US2743204A - Phosphate metal coatings - Google Patents

Phosphate metal coatings Download PDF

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Publication number
US2743204A
US2743204A US306961A US30696152A US2743204A US 2743204 A US2743204 A US 2743204A US 306961 A US306961 A US 306961A US 30696152 A US30696152 A US 30696152A US 2743204 A US2743204 A US 2743204A
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US
United States
Prior art keywords
phosphate
solution
coating
tetra
zinc
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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US306961A
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English (en)
Inventor
William S Russell
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
Original Assignee
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 BE522392D priority Critical patent/BE522392A/xx
Priority to DENDAT1072055D priority patent/DE1072055B/de
Priority to NL91161D priority patent/NL91161C/xx
Application filed by Parker Rust Proof Co filed Critical Parker Rust Proof Co
Priority to US306961A priority patent/US2743204A/en
Priority to GB29258/52A priority patent/GB733235A/en
Priority to FR1086955D priority patent/FR1086955A/fr
Priority to CH312218D priority patent/CH312218A/fr
Application granted granted Critical
Publication of US2743204A publication Critical patent/US2743204A/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
    • C23C22/07—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 phosphates
    • C23C22/08—Orthophosphates
    • C23C22/12—Orthophosphates containing zinc cations
    • C23C22/17—Orthophosphates containing zinc cations containing also organic acids
    • 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
    • C23C22/07—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 phosphates
    • C23C22/08—Orthophosphates
    • C23C22/18—Orthophosphates containing manganese cations

Definitions

  • the present invention relates to improvedphosphate coating compositionsv and. methods for forming. protective,
  • phosphate coatings on metallic surfaces including iron steel,.zinc and aluminum.
  • thisinvention is concerned with animproved solution of'the coating-phosphate type, c. g., zinc, iron or manganese phosphate,
  • Another object is to provide an improved coating solution which produces heavy phosphate coatings on metallic.
  • a further object of the present, invention is to provide a method for treating the surfaces of iron, steel and zinc to form a heavy phosphate coating thereon.
  • Still anotherobjective is to I provide an auxiliary accelerator which in combination with conventional oxidiiing -agents in a coating-phosphate solution greatly in creases the coating weights obtainable on me'tallic sur faces.
  • iLhas beenf oundham r d cati nate ca-s t e were phosphate type and having a pH in the range of 1.9 to 3.5
  • Coating-phosphate solu- V enter:t onal xi z ng g nt Q-h pre nt in: 0
  • Polycarbox-L yliq alph aminosacids such. as; ethylenediamine tetnm acetioaci have; even greater tendencies torfornistable metallic ions in comparable: fl ltiqnfin han. 9 h simpler minqiacidsi.
  • easin aodi y hus, heeatra heavy-coat n we h s. wh wereqbt ine i nd. u ed; by: he. addition? b -ED111013; ties of such c; r,ga nicv chelatingiagentsi to relatinely: a inapho phate o utions were; not e pected. or he re en sincr a e in. oatineweight s.no -.-co p e elynde st od; Coating wei htaresnlting.
  • oxidizing agents which may be used are potassium iodate, sodium meta-nitrobenzene sulfonate, picric acid, hydroxylamine, etc. Typical concentrations which may be used are 0.02% to 0.5% potassium iodate, 0.03% to .5 sodium meta-nitrobenzene sulfonate, 0.01% to 0.3% picric acid and .01 to .3% hydroxylamine.
  • the proportion given for each oxidizing agent is that proportion which causes a substantially equivalent amount of oxidizing or acceleration of the coating formation as 'is caused by any other oxidizing agent when present in the quantity shown.
  • Nitrates may be used in manganese phosphate solutions at a concentration between 0.1% and 5% and may likewise be used in zinc phosphate solutions, although in certain cases they are not the most beneficial oxidizing agents with the latter solutions.
  • nitrites it is preferable to maintain the temperature of the solution below about 140 F. inasmuch as the nitrite appears to react with the chelating agent and to decrease its effectiveness.
  • the upper limit is usually determined on the basis of economy and ease of operation and proportions above about 1% have not been found to be necessary in the majority of applications. A few simple tests under operating conditions will easily establish the most desirable concentration.
  • the preferred concentration of ethylene diamine tetra-acetic acid based on the tetra sodium salt, is in the range of about .1% to about .3%. Proportions below about .01% ethylene diamine tetra-acetic acid have some beneficial effect, but the effect is not as pronounced as with concentrations exceeding 0.01%.
  • Example 1 An aqueous solution was made up with the following composition:
  • the solution operated at a pH of 23-335.
  • Four inch by six inch cold rolled steel panels were cleaned of oil and other foreign material by conventional cleaning methods such as dry wiping followed by wiping in mineral spirits or a short pickle in sulfuric acid.
  • the panels were then immersed in a solution of the above composition heated to 160 F.-200 F. for periods of 1, 3, 5, 10 and minutes.
  • Coating weights received were 108 mg./sq. ft. after one minute, 110 mg./sq. ft. after three minutes and only 118 ing/sq. ft. after 15 minutes.
  • the solution was then altered by adding .5 grams/liter of tetra sodium ethylene diamine tetra-acetate.
  • a series of identi- 4 cally cleaned panels were then immersed in the new solution for l, 3, 5, 10 and 15 minutes. Coating weights obtained increased as follows:
  • the solution operated at a pH of 2.7-2.9.
  • Prelimi-narily cleaned cold rolled steel panels were immersed in the solution heated to about F. for three minutes. Coating weights averaging 55 rug/sq. it. were obtained. To the solution was then added 2.5 grams/ liter of the tetra sodium salt of ethylene diamine tetraacetic acid, and coating weights were observed to increase to an average of 313 rug/sq. ft. after otherwise identical treatment.
  • compositions similar to those of Example 1 and 2 were made up in which the sodium chlorate and sodium bromate was replaced with other oxidizing agents including sodium nitrate, sodium nitrite, sodium sulfite, nitrobenzene sulfonate, hydroxylamine, etc. A few of these variations are given in the following examples.
  • Example 3 Grams/liter Manganese dihydrogen phosphate 20 Sodium nitrate 10 Triglycine .5 to 30
  • Example 4 Grams/liter Zinc 3 Phosphoric acid 12 Sodium m-nitrobenzene sulfonate 3 Ethylene diamine tetra-acetic acid .4 to 27
  • Example 5 Grams/liter Manganese dihydrogen phosphate 15 Sodium m-nitrobenzene sulfonate 6 Tetra sodium ethylene diamine tetra-acetate .5-30
  • Corrosion resistance of the Coatings appeared to be somewhat better when thecoatingsfresulted from longer immersion periods, that -is,-; between-- and minutes and the temperature approaehed-"the upper" operating Bumper-bar stock, preliminarily-cleaned, was sprayedfor 6.0 seconds incthe above solution at 138 F.
  • Coating. weights obtained varied: from 48. to .135 nag/sq ft.- The. SQ JliQ wast-altered byadding l. 'gram/litenof tetra sodium ethylene diamine tetra acetate. The. solution then had a pH of 2.7 and coating weight after sixty-second p y ried between 33.65am, 416 met/sq. ft.
  • Optimum concentrations of tetra sodium ethylene diamine tetra acetate are as follows:
  • Example 10 A composition particularly useful for treating aluminum or aluminum alloy surfaces is given in Example 10.
  • Example 10 Pounds Phosphoric acid (75%) 37 Nitric acid, 42 B 71.5 Zinc oxide 42.5 Boric acid l8- Hydrofiuoric acid (60%) 16.5 Sodium bifiuoride 17 Water to make 500 gallons.
  • Example V A solution particularly adapted for-coating zinc, galvanized iron or the like is givenin Example V a
  • The. aqueous. solution .having theabove, analysis is: prefi stably f m d b a m rtqltq i ns oi sa lfi fh oluti n-@ 503 t fiv mi u e t menve a e coating weight of .445Qmgs pen. square, foot .was,. obtained,
  • a composition for producing heavy phosphatevcoathuge on, metallic-surfaces inshort periods'of time which consistsessentiallyof an aqueous acidic. solution of a phosphatwt et lf t the ewe s ns fiasqf itqu zinc and manganese, an oxidizing agent and an acetic amino acid, said solution having pH in the range of 1.9 to 3.5.
  • a solution for producing heavy phosphate coatings on metallic surfaces in short periods of time consisting essentially of an aqueous acidic solution of a phosphate selected from the group consisting of zinc phosphate, iron phosphate and manganese phosphate, an oxidizing agent selected from the group consisting of nitrates, nitrites, chlorates, bromates, sulfites, nitrobenzene sulfonate, picric acid, and hydroxylamine, and an acetic amino acid, said solution having a pH between 1.9 and 3.5.
  • a phosphate selected from the group consisting of zinc phosphate, iron phosphate and manganese phosphate
  • an oxidizing agent selected from the group consisting of nitrates, nitrites, chlorates, bromates, sulfites, nitrobenzene sulfonate, picric acid, and hydroxylamine
  • an acetic amino acid said solution having a pH between 1.9 and 3.5.
  • a solution for producing heavy phosphate coatings on metallic surfaces in short periods of time consisting essentially of an aqueous acidic solution of a phosphate selected from the group consisting of zinc phosphate, iron phosphate and manganese phosphate, an oxidizing agent selected from the group consisting of nitrates, nitrites, chlorates, bromates, sulfites, nitrobenzene sulfonate, picric acid, and hydroxylamine, and about .01% to about 3% of ethylene diamine tetra-acetic acid, said solution having a-pH between,1. 9 and 3.5.
  • a method which comprises obtaining a corrosion resistantheavy coating on iron, steel and zinc by subjecting the surface of said metal to the action of an aqueous acidic solution of a phosphate of a metal from the group consisting of iron, zinc and manganese; and an acetic amino acid, the pH of the said solution being between 1.9 and 3.5
  • a method which comprises obtaining a heavy, corrosion resistant coating on a metal selected from the group consisting of iron, steel and zinc by subjecting the surface of said metal to the action of an aqueous acidic solution of a phosphate selected from the group consisting of zinc phosphate, iron phosphate and manganese phosphate, an
  • oxidizing agent selected from the group consisting of ni-,
  • a method which comprises obtaining a heavy, corrosion resistant coating on a metal selected from the group consisting of iron, steel and zinc by'subjecting the surface of said metal to the action of an aqueous acidic solution of a phosphate and manganese phosphate, an oxidizing agent selected from the group consisting of nitrates, nitrites, chlorates, bromates, sulfites, nitrobenzene sulfonate, picric acid, and hydroxylamine, and at least about .0l% of ethylene diamine tetra-acetic acid, said solution having a pH between 1.9 and 3.5.
  • a method which comprises obtaining a heavy, corrosion resistant coating on a metal selected from the group consisting of iron, steel and zinc by subjecting the surface of said metal to the action of an aqueous acidic solution of a phosphate selected from the group consisting of zinc phosphate, iron phosphate and manganese phosphate, an oxidizing agent selected from the group consisting of nitrates, nitrites, chlorates, bromates, sulfites, nitrobenzene sulfonate, picric acid, and hydroxylamine, and a chelating agent selected from the group consisting of ethylene diamine tetra-acetic acid, triglycine, the tetra-acetic acid derivative of trimethylene diamine and the alkali metal salts thereof in an amount equivalent to .01% to 3% of ethylene diamine tetraacetic acid, said solution having a pH between 1.9 and 3.5.
  • a method which comprises obtaining a heavy, corrosion resistant coating on a metal selected from the group consisting of iron, steel and zinc by subjecting the surface of said metal to the action of an aqueous acidic solution of a phosphate selected from the group consisting of zinc phosphate, iron phosphate and manganese phosphate, an oxidizing agent selected from the group consisting of nitrates, nitrites, chlorates, bromates, sulfites, nitrobenzene sulfonate, picric acid, and hydroxylamine, and about .01% to about 3% of ethylene diamine tetra-acetic acid, said solution having a pH between 1.9 and 3.5.
  • a phosphate selected from the group consisting of zinc phosphate, iron phosphate and manganese phosphate
  • an oxidizing agent selected from the group consisting of nitrates, nitrites, chlorates, bromates, sulfites, nitrobenzene sulfonate,
  • a composition for producing heavy phosphate coatings on metallic surfaces in short periods of time which consists essentially of an aqueous acidic solution of a phosphate of a metal from the group consisting of iron, zinc and manganese, an oxidizing agent, a fluoride and an acetic amino acid, said solution having a pH in the range of 1.9 to 3.5.

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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)
  • Paints Or Removers (AREA)
US306961A 1952-08-28 1952-08-28 Phosphate metal coatings Expired - Lifetime US2743204A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
BE522392D BE522392A (en(2012)) 1952-08-28
DENDAT1072055D DE1072055B (en(2012)) 1952-08-28
NL91161D NL91161C (en(2012)) 1952-08-28
US306961A US2743204A (en) 1952-08-28 1952-08-28 Phosphate metal coatings
GB29258/52A GB733235A (en) 1952-08-28 1952-11-19 Improvements in processes of, and compositions for forming phosphate coatings on metallic surfaces
FR1086955D FR1086955A (fr) 1952-08-28 1953-08-27 Perfectionnements relatifs à l'enduisage des métaux
CH312218D CH312218A (fr) 1952-08-28 1953-08-27 Procédé de traitement de surfaces métalliques, en vue de les munir d'un revêtement phosphaté lourd.

Applications Claiming Priority (1)

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US306961A US2743204A (en) 1952-08-28 1952-08-28 Phosphate metal coatings

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US2743204A true US2743204A (en) 1956-04-24

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US (1) US2743204A (en(2012))
BE (1) BE522392A (en(2012))
CH (1) CH312218A (en(2012))
DE (1) DE1072055B (en(2012))
FR (1) FR1086955A (en(2012))
GB (1) GB733235A (en(2012))
NL (1) NL91161C (en(2012))

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2859145A (en) * 1956-01-25 1958-11-04 Parker Rust Proof Co Cold rolling of steel
US2930723A (en) * 1954-12-07 1960-03-29 Walterisation Company Ltd Surface treatment of metals
US3141797A (en) * 1961-09-07 1964-07-21 Lubrizol Corp Phosphating process
US3145082A (en) * 1959-12-07 1964-08-18 Dow Chemical Co Stabilized hydroxylamine and its method of preparation
US3146133A (en) * 1961-03-23 1964-08-25 Hooker Chemical Corp Process and compositions for forming improved phosphate coatings on metallic surfaces
US3346426A (en) * 1964-04-22 1967-10-10 Detrex Chem Ind Wipe-on phosphating composition
US4053328A (en) * 1974-08-30 1977-10-11 Nippon Paint Co., Ltd. Zinc phosphate coating process
US4149909A (en) * 1977-12-30 1979-04-17 Amchem Products, Inc. Iron phosphate accelerator
US4168983A (en) * 1978-04-13 1979-09-25 Vittands Walter A Phosphate coating composition
DE3543733A1 (de) * 1984-12-20 1986-07-03 Parker Chemical Co., Madison Heights, Mich. Verfahren zur erleichterung der kaltverformung
US4637838A (en) * 1984-03-09 1987-01-20 Metallgesellschaft, A.G. Process for phosphating metals
US4708744A (en) * 1985-02-22 1987-11-24 Henkel Kommanditgesellschaft Auf Aktien Process for phosphating metal surfaces and especially iron surfaces
US4865653A (en) * 1987-10-30 1989-09-12 Henkel Corporation Zinc phosphate coating process
US5234509A (en) * 1984-12-20 1993-08-10 Henkel Corporation Cold deformation process employing improved lubrication coating
US5261973A (en) * 1991-07-29 1993-11-16 Henkel Corporation Zinc phosphate conversion coating and process
US5344713A (en) * 1989-04-03 1994-09-06 Sumitomo Electric Industries Ltd. Method for manufacturing steel wire material for reinforcing optical fiber
WO1995012010A1 (en) * 1993-10-29 1995-05-04 Henkel Corporation Composition and process for treating magnesium-containing metals and product therefrom
US5588989A (en) * 1994-11-23 1996-12-31 Ppg Industries, Inc. Zinc phosphate coating compositions containing oxime accelerators
US5653790A (en) * 1994-11-23 1997-08-05 Ppg Industries, Inc. Zinc phosphate tungsten-containing coating compositions using accelerators
US5797987A (en) * 1995-12-14 1998-08-25 Ppg Industries, Inc. Zinc phosphate conversion coating compositions and process
US6179934B1 (en) * 1997-01-24 2001-01-30 Henkel Corporation Aqueous phosphating composition and process for metal surfaces
US6368426B1 (en) * 1991-07-29 2002-04-09 Henkel Corporation Zinc phosphate conversion coating and process
US20030155042A1 (en) * 2001-12-13 2003-08-21 Richard Church Use of substituted hydroxylamines in metal phosphating processes

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19538778A1 (de) * 1995-10-18 1997-04-24 Henkel Kgaa Schichtgewichtssteuerung bei Hydroxylamin-beschleunigten Phosphatiersystemen
DE102014005444A1 (de) * 2014-04-11 2015-10-15 Audi Ag Verfahren zur Passivierung einer metallischen Oberfläche
DE102016002852A1 (de) * 2016-03-10 2017-09-14 Audi Ag Verfahren zur Passivierung einer Oberfläche eines Metallbauteils

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1911726A (en) * 1931-07-07 1933-05-30 Metal Finishing Res Corp Production of phosphate coatings on metals
US2132883A (en) * 1937-04-30 1938-10-11 American Chem Paint Co Method of coating ferrous metal with a water insoluble metallic phosphate
US2298280A (en) * 1939-02-02 1942-10-13 Parker Rust Proof Co Treatment of metal
US2316811A (en) * 1940-04-13 1943-04-20 American Chem Paint Co Method of coating ferrous metal surfaces with water insoluble metallic phosphates
US2461519A (en) * 1948-03-17 1949-02-15 Frederick C Bersworth Method of producing carboxylic substituted aliphatic amines and metallic salts thereof
US2479423A (en) * 1946-02-07 1949-08-16 American Chem Paint Co Method of and materials for treating surfaces of iron, zinc, and alloys of each
GB663650A (en) * 1947-11-05 1951-12-27 Hans Bibus Chromatic mouth organ

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1911726A (en) * 1931-07-07 1933-05-30 Metal Finishing Res Corp Production of phosphate coatings on metals
US2132883A (en) * 1937-04-30 1938-10-11 American Chem Paint Co Method of coating ferrous metal with a water insoluble metallic phosphate
US2298280A (en) * 1939-02-02 1942-10-13 Parker Rust Proof Co Treatment of metal
US2316811A (en) * 1940-04-13 1943-04-20 American Chem Paint Co Method of coating ferrous metal surfaces with water insoluble metallic phosphates
US2479423A (en) * 1946-02-07 1949-08-16 American Chem Paint Co Method of and materials for treating surfaces of iron, zinc, and alloys of each
GB663650A (en) * 1947-11-05 1951-12-27 Hans Bibus Chromatic mouth organ
US2461519A (en) * 1948-03-17 1949-02-15 Frederick C Bersworth Method of producing carboxylic substituted aliphatic amines and metallic salts thereof

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2930723A (en) * 1954-12-07 1960-03-29 Walterisation Company Ltd Surface treatment of metals
US2859145A (en) * 1956-01-25 1958-11-04 Parker Rust Proof Co Cold rolling of steel
US3145082A (en) * 1959-12-07 1964-08-18 Dow Chemical Co Stabilized hydroxylamine and its method of preparation
US3146133A (en) * 1961-03-23 1964-08-25 Hooker Chemical Corp Process and compositions for forming improved phosphate coatings on metallic surfaces
US3141797A (en) * 1961-09-07 1964-07-21 Lubrizol Corp Phosphating process
US3346426A (en) * 1964-04-22 1967-10-10 Detrex Chem Ind Wipe-on phosphating composition
US4053328A (en) * 1974-08-30 1977-10-11 Nippon Paint Co., Ltd. Zinc phosphate coating process
US4149909A (en) * 1977-12-30 1979-04-17 Amchem Products, Inc. Iron phosphate accelerator
US4168983A (en) * 1978-04-13 1979-09-25 Vittands Walter A Phosphate coating composition
US4637838A (en) * 1984-03-09 1987-01-20 Metallgesellschaft, A.G. Process for phosphating metals
AU577424B2 (en) * 1984-12-20 1988-09-22 Parker Chemical Company Lubricant coating for metal working
EP0186823A3 (en) * 1984-12-20 1988-04-27 Parker Chemical Company Process for facilitating cold-forming
DE3543733A1 (de) * 1984-12-20 1986-07-03 Parker Chemical Co., Madison Heights, Mich. Verfahren zur erleichterung der kaltverformung
US5234509A (en) * 1984-12-20 1993-08-10 Henkel Corporation Cold deformation process employing improved lubrication coating
GB2169620A (en) * 1984-12-20 1986-07-16 Parker Chemical Co Phosphate coatings
US4708744A (en) * 1985-02-22 1987-11-24 Henkel Kommanditgesellschaft Auf Aktien Process for phosphating metal surfaces and especially iron surfaces
US4865653A (en) * 1987-10-30 1989-09-12 Henkel Corporation Zinc phosphate coating process
US5344713A (en) * 1989-04-03 1994-09-06 Sumitomo Electric Industries Ltd. Method for manufacturing steel wire material for reinforcing optical fiber
US6368426B1 (en) * 1991-07-29 2002-04-09 Henkel Corporation Zinc phosphate conversion coating and process
US5261973A (en) * 1991-07-29 1993-11-16 Henkel Corporation Zinc phosphate conversion coating and process
WO1995012010A1 (en) * 1993-10-29 1995-05-04 Henkel Corporation Composition and process for treating magnesium-containing metals and product therefrom
US5653790A (en) * 1994-11-23 1997-08-05 Ppg Industries, Inc. Zinc phosphate tungsten-containing coating compositions using accelerators
US5588989A (en) * 1994-11-23 1996-12-31 Ppg Industries, Inc. Zinc phosphate coating compositions containing oxime accelerators
US5797987A (en) * 1995-12-14 1998-08-25 Ppg Industries, Inc. Zinc phosphate conversion coating compositions and process
US5868874A (en) * 1995-12-14 1999-02-09 Ppg Industries, Inc. Zinc phosphate conversion coating compositions and process
US6179934B1 (en) * 1997-01-24 2001-01-30 Henkel Corporation Aqueous phosphating composition and process for metal surfaces
US20030155042A1 (en) * 2001-12-13 2003-08-21 Richard Church Use of substituted hydroxylamines in metal phosphating processes
US7294210B2 (en) 2001-12-13 2007-11-13 Henkel Kommanditgesellschaft Auf Aktien Use of substituted hydroxylamines in metal phosphating processes

Also Published As

Publication number Publication date
BE522392A (en(2012))
FR1086955A (fr) 1955-02-17
DE1072055B (en(2012))
GB733235A (en) 1955-07-06
CH312218A (fr) 1955-12-31
NL91161C (en(2012))

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