94192C (enrdf_load_stackoverflow)
DE1103109B (de) 1961-03-23
CH333944A (fr) 1958-11-15
FR1131540A (fr) 1957-02-22
GB769779A (en) 1957-03-13
NL197493A (enrdf_load_stackoverflow)

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