EP0765405A1 - Process for forming a phosphate conversion coating - Google Patents
Process for forming a phosphate conversion coatingInfo
- Publication number
- EP0765405A1 EP0765405A1 EP95926607A EP95926607A EP0765405A1 EP 0765405 A1 EP0765405 A1 EP 0765405A1 EP 95926607 A EP95926607 A EP 95926607A EP 95926607 A EP95926607 A EP 95926607A EP 0765405 A1 EP0765405 A1 EP 0765405A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- conversion coating
- fluoride
- process according
- sludge
- cationic polymeric
- 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.)
- Withdrawn
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
- C23C22/34—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
- C23C22/73—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
- C23C22/86—Regeneration of coating baths
Definitions
- This invention relates to a method for forming a phosphate conversion coating on metal surfaces that include at least some aluminiferous metal surfaces, which for the purposes of the present invention are to be understood as those containing at least 0.5 % of aluminum in their surfaces, are generally exemplified by aluminum sheet, steel sheet plated with Zn-AI alloy, aluminum- plated steel sheet, and the like, and are found, for example, on automotive outer body sheet, on colored sheet-metal roofing material, and so forth.
- Phosphate conversion coating of metals forms on the metal surface a coating, with a chemical composition typified by Zn 3 (P0 4 ) 2 *nH 2 0, Zn 2 Fe(P0 4 ) 2 * > n H 2 0, and/or Zn 2 Ca(P0 4 ) 2 «> nH 2 0 for the example of zinc phos ⁇ phate treatments.
- This is brought about by contacting the metal surface, usually by spraying or dipping, with a phosphate liquid conversion coating composition in order to dissolve the surface of the metal.
- Phosphate conversion coatings im ⁇ prove the metal's resistance to rusting and its paint adherence.
- Zinc phosphate liquid conversion coating compositions contain phosphoric acid, Zn 2+ ions, and water as their essential components and may contain, for ex- ample, Ni 2+ , Mn 2+ , Ca 2+ , Fe 2+ , H + , Na + , K + , NH 4 + , N0 3 " , NO/, fluoride (which may be simple fluoride and/or complex fluorides such as fluozirocnate, fluosilicate, fluoborate, and the like), S0 4 2" , Cl " , or the like, as optional components.
- the list ⁇ ed components represent those in general use for phosphate liquid conversion coating compositions.
- Phosphate sludge i.e., FeP0 4 » n H 2 0, Zn 3 (P0 4 ) 2 * n H 2 0, etc.
- Sludge-eliminating measures such as filtration and sedimentation are therefore ordinarily used since a low sludge content in the liquid conversion coating composition is desirable for forming phosphate conversion coatings.
- Zn-AI alloy-plated steel sheet exhibits a better corrosion resistance and heat resistance than ordinary Zn-plated steel sheet, and as a result its applica ⁇ tions as a corrosion-resistant material have in recent years been undergoing act ⁇ ive development.
- steel sheet plated with Zn containing approxi ⁇ mately 5 % of aluminum is widely used where painting is to be executed on the steel sheet.
- this type of steel sheet is subjected to phosphate conversion coating, aluminum ions accumulate in the treatment bath. Removal of aluminum ions from the reaction system is desired because aluminum ions are unnecessary and in fact detrimental to phosphate conversion coating.
- a sludge such as Nal AIFg, NasAIFg, etc., may also be deliberately produced, in addition to the phosphate sludge which arises spontaneously during conversion coating of any ferrous and/or zinciferous surface.
- the term "sludge” designates a mixture of (a) solids, such as the phos ⁇ phates and aluminum compounds produced by the reactions occurring during phosphate conversion coating of the metal or produced by the addition of NaHF 2 , KHF 2 , etc., plus (b) small amounts of metal salts not due to the aforesaid reac- tions, plus (c) atmospheric dust and entrained contamination adhering on the metal.
- This sludge is therefore typically a mixture of components such as zinc phosphate, iron phosphate, aluminum compounds such as cryolite (Na 3 AIF 6 ) or elpasolite (Naf AIFg), entrained contaminants, dust, and the like.
- Japanese Patent Application Laid Open [Kokai or Unexamined] Number Sho 57-70281 [70,281/1982] discloses a phosphate conversion coating method that maintains the Al ion concentration in a zinc phosphate liquid conversion coating composition at 50 parts per million (hereinafter usually abbreviated "ppm") or less.
- the Al elution into a zinc phosphate liquid conversion coating composition is 0.2 x 10 "3 to 1.0 x 10 "3 moles per square meter, herein ⁇ after usually abbreviated as "mol/m 2 ".
- the prescribed Al ion concentration is ob ⁇ tained in this method by the precipitative removal of Al from the reaction system as elpasolite (NaKzAIFe).
- Japanese Patent Application Laid Open [Kokai or Unexamined] Number Sho 60-204889 [204,889/1985] discloses a phosphate conversion coating meth ⁇ od that is directed to zinc phosphate conversion coating liquid compositions whose principal ingredients are 0.85 to 1.7 grams per liter (hereinafter usually ab- breviated as "g/L") of Zn ions, 1.0 to 2.5 g/L of Ni ions, 5.5 to 10 g/L of P0 4 ions, 0.8 to 1.5 g/L of N0 3 ions, 1.3 to 5.5 g/L of F ions, and small quantities of addit ⁇ ives.
- g/L grams per liter
- NaHF 2 and KHF 2 — or NaHF 2 and KF — are intermittently added to such liquid compositions in a quantity no more than equimolar with the quantity of Al in the liquid conversion coating composition.
- Japanese Patent Application Laid Open [Kokai or Unexamined] Number Sho 56-105485 [105,485/1981] teaches a method that facilitates sludge filtration.
- a polymeric coagulant is added to the conversion coating liquid composition in the phosphate conversion coating of cold-rolled steel sheet.
- the addition of this polymeric coagulant improves the sedimentability of the phos ⁇ phate compound-containing sludge.
- this method was not investigated with regard to the sedimentation of aluminum compound-containing sludge.
- One object of the present invention is to solve the quality and mainte ⁇ nance problems during phosphate conversion coatings, by prior art methods, that are caused by aluminum compound-containing sludges, especially the problems noted above.
- percent, "parts of, and ratio values are by weight;
- the term “polymer” includes “oligomer”, “copolymer”, “terpolymer”, and the like;
- the first definition or description of the meaning of a word, phrase, acro- nym, abbreviation or the like applies to all subsequent uses of the same word, phrase, acronym, abbreviation or the like and applies, mutatis mutandis, to nor ⁇ mal grammatical variations thereof;
- the description of a group or class of mater ⁇ ials as suitable or preferred for a given purpose in connection with the invention implies that mixtures of any two or more of the members of the group or class are equally suitable or preferred;
- specification of materials in ionic form implies the presence of sufficient counterions to produce electrical neutrality for the com ⁇ position as a whole; and any counterions thus implicitly specified preferably are selected from among other constituents explicitly specified in ionic form, to the extent possible; otherwise such counterions may be freely selected, except for avoiding counter
- Aluminum compound-containing sludge at some point becomes suspend ⁇ ed in the liquid conversion coating composition during processes that remove Al ions — which can prevent formation of the phosphate conversion coating — from the reaction system, and, since aluminum compound-containing sludge has a low sedimentability, it gradually accumulates in the liquid conversion coating composition.
- Aluminum compound-containing sludge is more soluble in water than other phosphate-based sludges; therefore, the former is more easily dis ⁇ solved by the moisture permeating through paint films.
- the invention applies to the use of a phosphate conversion coating liquid composition that contains fluoride, in addition to the essential components listed above (phosphoric acid, zinc, and water).
- the fluoride is desired for its good etching activity on aluminiferous surfaces, which is necessary for the production of the best quality phosphate films on aluminiferous metals.
- the essence of the invention is the use of at least one cationic coagulant to cause coagulation and sedimentation of sludge suspended in a fluoride-containing phosphate conver ⁇ sion coating liquid composition, in which at least part of the sludge includes alum- inum compounds.
- cationic polymeric coagulant is able to prevent quality deterioration during prolonged use of the same volume of phosphating liquid composition, by preventing substantial contact between the aluminum compound-containing sludge and the conversion coated workpiece.
- the inventors obtained the following information from experiments into a means by which polymeric coagulant(s) would be able to induce the coagulation, enlargement, and sedimentation of each sludge component present in a fluoride- containing phosphate conversion coating liquid composition.
- the addition of the cationic polymeric coagulant first is pre- ferred.
- the cationic coagulant whose addition is necessary to induce coagulation and en ⁇ largement—is preferably added in a quantity at least as large as that of the anionic coagulant.
- the aluminum compound- free sludge is first coagulated and sedimented using an anionic polymeric coagulant, a condition is produced in which aluminum compound-contain ⁇ ing sludge is suspended in the liquid conversion coating composition.
- the cationic polymeric coagulant When the cationic polymeric coagulant is then added to liquid conversion coating composition in this state, it is preferably added in a quantity at least as large as the addition of anionic coagulant.
- the method for introducing the cationic coagulant into the phosphate liquid conversion coating composition is not critical to the present invention, and any method may be used that establishes the presence of the cationic coagulant in the liquid conversion coating composition. Preferred specific methodologies are (1) replenishment with a base or secondary ingredient to which the cationic coagulant has been preliminarily added, and (2) addition of an aqueous solution prepared by dilution of the cationic coagulant in phosphate liquid conversion coating composition.
- the cationic coagulant should as a general rule be used at a concentra ⁇ tion of 1 to 100 ppm, and preferably 2 to 10 ppm. Within these ranges, the opti ⁇ mum concentration is more or less determined by the content and particle size of the sludge.
- the cationic coagulant has a reduced effect at a concentration be- low 1 ppm, while concentrations exceeding 100 ppm are economically undesir ⁇ able.
- the cationic polymeric coagulant may have a strong, moderate, or weak ionic strength, be ⁇ cause all of these are effective and practical.
- the molecular weight of the cation ⁇ ic polymeric coagulant is preferably 1*10 5 to 2*10 7 .
- the suspended sludge concentration prior to addition of the cationic poly- meric coagulant is not narrowly limited for the present invention, but as a general rule will be 100 to 10,000 ppm, assuming treatment in existing continuous con ⁇ version coating lines.
- the proportion of aluminum compound-containing sludge in this concentration increases with elapsed treatment time and in some cases may reach as high as 50 % of the total sludge, or 5,000 ppm, based on the entire phosphating liquid composition.
- Either of the above-described addition methods (1) and (2) can reduce the suspended sludge concentration to 0.1 to 10 ppm within a few minutes after coagulant addition.
- Nonionic coagulant or anionic coagulant may also be added on an option ⁇ al basis in the execution of the present invention in order to sediment sludge other than aluminum compound-containing sludge.
- test liquid conversion coating composition was prepared as follows: First, Al sheet and cold-rolled steel sheet were subjected to zinc phosphate con ⁇ version coating to give approximately 100 ppm of Al ions and approximately 2,000 ppm of phosphate sludge in the liquid conversion coating composition. After this, aluminum compound-containing sludge was produced by adding a co ⁇ agulant, thus yielding the test liquid conversion coating composition. The evalu ⁇ ations were conducted by the methods described below.
- Aluminum sheet was treated using liquid conversion coating composition obtained by the addition of coagulant to test liquid conversion coating composi ⁇ tion. The status of the coating was then visually inspected. ⁇ 4 ⁇ Water-resistant secondary adherence Aluminum sheet was treated with test liquid conversion coating composi ⁇ tion and then rinsed with water and dried. This was followed by cationic electro- deposition of a base protective coating, an intermediate coating, and a top coat- ing, in each case equivalent to automotive applications, to give the test coupon. After the test coupon had been immersed for 240 hours in deionized water at 40 °C, a Crosshatch pattern (2 x 2 mm, 100 squares) was scribed down to the alum ⁇ inum sheet. An adherence test was then conducted by tape peeling. Test liquid conversion coating composition
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)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP15990194A JPH0820876A (en) | 1994-07-12 | 1994-07-12 | Phosphate chemical conversion treatment |
JP159901/94 | 1994-07-12 | ||
PCT/US1995/008228 WO1996001914A1 (en) | 1994-07-12 | 1995-07-11 | Process for forming a phosphate conversion coating |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0765405A1 true EP0765405A1 (en) | 1997-04-02 |
EP0765405A4 EP0765405A4 (en) | 1997-06-04 |
Family
ID=15703651
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95926607A Withdrawn EP0765405A4 (en) | 1994-07-12 | 1995-07-11 | Process for forming a phosphate conversion coating |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0765405A4 (en) |
JP (1) | JPH0820876A (en) |
CA (1) | CA2194910A1 (en) |
WO (1) | WO1996001914A1 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100317680B1 (en) * | 1999-04-29 | 2001-12-22 | 이계안 | Surface treatment agent for treating aluminium alloy and steel plate simultaneously before painting |
AU2002237525B2 (en) | 2001-02-26 | 2005-03-10 | Nippon Steel Corporation | Surface treated steel product, method for production thereof and chemical conversion treatment solution |
JP4815072B2 (en) * | 2001-07-31 | 2011-11-16 | 日本ペイント株式会社 | Sludge concentration method, concentrated sludge obtained by this method, and sludge concentration device |
EP1521863B1 (en) | 2002-07-10 | 2008-06-25 | Chemetall GmbH | Method for coating metallic surfaces |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS53109871A (en) * | 1977-03-07 | 1978-09-26 | Nippon Paint Co Ltd | Treating method for sludge by-product formed in chemical treatment of zinc phosphate film |
JPS56105485A (en) * | 1980-01-24 | 1981-08-21 | Nippon Parkerizing Co Ltd | Chemical conversion process for phosphate coating |
JPS5770281A (en) * | 1980-10-20 | 1982-04-30 | Nisshin Steel Co Ltd | Zinc phosphate treatment of zinc hot dipping steel plate |
JPS60204889A (en) * | 1984-03-29 | 1985-10-16 | Nisshin Steel Co Ltd | Zinc phosphate treatment of steel sheet plated with zn-al alloy |
EP0434358A2 (en) * | 1989-12-19 | 1991-06-26 | Nippon Paint Co., Ltd. | Method for phosphating metal surface with zinc phosphate |
-
1994
- 1994-07-12 JP JP15990194A patent/JPH0820876A/en active Pending
-
1995
- 1995-07-11 WO PCT/US1995/008228 patent/WO1996001914A1/en not_active Application Discontinuation
- 1995-07-11 CA CA 2194910 patent/CA2194910A1/en not_active Abandoned
- 1995-07-11 EP EP95926607A patent/EP0765405A4/en not_active Withdrawn
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS53109871A (en) * | 1977-03-07 | 1978-09-26 | Nippon Paint Co Ltd | Treating method for sludge by-product formed in chemical treatment of zinc phosphate film |
JPS56105485A (en) * | 1980-01-24 | 1981-08-21 | Nippon Parkerizing Co Ltd | Chemical conversion process for phosphate coating |
JPS5770281A (en) * | 1980-10-20 | 1982-04-30 | Nisshin Steel Co Ltd | Zinc phosphate treatment of zinc hot dipping steel plate |
JPS60204889A (en) * | 1984-03-29 | 1985-10-16 | Nisshin Steel Co Ltd | Zinc phosphate treatment of steel sheet plated with zn-al alloy |
EP0434358A2 (en) * | 1989-12-19 | 1991-06-26 | Nippon Paint Co., Ltd. | Method for phosphating metal surface with zinc phosphate |
Non-Patent Citations (5)
Title |
---|
PATENT ABSTRACTS OF JAPAN vol. 002, no. 144 (C-029), 30 November 1978 & JP 53 109871 A (NIPPON PAINT CO LTD), 26 September 1978, * |
PATENT ABSTRACTS OF JAPAN vol. 005, no. 180 (C-079), 19 November 1981 & JP 56 105485 A (NIPPON PARKERIZING CO LTD), 21 August 1981, * |
PATENT ABSTRACTS OF JAPAN vol. 006, no. 149 (C-118), 10 August 1982 & JP 57 070281 A (NISSHIN STEEL CO LTD), 30 April 1982, * |
PATENT ABSTRACTS OF JAPAN vol. 010, no. 067 (C-333), 15 March 1986 & JP 60 204889 A (NITSUSHIN SEIKOU KK), 16 October 1985, * |
See also references of WO9601914A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO1996001914A1 (en) | 1996-01-25 |
JPH0820876A (en) | 1996-01-23 |
EP0765405A4 (en) | 1997-06-04 |
CA2194910A1 (en) | 1996-01-25 |
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