EP0675972A4 - - Google Patents
Info
- Publication number
- EP0675972A4 EP0675972A4 EP94904428A EP94904428A EP0675972A4 EP 0675972 A4 EP0675972 A4 EP 0675972A4 EP 94904428 A EP94904428 A EP 94904428A EP 94904428 A EP94904428 A EP 94904428A EP 0675972 A4 EP0675972 A4 EP 0675972A4
- Authority
- EP
- European Patent Office
- Prior art keywords
- ions
- range
- phosphate coating
- forming
- dissolved
- 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.)
- Granted
Links
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
-
- 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
- C23C22/13—Orthophosphates containing zinc cations containing also nitrate or nitrite anions
-
- 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
- C23C22/186—Orthophosphates containing manganese cations containing also copper cations
-
- 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
- C23C22/34—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 fluorides or complex fluorides
- C23C22/36—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 fluorides or complex fluorides containing also phosphates
- C23C22/362—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 fluorides or complex fluorides containing also phosphates containing also zinc cations
-
- 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
- C23C22/34—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 fluorides or complex fluorides
- C23C22/36—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 fluorides or complex fluorides containing also phosphates
- C23C22/368—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 fluorides or complex fluorides containing also phosphates containing magnesium cations
Definitions
- This invention relates to a composition and process for forming a phosphate conversion coating on active metal surfaces in order to increase the corrosion resist- ance of the surfaces, either as treated or after subsequent conventional overcoating of the conversion coating layer formed by an organic based protective coating such as a paint or lacquer.
- a composition according to this invention is well adapted to treat ⁇ ing any of a variety of base metals, including at least steel and galvanized steel and aluminum and aluminum based alloys.
- Nickel has been implicated as a carcinogen in some studies, so that avoidance of its use in metal finishing is desirable for health reasons. Nickel is also considered a serious pollutant, and at the levels of 0.5 - 1.5 grams per liter (hereinafter often ab- breviated "g/L") at which it is conventionally used, nickel contributes significantly to the cost of the zinc phosphate conversion coating compositions. It is an object of this invention to minimize or eliminate the use of nickel, without worsening the quality of conversion coating obtained with conventional compositions containing zinc, nickel, and manganese.
- a working composition according to this invention is an aqueous liquid compo- 5 sition that comprises, preferably consists essentially of, still more preferably consists of, water and:
- (C) from 1 to 200, or with increasing preference in the order given, from 20 to 100, 24 to 74, or 24 to 60 milligrams per liter ("mg/L") of dissolved Cu +2 ions;
- Points of free acid and total acid are defined for use herein as the number of milliliters (hereinafter “ml") of 0.1 N ⁇ aOH solution required to titrate a 10 ml sample of the composition, to a phenolphthalein end point (pH 9.0) for total acid and a bromthymol blue end point (pH 3.8) for free acid, except that if the composition has a pH greater than 3.8 initially, the points of free acid are defined as the negative of the number of ml of 0.1 N strong acid solution required to titrate a 10 ml sample of the composition to a pH of 3.8.
- a process according to this invention comprises at a minimum a step of con ⁇ tacting a metal surface to be treated with a composition according to the invention for a sufficient time to form on the metal surface a detectable conversion coating.
- Con- ventional metal surface cleaning and/or activation steps before contact between the metal to be treated and compositions according to the invention may be used if de ⁇ sired, and are generally preferred, as part of a process according to this invention.
- a process according to the invention also may, and usually preferably does, include con ⁇ ventional steps subsequent to the contact between the metal surface to be treated and the compositions according to the invention.
- the phosphate ions required for the compositions according to this invention are preferably PO 4 "3 ions or other ions derivable from less complete ionization of ortho- phosphoric acid (H 3 PO 4 ). Any free unionized phosphoric acid that may be present is considered part of the content of phosphate ions, to the extent of its stoichiometric cor ⁇ respondence to PO 4 '3 ions. Other free phosphoric acids such as metaphosphoric acid and condensed phosphoric acids such as pyrophosphoric acid and all anions derivable from them may also be used to supply the necessary phosphate ions.
- the phosphate ions are derived from orthophosphoric acid and/or its neutral or acid salts of the metal cations also specified above as part of the compositions according to this invention.
- the zinc cations required as part of the compositions are preferably derived from neutral or acid zinc salts of orthophosphoric acid, which may be formed in situ by dissolving zinc or zinc oxide or hydroxide in a solution containing the acid.
- cupric cations required as part of the compositions according to this inven ⁇ tion may be derived from salts such as cupric sulfate and/or nitrate, or may be ob ⁇ tained by dissolving cupric oxide in part of the phosphoric acid used.
- the accelerator component required in compositions according to the invention preferably includes at least one of the following: (i) from 0.01 to 0.2 g/1 of nitrite ions, (ii) from 0.5 to 5 g/1 of H 2 O 2 , (iii) from 0.05 to 2 g/1 of m-nitrobenzenesulfonate ions, (iv) from 0.05 to 2 g/1 of m-nitrobenzoate ions, (v) from 0.05 to 2 g/1 of p-nitro- phenol, and (vi) from 0.1 to 10, more preferably from 0.5 to 6, or still more preferably from 0.5 to 2.0, g L, measured as it stoichiometric equivalent as hydroxylamine, of a component capable of furnishing hydroxylamine in water solution.
- the accelerator is hydroxylamine sulfate (hereinafter often abbreviated "HAS") or a similar safe and readily available source of dissolved hydroxylamine.
- HAS hydroxylamine sulfate
- the second most preferable accelerator is nitrite ions.
- the acidity of the compositions according to the invention is preferably derived from phosphoric, sulfuric, and/or nitric acids.
- the free fluoride may be derived from complex fluoride ions such as fluoborate (BF 4 2 ), fluohafnate (HfF 6 "2 ), fluosilicate (SiF 6 '2 ), fluotitanate (TiF 6 "2 ), fluozirconate (ZrF 6 “2 ), and mixtures thereof; more preferably, from fluoborate and fluo- silicate and mixtures thereof.
- complex fluoride ions such as fluoborate (BF 4 2 ), fluohafnate (HfF 6 "2 ), fluosilicate (SiF 6 '2 ), fluotitanate (TiF 6 "2 ), fluozirconate (ZrF 6 “2 ), and mixtures thereof; more preferably, from fluoborate and fluo- silicate and mixtures thereof.
- simple fluorides such as alkali metal fluorides are also entirely satisfactory sources of free fluoride.
- compositions according to the invention contain no more than 0.5, 0.2, 0.10, 0.07, 0.03, 0.01, 0.005, or 0.001 g/L of each of Ni +2 , any cation with a valence of three or higher, chloride ions including complex chloride ions, and chlorate ions.
- chloride ions are present in sufficient quantity to be readily determined analytically, it is preferred that the ratio of the concentration in g/L of complex fluoride ions to the concentration in g/L of chloride ions have a value of at least 8:1, or more preferably a value of at least 14:1.
- contact between the metal surface to be treated and a composition according to the invention may be accomplished by spraying, dipping, or any other convenient method or combination of methods.
- the temperature during contact between the metal treated and the composition according to the invention preferably is, with increasing preference in the order given, in the range from 21 to 85, 25 to 55, or 31 to 44, ° C.
- the total time of contact between the composition according to the invention and the metal surface to be conversion coated preferably is, with increasing preference in the order given, in the range from 5 sec to 15 minutes (hereinafter often abbreviated "min"), 15 seconds (hereinafter often abbreviated "sec”) to 10 min, 30 sec to 5 min, or 90 to 120 sec.
- the add-on mass of the phosphate coating formed preferably is, with increasing preference in the order given, in the range from 1.1 to 5.4, 1.6 to 4.3, or 2.2 to 3.8, grams per square meter (hereinafter "g/m 2 ) of surface treated.
- the weight percent of copper in the coat ⁇ ing formed preferably is, with increasing preference in the order given, from 0.50 to 10, 1.0 to 8.0, 2.0 to 6.0, 3.0 to 4.1.
- compositions except for one comparison example, illustrate the use of
- HAS accelerator HAS accelerator. Specific compositions are shown in Table 1 below. These composi- tions, except for comparison example 13 which was prepared from a commercially compounded concentrate, were prepared according to the following general procedure: An amount of water equal to about three-quarters of the volume eventually desired for the composition was initially used, and an amount of zinc dihydrogen phosphate suffi ⁇ cient to provide the desired zinc ion concentration in the final desired volume was dis ⁇ solved in this water. An amount of 75 % aqueous solution of orthophosphoric acid that was sufficient, together with the previously added zinc dihydrogen phosphate, to provide the desired final concentration of phosphate ions in the desired final volume was then added.
- Test panels of cold rolled steel, galvanized steel, and/or conventional aluminum alloys used in automobile and appliance manufacture were used and subjected to the following general sequence of process steps: (1) Conventional alkaline cleaner for 120 sec at 43° C; (2) Water rinse at 38° C for 60 sec; (3) Conventional colloidal titanium phosphate activator for 30 sec at 38° C; (4) Contact with one of Composi ⁇ tions 1 - 12 from Table 1 below for 120 sec at 35° C or at 43° C; (5) Cold water rinse at 20 - 25 ° C for 60 sec; (6) Post treatment for 30 sec with a conventional commer ⁇ cial post treatment composition containing hexavalent and trivalent chromium; and (7) Rinse with deionized water for 30 sec at 20 - 25 ° C.
- compositions were prepared in the same general manner as for Group I, except that sodium nitrite instead of HAS was used as the accelerator and cupric ni ⁇ trate with an average of 2.5 molecules of water of hydration per cupric ion was used as the copper source.
- Compositions are as follows:
- Example 14 was used for spray phosphating at 33° C in a process sequence other ⁇ wise like those of Group I above.
- Example 14 was used for immersion phosphating at 57° C in a process sequence otherwise like those of Group I above.
Landscapes
- 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)
- Glass Compositions (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US99546592A | 1992-12-22 | 1992-12-22 | |
PCT/US1993/012044 WO1994014999A1 (en) | 1992-12-22 | 1993-12-15 | Substantially nickel-free phosphate conversion coating composition and process |
US995465 | 1997-10-06 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0675972A1 EP0675972A1 (en) | 1995-10-11 |
EP0675972A4 true EP0675972A4 (en) | 1995-11-02 |
EP0675972B1 EP0675972B1 (en) | 1999-08-11 |
Family
ID=25541841
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP94904428A Expired - Lifetime EP0675972B1 (en) | 1992-12-22 | 1993-12-15 | Substantially nickel-free phosphate conversion coating composition and process |
Country Status (14)
Country | Link |
---|---|
EP (1) | EP0675972B1 (en) |
JP (1) | JPH08504890A (en) |
CN (1) | CN1092245C (en) |
AT (1) | ATE183247T1 (en) |
AU (1) | AU5848194A (en) |
BR (1) | BR9307702A (en) |
CA (1) | CA2150545A1 (en) |
CZ (1) | CZ287997B6 (en) |
DE (1) | DE69326021T2 (en) |
ES (1) | ES2136726T3 (en) |
PL (1) | PL309404A1 (en) |
SG (1) | SG55084A1 (en) |
WO (1) | WO1994014999A1 (en) |
ZA (1) | ZA939636B (en) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4440300A1 (en) * | 1994-11-11 | 1996-05-15 | Metallgesellschaft Ag | Process for applying phosphate coatings |
DE19511573A1 (en) * | 1995-03-29 | 1996-10-02 | Henkel Kgaa | Process for phosphating with metal-containing rinsing |
DE19538778A1 (en) * | 1995-10-18 | 1997-04-24 | Henkel Kgaa | Layer weight control in hydroxylamine-accelerated phosphating systems |
DE19540085A1 (en) * | 1995-10-27 | 1997-04-30 | Henkel Kgaa | Low nitrate, manganese-free zinc phosphating |
DE19606017A1 (en) * | 1996-02-19 | 1997-08-21 | Henkel Kgaa | Zinc phosphating with low copper and manganese contents |
DE19740953A1 (en) * | 1997-09-17 | 1999-03-18 | Henkel Kgaa | High speed spray or dip phosphating of steel strip |
DE10320313B4 (en) * | 2003-05-06 | 2005-08-11 | Chemetall Gmbh | A method of coating metallic bodies with a phosphating solution, phosphating solution and the use of the coated article |
CN101091007B (en) * | 2004-12-28 | 2011-01-26 | 亨克尔两合股份公司 | Iron phosphating process that reduces laser scale resulting in improved paint adhesion |
DE102006052919A1 (en) * | 2006-11-08 | 2008-05-15 | Henkel Kgaa | Zr / Ti-containing phosphating solution for the passivation of metal composite surfaces |
CN103924226B (en) * | 2014-04-25 | 2016-06-15 | 山东大学 | A kind of preparation method of hierarchy zinc phosphate chemical composition coating |
CN104032293B (en) * | 2014-06-11 | 2016-02-17 | 安徽江南机械有限责任公司 | One not nickeliferous single component high anti-corrosion environmental protection black phosphating solution |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB526816A (en) * | 1939-03-14 | 1940-09-26 | Samuel Thomas Roberts | Improvements in the conversion of zinc, zinc alloy, galvanised, cadmium and cadmium alloy surfaces for ensuring paint and enamel adhesion |
US2813812A (en) * | 1952-06-24 | 1957-11-19 | Parker Rust Proof Co | Method for coating iron or zinc with phosphate composition and aqueous solution therefor |
FR1465983A (en) * | 1965-11-06 | 1967-01-13 | Parker Ste Continentale | Process for treating steel for the application of electrophoresis paint |
DE2049350A1 (en) * | 1969-10-08 | 1971-04-15 | Lubrizol Corp | Phosphating solutions and their use for the corrosion protection of ferrous metal and zinc surfaces |
FR2203893A1 (en) * | 1972-10-20 | 1974-05-17 | Fosfa Col Sas Di A Dal Pane Et | Ambient temp. phosphating - using accelerator contg. bath to produce coating espec. amenable to accepting electrophoretic paint coatings |
EP0123980A1 (en) * | 1979-05-02 | 1984-11-07 | Amchem Products, Inc. | Composition and process for zinc phosphate coating a metal surface and a process for painting the coated surface |
US4717431A (en) * | 1987-02-25 | 1988-01-05 | Amchem Products, Inc. | Nickel-free metal phosphating composition and method for use |
WO1993022474A1 (en) * | 1992-05-06 | 1993-11-11 | Henkel Kommanditgesellschaft Auf Aktien | Copper-containing, nickel-free phosphatizing process |
EP0633950A1 (en) * | 1992-03-31 | 1995-01-18 | Henkel Kgaa | Nickel-free phosphatization process. |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4013483A1 (en) * | 1990-04-27 | 1991-10-31 | Metallgesellschaft Ag | METHOD FOR PHOSPHATING METAL SURFACES |
CN1022496C (en) * | 1991-06-29 | 1993-10-20 | 兰州中进高新技术公司 | Room temp. phosphorized solution and preparing method |
CN1026341C (en) * | 1992-04-21 | 1994-10-26 | 陈金田 | Low temp. rapid phosphorization agent |
-
1993
- 1993-12-15 DE DE69326021T patent/DE69326021T2/en not_active Expired - Fee Related
- 1993-12-15 CA CA002150545A patent/CA2150545A1/en not_active Abandoned
- 1993-12-15 SG SG1996005336A patent/SG55084A1/en unknown
- 1993-12-15 EP EP94904428A patent/EP0675972B1/en not_active Expired - Lifetime
- 1993-12-15 BR BR9307702-5A patent/BR9307702A/en not_active IP Right Cessation
- 1993-12-15 JP JP6515227A patent/JPH08504890A/en active Pending
- 1993-12-15 CZ CZ19951649A patent/CZ287997B6/en not_active IP Right Cessation
- 1993-12-15 PL PL93309404A patent/PL309404A1/en unknown
- 1993-12-15 AU AU58481/94A patent/AU5848194A/en not_active Abandoned
- 1993-12-15 AT AT94904428T patent/ATE183247T1/en not_active IP Right Cessation
- 1993-12-15 WO PCT/US1993/012044 patent/WO1994014999A1/en active IP Right Grant
- 1993-12-15 ES ES94904428T patent/ES2136726T3/en not_active Expired - Lifetime
- 1993-12-22 CN CN93119949A patent/CN1092245C/en not_active Expired - Fee Related
- 1993-12-22 ZA ZA939636A patent/ZA939636B/en unknown
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB526816A (en) * | 1939-03-14 | 1940-09-26 | Samuel Thomas Roberts | Improvements in the conversion of zinc, zinc alloy, galvanised, cadmium and cadmium alloy surfaces for ensuring paint and enamel adhesion |
US2813812A (en) * | 1952-06-24 | 1957-11-19 | Parker Rust Proof Co | Method for coating iron or zinc with phosphate composition and aqueous solution therefor |
FR1465983A (en) * | 1965-11-06 | 1967-01-13 | Parker Ste Continentale | Process for treating steel for the application of electrophoresis paint |
DE2049350A1 (en) * | 1969-10-08 | 1971-04-15 | Lubrizol Corp | Phosphating solutions and their use for the corrosion protection of ferrous metal and zinc surfaces |
FR2203893A1 (en) * | 1972-10-20 | 1974-05-17 | Fosfa Col Sas Di A Dal Pane Et | Ambient temp. phosphating - using accelerator contg. bath to produce coating espec. amenable to accepting electrophoretic paint coatings |
EP0123980A1 (en) * | 1979-05-02 | 1984-11-07 | Amchem Products, Inc. | Composition and process for zinc phosphate coating a metal surface and a process for painting the coated surface |
US4717431A (en) * | 1987-02-25 | 1988-01-05 | Amchem Products, Inc. | Nickel-free metal phosphating composition and method for use |
EP0633950A1 (en) * | 1992-03-31 | 1995-01-18 | Henkel Kgaa | Nickel-free phosphatization process. |
WO1993022474A1 (en) * | 1992-05-06 | 1993-11-11 | Henkel Kommanditgesellschaft Auf Aktien | Copper-containing, nickel-free phosphatizing process |
Non-Patent Citations (1)
Title |
---|
CHEMICAL ABSTRACTS, vol. 80, no. 1, 14 January 1974, Columbus, Ohio, US; abstract no. 6279w, IMAO H.: "Pretreating metal before electrocoating" page 195; * |
Also Published As
Publication number | Publication date |
---|---|
EP0675972B1 (en) | 1999-08-11 |
EP0675972A1 (en) | 1995-10-11 |
CA2150545A1 (en) | 1994-07-07 |
CN1090606A (en) | 1994-08-10 |
PL309404A1 (en) | 1995-10-02 |
CZ164995A3 (en) | 1996-01-17 |
CN1092245C (en) | 2002-10-09 |
WO1994014999A1 (en) | 1994-07-07 |
ZA939636B (en) | 1994-08-15 |
DE69326021D1 (en) | 1999-09-16 |
CZ287997B6 (en) | 2001-03-14 |
JPH08504890A (en) | 1996-05-28 |
DE69326021T2 (en) | 1999-12-23 |
AU5848194A (en) | 1994-07-19 |
BR9307702A (en) | 1999-08-31 |
ES2136726T3 (en) | 1999-12-01 |
ATE183247T1 (en) | 1999-08-15 |
SG55084A1 (en) | 1998-12-21 |
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