US3819385A - Method for applying a phosphate coating to iron and steel - Google Patents

Method for applying a phosphate coating to iron and steel Download PDF

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Publication number
US3819385A
US3819385A US00283446A US28344672A US3819385A US 3819385 A US3819385 A US 3819385A US 00283446 A US00283446 A US 00283446A US 28344672 A US28344672 A US 28344672A US 3819385 A US3819385 A US 3819385A
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US
United States
Prior art keywords
solution
iron
vanadium
chlorate
calculated
Prior art date
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Expired - Lifetime
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US00283446A
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English (en)
Inventor
H Schumichen
G Mueller
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
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Oxy Metal Finishing Corp
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Assigned to HOOKER CHEMICALS & PLASTICS CORP, A CORP OF NY reassignment HOOKER CHEMICALS & PLASTICS CORP, A CORP OF NY ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: OXY METAL INDUSTRIES CORPORATION
Assigned to OXY METAL INDUSTRIES CORPORATION reassignment OXY METAL INDUSTRIES CORPORATION CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). 4-09-74 Assignors: OXY METAL FINISHING CORPORATION
Assigned to OCCIDENTAL CHEMICAL CORPORATION reassignment OCCIDENTAL CHEMICAL CORPORATION CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). EFFECTIVE MARCH 30, 1982. Assignors: HOOKER CHEMICAS & PLASTICS CORP.
Assigned to PARKER CHEMICAL COMPANY, A DE CORP. reassignment PARKER CHEMICAL COMPANY, A DE CORP. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: OCCIDENTAL CHEMICAL CORPORATION
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • C23C22/40Chemical 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 molybdates, tungstates or vanadates
    • C23C22/42Chemical 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 molybdates, tungstates or vanadates containing also phosphates

Definitions

  • the invention pertains to an improved method for applying a phosphate coating to iron and steel using an aqueous zinc phosphate solution containing acid chlorate.
  • nitrite in addition to chlorate, to be sure, represents a highly effective procedure with respect to the removal of the iron which goes into solution, and the related possibility of maintaining constant, short treatment times; however, the use of nitrite also entails 2 procedural disadvantages, e.g., the necessity of waste water processing and of removingnitrogen-containing gases from the waste air. The nitrous gases can also lead to corrosion at the transmission points before and after the treating zone.
  • the continuous analytical monitoring of the nitrite content in the bath solution entails a certain expense. It has been found that zinc phosphate coatings which are applied from solutions containing chlorate and nitrite provide poorer corrosion protection in combination with an organic covering layer than corresponding coatings produced with a chlorate-containing but nitrite-free solution.
  • the object of the invention is now a method for applying a phosphate coating to iron and steel with the aid of a chlorate-accelerated zinc phosphate solution at temperatures below 65 C, which is characterized by the fact that a zinc phosphate solution containing 1-10 g/l C10 and 0.1 to 10 mg/l vanadium, calculated as V 0 is used.
  • the vanadium can be added to the chloratecontaining zinc phosphate solution in accordance with the invention in the form of vanadium pentoxide (V 0 or in the form of other vanadium compounds. It' can also be added to the concentrate used in making up the solution.
  • the vanadium content of the treating solution preferably amounts to 0.4-7 mg/l, calculated as V 0
  • the range of 0.4-2.7 mg/l is particularly suitable.
  • the significance of the vanadium content is independent of the valence of the vanadium actually present in the solution. Contents of more than 10 mg/l can interfere with layer formation by passivation of the surface.
  • the zinc phosphate solution used advantageously contains about 1 to 10 g/l zinc, corresponding quantities of phosphate and l to 10 g/l chlorate. It can also contain nitrate and other customary additives, such as nickel, calcium, simple or complex fluoride, boron compounds and the like. The further use of nitrite is undesirable because of the disadvantages mentioned above.
  • the iron and steel surfaces to be provided with the coating can be brought into contact with the treating solution in any desired manner, e.g., by immersion in the solution or spraying with the solution.
  • the spray method is advantageously used.
  • the spraying time advantageously amounts to a maximum of 150 seconds. Somewhat longer contact times may be required in the immersion process.
  • the method according to the present invention is advantageously carried out in the temperature range of 40 to 65 C. At temperatures above 55 C, the treating bath also remains essentially free from divalent iron even at higher throughputs. At temperatures below 55 C, certain quantities of divalent iron can enter the solution, without an appreciable accumulation occurring.
  • the replenishment of vanadium in the solution used in accordance with the present invention can be easily accomplished by adding 0.044 mg vanadium, calculated as V 0 to the solution per square meter of treated surface.
  • Supplemental zinc, P 0 and chlorate is provided in the customary manner, to provide point constancy or corresponding to use.
  • the vanadium compound may be added to the supplemental concentrate if desired.
  • a treating solution was prepared, which contained 3.1 g/l Zn, 8.3 g/l P 0 5.2 g/l C10 13.8 g/l N0 and 0.1 g/l Ni. Sheets of steel were treated by spraying at temperatures of 53 C and 60 C. In accordance with It is obvious that the addition of vanadium has resulted in a marked reduction in the iron (11) content of the solution, and that the layer weight of the coating was scarcely affected by this addition.
  • the corrosion behavior of the coatings produced at 60 C in accordance with the invention was likewise compared with coatings obtained from vanadium-free solutions, containing only chlorate, and containing iron (11) (Experiment No. 2) and the coatings produced at 60 C from solutions containing chlorate and nitrite (Experiment No. 5).
  • the solution used in Experiment No. 5 contained 3.1 g/l Zn, 8.3 g/l P 0 5.2 g/lC10 13.8 g/l NO;,, 0.1 g/l Ni and 0.11
  • a method for applying a phosphate coating to an iron or steel surface comprising contacting said surface with an aqueous solution comprising acidic zinc phosphate, chlorate ion and from 0.1 to 10 mg/l of vanadium, calculated as V 0 at a temperature of less than 65 C.
  • vanadium is present in an amount of from 0.4 to 2.7 mg/l, calculated as V205- 6 g/l chlorate and from 0.1 to 10 mg/l vanadium, calculated as V 0 8.
  • the chlorate content is from ll0 g/l and the zinc content is from l-lO g/l.

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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)
  • Application Of Or Painting With Fluid Materials (AREA)
US00283446A 1971-09-02 1972-08-31 Method for applying a phosphate coating to iron and steel Expired - Lifetime US3819385A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE2143957A DE2143957A1 (de) 1971-09-02 1971-09-02 Verfahren zum aufbringen eines phosphatueberzuges auf eisen und stahl

Publications (1)

Publication Number Publication Date
US3819385A true US3819385A (en) 1974-06-25

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ID=5818462

Family Applications (1)

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US00283446A Expired - Lifetime US3819385A (en) 1971-09-02 1972-08-31 Method for applying a phosphate coating to iron and steel

Country Status (15)

Country Link
US (1) US3819385A (enExample)
AR (1) AR196082A1 (enExample)
AT (1) AT314932B (enExample)
AU (1) AU4577672A (enExample)
BE (1) BE780333A (enExample)
BR (1) BR7205983D0 (enExample)
CH (1) CH580168A5 (enExample)
DE (1) DE2143957A1 (enExample)
ES (1) ES401733A1 (enExample)
FR (1) FR2150659B1 (enExample)
GB (1) GB1355739A (enExample)
IT (1) IT964406B (enExample)
NL (1) NL7211797A (enExample)
SE (1) SE376772B (enExample)
ZA (1) ZA725433B (enExample)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0015021A1 (de) * 1979-02-23 1980-09-03 Metallgesellschaft Ag Verfahren zur Vorbereitung von Metalloberflächen für die elektrophoretische Tauchlackierung
US4233088A (en) * 1979-03-29 1980-11-11 International Lead Zinc Research Organization, Inc. Phosphatization of steel surfaces and metal-coated surfaces
US4264378A (en) * 1979-02-14 1981-04-28 Oxy Metal Industries Corporation Chromium-free surface treatment
US4490185A (en) * 1982-12-03 1984-12-25 Henkel Kommanditgesellschaft Auf Aktien Phosphating solutions and process
US4880476A (en) * 1986-12-09 1989-11-14 Nippondenso Co., Ltd. Process for the phosphate chemical conversion treatment of a steel material
GB2374088A (en) * 2001-03-29 2002-10-09 Macdermid Plc Conversion treatment of zinc and zinc alloy surfaces
US20060228505A1 (en) * 2005-03-29 2006-10-12 Kunio Goto Threaded joint for steel pipes

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3392008B2 (ja) * 1996-10-30 2003-03-31 日本表面化学株式会社 金属の保護皮膜形成処理剤と処理方法
US4881975A (en) * 1986-12-23 1989-11-21 Albright & Wilson Limited Products for treating surfaces
GB9207725D0 (en) * 1992-04-08 1992-05-27 Brent Chemicals Int Phosphating solution for metal substrates
AU1887601A (en) * 1999-12-13 2001-06-18 Toyo Kohan Co. Ltd. Method for producing surface treated steel sheet, surface treated steel sheet and surface treated steel sheet coated with resin

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB495098A (en) * 1936-02-04 1938-11-04 American Chem Paint Co Improvements in or relating to a method for applying a phosphatic coating to metallic surfaces
US2854370A (en) * 1957-10-04 1958-09-30 Oakite Prod Inc Composition and method for phosphate coating of metal
US3218200A (en) * 1953-08-10 1965-11-16 Lubrizol Corp Phosphate coating of metals
US3261723A (en) * 1962-11-30 1966-07-19 Lubrizol Corp Method for reducing combustion chamber deposits in internal combustion engines
US3617393A (en) * 1969-10-08 1971-11-02 Dainippon Toryo Kk Pretreatment before electrophoretic painting
US3676224A (en) * 1970-10-16 1972-07-11 Lubrizol Corp Phosphating solution with scale suppressing characteristics

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB495098A (en) * 1936-02-04 1938-11-04 American Chem Paint Co Improvements in or relating to a method for applying a phosphatic coating to metallic surfaces
US3218200A (en) * 1953-08-10 1965-11-16 Lubrizol Corp Phosphate coating of metals
US2854370A (en) * 1957-10-04 1958-09-30 Oakite Prod Inc Composition and method for phosphate coating of metal
US3261723A (en) * 1962-11-30 1966-07-19 Lubrizol Corp Method for reducing combustion chamber deposits in internal combustion engines
US3617393A (en) * 1969-10-08 1971-11-02 Dainippon Toryo Kk Pretreatment before electrophoretic painting
US3676224A (en) * 1970-10-16 1972-07-11 Lubrizol Corp Phosphating solution with scale suppressing characteristics

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4264378A (en) * 1979-02-14 1981-04-28 Oxy Metal Industries Corporation Chromium-free surface treatment
EP0015021A1 (de) * 1979-02-23 1980-09-03 Metallgesellschaft Ag Verfahren zur Vorbereitung von Metalloberflächen für die elektrophoretische Tauchlackierung
US4233088A (en) * 1979-03-29 1980-11-11 International Lead Zinc Research Organization, Inc. Phosphatization of steel surfaces and metal-coated surfaces
US4490185A (en) * 1982-12-03 1984-12-25 Henkel Kommanditgesellschaft Auf Aktien Phosphating solutions and process
US4880476A (en) * 1986-12-09 1989-11-14 Nippondenso Co., Ltd. Process for the phosphate chemical conversion treatment of a steel material
GB2374088A (en) * 2001-03-29 2002-10-09 Macdermid Plc Conversion treatment of zinc and zinc alloy surfaces
US20060228505A1 (en) * 2005-03-29 2006-10-12 Kunio Goto Threaded joint for steel pipes
US20110025052A1 (en) * 2005-03-29 2011-02-03 Sumitomo Metal Industries, Ltd. Threaded Joint for Steel Pipes
US7883118B2 (en) * 2005-03-29 2011-02-08 Sumitomo Metal Industries, Ltd. Threaded joint for steel pipes
US20110163538A1 (en) * 2005-03-29 2011-07-07 Sumitomo Metal Industries, Ltd. Threaded joint for steel pipes
US8409718B2 (en) 2005-03-29 2013-04-02 Nippon Steel & Sumitomo Metal Corporation Threaded joint for steel pipes
US8741406B2 (en) 2005-03-29 2014-06-03 Nippon Steel & Sumitomo Metal Corporation Oil well pipe with threaded joint

Also Published As

Publication number Publication date
ES401733A1 (es) 1975-03-16
BE780333A (fr) 1972-07-03
FR2150659B1 (enExample) 1974-04-05
AT314932B (de) 1974-04-25
NL7211797A (enExample) 1973-03-06
IT964406B (it) 1974-01-21
AR196082A1 (es) 1973-11-30
CH580168A5 (enExample) 1976-09-30
GB1355739A (en) 1974-06-05
AU4577672A (en) 1974-02-28
DE2143957A1 (de) 1973-03-08
SE376772B (enExample) 1975-06-09
ZA725433B (en) 1973-09-26
BR7205983D0 (pt) 1973-08-21
FR2150659A1 (enExample) 1973-04-13

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AS Assignment

Owner name: HOOKER CHEMICALS & PLASTICS CORP 32100 STEPHENSON

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:OXY METAL INDUSTRIES CORPORATION;REEL/FRAME:003942/0016

Effective date: 19810317

AS Assignment

Owner name: OXY METAL INDUSTRIES CORPORATION

Free format text: CHANGE OF NAME;ASSIGNOR:OXY METAL FINISHING CORPORATION;REEL/FRAME:003967/0084

Effective date: 19741220

AS Assignment

Owner name: OCCIDENTAL CHEMICAL CORPORATION

Free format text: CHANGE OF NAME;ASSIGNOR:HOOKER CHEMICAS & PLASTICS CORP.;REEL/FRAME:004126/0054

Effective date: 19820330

AS Assignment

Owner name: PARKER CHEMICAL COMPANY, 32100 STEPHENSON HWY., MA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:OCCIDENTAL CHEMICAL CORPORATION;REEL/FRAME:004194/0047

Effective date: 19830928