WO1998024946A1 - Sludge reducing zinc phosphating process and composition - Google Patents
Sludge reducing zinc phosphating process and composition Download PDFInfo
- Publication number
- WO1998024946A1 WO1998024946A1 PCT/US1997/020542 US9720542W WO9824946A1 WO 1998024946 A1 WO1998024946 A1 WO 1998024946A1 US 9720542 W US9720542 W US 9720542W WO 9824946 A1 WO9824946 A1 WO 9824946A1
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- WO
- WIPO (PCT)
- Prior art keywords
- amount
- component
- zinc
- composition according
- composition
- Prior art date
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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
- C23C22/13—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
- C23C22/34—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
- C23C22/364—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 manganese cations
- C23C22/365—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 manganese cations containing also zinc and nickel 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
- C23C22/73—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 characterised by the process
-
- 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
- C23C22/73—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 characterised by the process
- C23C22/77—Controlling or regulating of the coating process
Definitions
- the invention relates to a process for forming a zinc containing phosphate conversion coating layer on an active metal surface, more particularly a surface selected from the group consisting of (i) steel and other non-passivating ferrous alloys that contain at least
- FePO 4 the principal surface that is conversion coated is zinc
- Sludge is generated through three main pathways: Zinc dihydrogen phosphate, the zinc phosphate species with which most zinc phosphating liquid compositions are most nearly at equilibrium, is less soluble at higher temperatures than at lower temperatures, so that some sludge may form during the heating of the composition.
- the solubility of zinc dihydrogen phosphate is also pH dependent. As a result, some sludge will also form during the neutralization of the bath necessary to maintain the optimum free acid value during continued use of a composition.
- the third, and unavoidable, source of sludge when treating iron stems from the reactions that produce the phosphate conversion coating itself.
- a typical zinc phosphating bath includes phosphate ions, divalent metal ions, hydrogen ions, and an oxidizing compound such as nitrite or chlorate as the process accelerator.
- the mechanism of the reaction involves acid attack on the substrate metal, iron in this instance, at micro anodes and deposition of phosphate crystals at micro cathodes. It also involves the liberation of hydrogen and the formation of phosphate sludge. Changes in accelerator can affect the amount of sludge formed, but in general no completely satisfactory theoretical analysis for predicting the amount of sludge under a wide variety of operating conditions has been known. DESCRIPTION OF THE INVENTION Objectives of the Invention
- One major objective of the invention is to provide a method for predicting the amount of sludge generated under varying operating conditions.
- Another concurrent or alternative major objective is to provide process conditions that will lead to less sludge generation than previously used process condition, while not substantially worsening the protective and/or aesthetic quality of the phosphate coating achieved.
- Other objectives will appear from the description below.
- the amount of sludge produced and values for various protective quality related characteristics of the conversion coatings formed by zinc-manga- nese-nickel phosphating within a range of zinc, nitrite accelerator, and free acid concentrations and phosphating temperatures can be closely predicted with empirical equations, and that these equations can be used to define improved narrow operating ranges that reduce sludge without substnatially lowering protective and aesthetic values achieved by the conversion coating.
- the amount of sludge produced is defined for the purposes of this description as the stoichiometric equivalent as ferric phosphate dihydrate of the iron that is dissolved from a cold rolled steel substrate during formation of a phosphate conversion coating but is not incorporated into the coating.
- Dry Sludge Mass ⁇ Metal Loss - [Coating Weight * P-ratio * (56/449)] ⁇ x 187/56 g/ ⁇ r.
- the fraction 56/449 represents the ratio of the atomic weight of iron to the formula weight of phosphophyllite, which has the chemical formula Zn 2 Fe(PO 4 ) 2 , 4H 2 O).
- the fraction 187/56 represents the inverse ratio of the atomic weight of iron to the formula weight of FePO 4 • 2H 2 0 (sludge).
- This treatment does not ignore the facts that, in practice, the best sludge composition for easy removal has a Fe/Zn ratio of 3 : 1 and that manganese modified phosphating compositions will normally contain other metal ions than iron in the sludge. It is believed, however, and therefore assumed for purposes of this description, that the major contribution to a reduction in sludge will come from a reduction in the amount of iron dissolved in the course of phosphating but not incorporated into the coating as phosphophy
- the amounts of sludge produced during a two minute immersion time when phosphate conversion coating a cold-rolled steel surface with a coating form- ing composition having an acidic pH value and containing zinc cations, phosphate anions, and nitrite accelerator and, optionally, also one or more of manganese cations, nickel cations, simple and complex fluoride anions, and nitrate anions, varies as a function of the zinc ("z"), nitrite accelerator ("n”), and Free Acid (“f ') concentrations of the composition and the temperature ("T") at which the coating forming composition is maintained during the immersion contact, with all concentrations of other necessary and optional components recited above being held constant, according to the equation shown in Table 1 below.
- CRS Cold Rolled Steel
- Ct.Wt Coating Weight
- g/m 2 means “grams pe”
- APGE is an arbitrary designation given by the Ford Motor Company to a particular type of accelerated corrosion test procedure designed to predict the likely extent of "cosmetic” corrosion, with the test results being reported in millimeters of creep and/or corrosion from a scribe through the painted surface tested, so that lower values are preferable
- mm means “millimeters”
- * ⁇ G means ⁇ lectrogalvanized Steel", and this substrate was coated on the galvanized side
- EVA means "steel electroplated on both sides with a zinc-iron alloy”.
- one embodiment of this invention is a process for reducing the amount of sludge formed in a nitrite accelerated zinc phosphating process initially accomplished by contact at a first process temperature value ("T") between a metal substrate being phosphated and a first zinc phosphating liquid composition, the process according to the invention for reducing the amount of sludge formed comprising steps of:
- step (III) selecting at least one of a second zinc, second nitrite accelerator, and second Free Acid concentration value and a second process temperature value having the property that, when said selected second value or values is or are substituted for the corresponding first values, a second predicted sludge value calculated according to the equation recited in step (II) with the selected second value(s) substituted for the corresponding first values is smaller than said first predicted sludge value; and (IV) resuming the nitrite accelerated zinc phosphating process with a second zinc phosphating liquid composition that differs from said first zinc phosphating liquid composition by having the second value(s) selected in step (III) instead of the corresponding first values, but with other compositional characteristics the same as in said first zinc phosphating liquid.
- Table 1 The empirical equations in Table 1 were determined in the manner set forth below.
- Variable Range of Variations zinc 0.8 to l.2 g/l free acid 0.4 to 1.2 points temperature 40 to 52 °C sodium nitrite accelerator 0.09 to 0.25 g 1
- the cold rolled steel test panels used to measure metal loss and coating weight were acetone cleaned, dried, and weighed before phosphating. After phosphating the panels were reweighed, stripped of their phosphate coating using a 5 % chromic acid solution in water and then rinsed, dried, and weighed again. All other substrates were processed as received and stripped of their phosphate coatings at room temperature using a solution of 40 grams of ammonium dichromate dissolved in 2.5 liters of reagent grade aqueous ammonia. The difference in the weight of the panel before phosphating and after stripping is considered the etch weight or metal loss, while the difference in weight just before and af- ter stripping is considered the coating weight. Both metal loss and coating weight are expressed as weight per unit area.
- P-ratios of the cold rolled steel coatings were obtained by x-ray diffraction according to methods taught by T. Miyawaki, H. Okita, S. Umehara, and M. Okabe, Proc. Inter- finish, 80, 303 (1980) and/or by M. O. W. Richardson and D. B. Freeman, Tran. IMF, 64(1), 16 (1986). Analysis was made at room temperature using a copper x-ray source.
- the intensities of the peaks related to the plane (100) of phosphophyllite and to the plane (020) of hopeite were measured and used to calculate coating P-ratio, which is defined as the ratio of phosphophyllite (Fe-containing zinc phosphate) to the total of phosphophyllite and hopeite (Zn-only zinc phosphate). Metal loss, coating weight, and P-ratio results are reported as an average of triplicate samples in Table 2.
- Table 3 Listed in Table 3 are the standard deviation and R statistics for each of the regression equations in Table 1. Within the region of study, the R 2 value indicates the degree to which the regression equation explains the observed variation of the characteristic about its mean. Any single additional measurement of the characteristic should fall, with roughly a 70 % probability, within the range of the regression equation's predicted response, plus or minus the standard deviation.
- Table 4 summarizes the regression equations' predicted results for some "what if phosphating condition scenarios and the computer-determined minimum sludge conditions when performance constraints for coating weight, P-ratio, and Ford APGE cosmetic corrosion are simultaneously applied.
- Simply decreasing the free acid to its lowest setting (0.4 points, or -1) results in a 21 % reduction in sludge compared with the DOE center point.
- Operating the variables at their half-way points between their individual beneficial extremes results in a 16.5 % reduction in sludge and would present less of an operational stability problem for the zinc phosphate solution than the low free acid TABLE 3
- aqueous liquid composition for zinc phosphating said composition comprising in addition to water:
- G an amount of dissolved fluoride anions, including the stoichiometric equivalent as fluoride ions of all dissolved hydrofluoric, fluoboric (i.e., HBF 4 ), fluozirconic (i.e., H 2 ZrF 6 ), fluohafhic (i.e., H 2 HfF 6 ), fluotitanic (i.e., H 2 T ⁇ F 6 ), fluoaluminic (i.e., H 3 ASF , fluoferric (i.e., H 3 FeF 6 ), and fluosilicic (i.e., H 2 SiF 6 ) acids and of all of the partially and completely neutralized salts of all of these acids, irrespective of the actual degree of ionization prevailing in the composition, that is at least, with increasing preference in the order given, 0.10, 0.30, 0.50, 0.60, 0.70, 0.80, 0.85, 0.90, or 0.95 g/kg and independently preferably is not more than
- Another embodiment of the invention is a process of forming a zinc phosphate conversion coating on a metal substrate surface, preferably one which contains at least 50 % of at least one metal selected from the group consisting of iron, zinc, and aluminum, by contacting said surface with a composition according to the invention as described above at a temperature that preferably is at least, with increasing preference in the order given, 30, 33, 36, or 39 °C and independently preferably is, with increasing preference in the order given, not more than 60, 58, 56, 54, or 52 °C.
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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)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR9713822-3A BR9713822A (en) | 1996-12-04 | 1997-11-19 | Processes for reducing the amount of sludge formed in a nitrite-accelerated zinc phosphating process and for forming a zinc phosphate conversion coating on a metal substrate surface, and aqueous liquid composition for zinc phosphating |
CA002271921A CA2271921A1 (en) | 1996-12-04 | 1997-11-19 | Sludge reducing zinc phosphating process and composition |
EP97949395A EP1012355A1 (en) | 1996-12-04 | 1997-11-19 | Sludge reducing zinc phosphating process and composition |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/760,023 US5900073A (en) | 1996-12-04 | 1996-12-04 | Sludge reducing zinc phosphating process and composition |
US08/760,023 | 1996-12-04 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1998024946A1 true WO1998024946A1 (en) | 1998-06-11 |
Family
ID=25057820
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1997/020542 WO1998024946A1 (en) | 1996-12-04 | 1997-11-19 | Sludge reducing zinc phosphating process and composition |
Country Status (9)
Country | Link |
---|---|
US (1) | US5900073A (en) |
EP (1) | EP1012355A1 (en) |
JP (1) | JPH10168580A (en) |
CN (1) | CN1245539A (en) |
AR (1) | AR010329A1 (en) |
BR (1) | BR9713822A (en) |
CA (1) | CA2271921A1 (en) |
WO (1) | WO1998024946A1 (en) |
ZA (1) | ZA9710607B (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
MXPA02004037A (en) | 1999-11-04 | 2002-10-11 | Henkel Corp | Zinc phosphating process and composition with reduced pollution potential. |
US20050145303A1 (en) * | 2003-12-29 | 2005-07-07 | Bernd Schenzle | Multiple step conversion coating process |
US7497481B2 (en) * | 2005-05-13 | 2009-03-03 | Hydril Llc | Treating method and design method for tubular connections |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4793867A (en) * | 1986-09-26 | 1988-12-27 | Chemfil Corporation | Phosphate coating composition and method of applying a zinc-nickel phosphate coating |
US4838957A (en) * | 1982-08-24 | 1989-06-13 | Amchem Products, Inc. | Phosphate coatings for metal surfaces |
US5232523A (en) * | 1989-03-02 | 1993-08-03 | Nippon Paint Co., Ltd. | Phosphate coatings for metal surfaces |
US5536336A (en) * | 1993-12-21 | 1996-07-16 | Nippon Paint Co., Ltd. | Method of phosphating metal surfaces and treatment solution |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2389683A1 (en) * | 1977-05-03 | 1978-12-01 | Parker Ste Continentale | Phosphating soln. contg. boron fluoride - for phosphating ferrous and non-ferrous surfaces, e.g. steel, zinc and aluminium |
EP0135622B1 (en) * | 1983-08-22 | 1988-12-07 | Nippon Paint Co., Ltd. | Phosphating metal surfaces |
JPS57152472A (en) * | 1981-03-16 | 1982-09-20 | Nippon Paint Co Ltd | Phosphating method for metallic surface for cation type electrodeposition painting |
DE3244715A1 (en) * | 1982-12-03 | 1984-06-07 | Gerhard Collardin GmbH, 5000 Köln | METHOD FOR PHOSPHATING METAL SURFACES, AND BATH SOLUTIONS SUITABLE FOR THIS |
JPH0784663B2 (en) * | 1986-12-12 | 1995-09-13 | 日産自動車株式会社 | Aluminum member processing method |
JPS63227786A (en) * | 1987-03-16 | 1988-09-22 | Nippon Parkerizing Co Ltd | Phosphating method for pretreating steel sheet before coating by electrodeposition |
JPH0730455B2 (en) * | 1988-09-27 | 1995-04-05 | 日本パーカライジング株式会社 | Phosphate chemical treatment liquid |
ES2036023T3 (en) * | 1988-11-25 | 1993-05-01 | Metallgesellschaft Aktiengesellschaft | PROCEDURE FOR THE APPLICATION OF PHOSPHATE COATING. |
US5200000A (en) * | 1989-01-31 | 1993-04-06 | Nihon Parkerizing Co., Ltd. | Phosphate treatment solution for composite structures and method for treatment |
DE3918136A1 (en) * | 1989-06-03 | 1990-12-06 | Henkel Kgaa | METHOD FOR PRODUCING MANAGE-CONTAINING PHOSPHATE COATINGS ON METAL SURFACES |
DE3920296A1 (en) * | 1989-06-21 | 1991-01-10 | Henkel Kgaa | METHOD FOR PRODUCING ZINC PHOSPHATE CONTAINING MANGANE AND MAGNESIUM |
JPH07100870B2 (en) * | 1990-04-24 | 1995-11-01 | 日本ペイント株式会社 | Method for treating zinc phosphate coating on metal surface |
JP2794013B2 (en) * | 1990-10-24 | 1998-09-03 | 日本パーカライジング株式会社 | Phosphate chemical conversion treatment solution for iron-aluminum metal sheet metal construction |
-
1996
- 1996-12-04 US US08/760,023 patent/US5900073A/en not_active Expired - Lifetime
-
1997
- 1997-11-19 CN CN97180347A patent/CN1245539A/en active Pending
- 1997-11-19 BR BR9713822-3A patent/BR9713822A/en not_active Application Discontinuation
- 1997-11-19 EP EP97949395A patent/EP1012355A1/en not_active Withdrawn
- 1997-11-19 CA CA002271921A patent/CA2271921A1/en not_active Abandoned
- 1997-11-19 WO PCT/US1997/020542 patent/WO1998024946A1/en not_active Application Discontinuation
- 1997-11-25 JP JP9339406A patent/JPH10168580A/en active Pending
- 1997-11-25 ZA ZA9710607A patent/ZA9710607B/en unknown
- 1997-12-03 AR ARP970105670A patent/AR010329A1/en unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4838957A (en) * | 1982-08-24 | 1989-06-13 | Amchem Products, Inc. | Phosphate coatings for metal surfaces |
US4793867A (en) * | 1986-09-26 | 1988-12-27 | Chemfil Corporation | Phosphate coating composition and method of applying a zinc-nickel phosphate coating |
US5232523A (en) * | 1989-03-02 | 1993-08-03 | Nippon Paint Co., Ltd. | Phosphate coatings for metal surfaces |
US5536336A (en) * | 1993-12-21 | 1996-07-16 | Nippon Paint Co., Ltd. | Method of phosphating metal surfaces and treatment solution |
Non-Patent Citations (1)
Title |
---|
See also references of EP1012355A4 * |
Also Published As
Publication number | Publication date |
---|---|
JPH10168580A (en) | 1998-06-23 |
AR010329A1 (en) | 2000-06-07 |
BR9713822A (en) | 2000-03-14 |
EP1012355A4 (en) | 2000-06-28 |
CN1245539A (en) | 2000-02-23 |
US5900073A (en) | 1999-05-04 |
CA2271921A1 (en) | 1998-06-11 |
ZA9710607B (en) | 1998-06-12 |
EP1012355A1 (en) | 2000-06-28 |
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