EP0304108A1 - Procédé de phosphatation de métaux - Google Patents
Procédé de phosphatation de métaux Download PDFInfo
- Publication number
- EP0304108A1 EP0304108A1 EP88201613A EP88201613A EP0304108A1 EP 0304108 A1 EP0304108 A1 EP 0304108A1 EP 88201613 A EP88201613 A EP 88201613A EP 88201613 A EP88201613 A EP 88201613A EP 0304108 A1 EP0304108 A1 EP 0304108A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- phosphating
- value
- phosphating solutions
- range
- spray
- 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
- C23C22/34—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
- the invention relates to a method for phosphating steel and / or galvanized steel, optionally together with additionally present aluminum, before painting with phosphating solutions based on zinc magnesium phosphate.
- the object of the invention is to provide a process for the phosphating of steel and / or galvanized steel, optionally together with additionally present aluminum, as a pretreatment for the coating, which does not have the aforementioned disadvantages, but rather enables uniform phosphate layers to be produced on the metals , which are excellent as a basis for painting.
- the method according to the invention is suitable for the phosphating of all unalloyed and low-alloy steels.
- galvanized steel is understood to mean steel which, for example, on the hot-dip path or in the electrolytic process with zinc or zinc alloy coatings e.g. Pure zinc, zinc nickel, zinc iron, zinc aluminum was coated.
- zinc or zinc alloy coatings e.g. Pure zinc, zinc nickel, zinc iron, zinc aluminum was coated.
- aluminum in the sense of the invention includes Pure aluminum and alloys of aluminum with magnesium, zinc, copper, silicon, manganese etc.
- the concentration of fluoride detected with the fluoride-sensitive electrode corresponds approximately to that in the Phosphating solution present proportion of dissociated fluoride (F ⁇ ).
- F (el) value 80 to 400 mg / l at the usual phosphating bath pH values of the baths, about 0.4 to 0.9 g / l NH4HF2 or equivalent amounts of other single fluoride-containing compounds must be added will.
- the bath is preferably supplemented by adding enough fluoride-containing compound to the phosphating bath until the desired measured value of F (el) is reached.
- the metal surfaces to be treated must be free from disruptive deposits of oils, lubricants, oxides and the like, which can impair proper layer formation.
- the surfaces are cleaned in a suitable manner.
- the surface is preferably coated with an activating agent known per se, e.g. an aqueous suspension containing titanium phosphate, activated.
- the activating agent can be used in the cleaning bath or as a separate process step.
- the phosphating solutions according to the invention are used in spraying, spray-immersion or immersion at temperatures between 40 and 60 ° C.
- the times during which the metal surfaces are brought into contact with the phosphating solution to form a covering phosphate layer are in the case of galvanized steel, e.g. between 20 sec and 10 min, for steel and aluminum e.g. between 1 and 10 min.
- the cations zinc, magnesium and nickel are in the Phosphating solution introduced, for example, as metal, oxide, carbonate, phosphate, nitrate, chloride and / or complex fluoride.
- the phosphate portion is fed to the solution via phosphates and / or phosphoric acid.
- additional cations for example Na, K, NH4 or anions, for example nitrate, chloride, sulfate, are used.
- the value of the free acid (total acid) is identical to the consumption of ml 0.1 n NaOH for neutralizing a 10 ml bath sample against the first turning point (second turning point) of the phosphoric acid.
- the phosphating bath also contains at least one oxidizing agent from the group consisting of nitrate, nitrite, chlorate, bromate, peroxide and nitrobene sulfonate, e.g. the following quantities can be used: 2 to 20 g / l nitrate; 0.05 to 0.5 g / l nitrite; 0.5 to 5 g / l chlorate; 0.2 to 3 g / l bromate; 0.02 to 0.1 g / l peroxide; 0.1 to 1 g / l nitrobenzenesulfonate.
- the oxidizing agents can also be combined with one another, e.g. Nitrate nitrite, (nitrate) chlorate nitrite, nitrate bromate, (nitrate) chlorate nitrobenzenesulfonate, nitrate nitrobenzenesulfonate.
- the three components chloride and / or Bromide), (nitrate) and (nickel) only two each in a concentration of more than 0.1 g / l, while the third may only be present in a maximum concentration of 0.1 g / l.
- Chloride and bromide are counted as one component and their individual concentrations are added. Chloride can, for example, get into the phosphating bath from the preparation water for the phosphating solution and / or as a reduction product of chlorate.
- the bromate accelerator in particular is to be regarded as the source.
- the phosphating bath preferably contains simple and / or complex fluoride.
- the group of suitable complex fluorides includes e.g. Fluoroborates and fluorosilicates.
- the phosphating solutions used in the process according to the invention can also contain further additives, but mostly in minor amounts. These include Copper, manganese, calcium, iron, cobalt, polyphosphates, polyhydroxycarboxylic acids, surfactants and agents for influencing the sludge separation.
- the phosphate layers produced according to the invention are used as preparation for a subsequent painting. They are preferably used for workpieces which are subsequently electrocoated, in particular cathodically electrocoated. In this way you get layers of paint, which are characterized by a high resistance to infiltration when exposed to corrosion, e.g. normal outdoor weathering, outdoor weathering accelerated with salt, moisture, salt spray and washing liquor and have very good adhesion to scratching and impact stress before and after corrosion.
- the method according to the invention is particularly suitable for the pretreatment of housings for household appliances and technical apparatus, of metal furniture, of vehicle bodies and of vehicle accessories before painting.
- Sheets made of steel, electrolytically galvanized steel, hot-dip galvanized steel and AlMgSi were treated after alkaline cleaning, water rinsing and activation in an aqueous titanium phosphate suspension with the phosphating solutions listed in the table at 50 ° C for 2 minutes by spraying or 3 minutes by immersion. This was followed by rinsing with water, an aqueous passivating solution containing chromium (VI), demineralized water and a drying stage.
- VI chromium
- the layers were provided with a cathodic electrodeposition paint and an automotive paint structure and subjected to the usual technical tests. In all cases where crystalline layers were present on the metal substrate, excellent test results were achieved.
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)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3727613 | 1987-08-19 | ||
DE3727613 | 1987-08-19 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0304108A1 true EP0304108A1 (fr) | 1989-02-22 |
EP0304108B1 EP0304108B1 (fr) | 1992-05-13 |
Family
ID=6334038
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP88201613A Expired - Lifetime EP0304108B1 (fr) | 1987-08-19 | 1988-07-26 | Procédé de phosphatation de métaux |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0304108B1 (fr) |
JP (1) | JP2680618B2 (fr) |
CA (1) | CA1333147C (fr) |
DE (1) | DE3871031D1 (fr) |
ES (1) | ES2036666T3 (fr) |
GB (1) | GB2208876B (fr) |
ZA (1) | ZA886167B (fr) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1991004354A1 (fr) * | 1989-09-21 | 1991-04-04 | Henkel Corporation | Articles a surfaces zinciferes presentant une resistance a la corrosion avant peinture amelioree, et leurs procedes de fabrication et d'utilisation |
EP0434358A2 (fr) * | 1989-12-19 | 1991-06-26 | Nippon Paint Co., Ltd. | Procédé de phosphatation au phosphate de zinc de surfaces métalliques |
EP0452638A1 (fr) * | 1990-03-16 | 1991-10-23 | Mazda Motor Corporation | Méthode de traitement pour la phosphatation de surfaces métalliques |
WO1993014241A1 (fr) * | 1992-01-13 | 1993-07-22 | Henkel Corporation | Procede de traitement par conversion acide d'un metal contenant de l'aluminium |
EP0613964A1 (fr) * | 1993-03-02 | 1994-09-07 | Metallgesellschaft Aktiengesellschaft | Procédé facilitant la déformation à froid |
EP0659906A1 (fr) * | 1993-12-21 | 1995-06-28 | Mazda Motor Corporation | Procédé et solution de phosphatation de surfaces métalliques |
US5454882A (en) * | 1992-01-13 | 1995-10-03 | Henkel Corporation | Process for controlling a fluoride containing conversion coating forming composition during its use for conversion coating aluminum containing metal |
WO1997021850A1 (fr) * | 1995-12-14 | 1997-06-19 | Ppg Industries, Inc. | Compositions pour revetement de conversion en phosphate de zinc et procede afferent |
WO1997030189A1 (fr) * | 1996-02-19 | 1997-08-21 | Henkel Kommanditgesellschaft Auf Aktien | Procede de phosphatisation au zinc a l'aide de faibles teneurs en nickel et/ou en cobalt |
EP0728851B1 (fr) * | 1994-12-27 | 2000-03-15 | Sermatech International Inc. | Composition de revêtement respectant l'environnement |
WO2000068154A1 (fr) * | 1999-05-07 | 2000-11-16 | Henkel Kommanditgesellschaft Auf Aktien | Procede de phosphatation au zinc au moyen d'une solution a faible teneur en nickel et traitement consecutif des eaux usees |
CN102430506A (zh) * | 2011-12-15 | 2012-05-02 | 江苏腾奇电力设备科技有限公司 | 用于散热器铸件的涂漆工艺 |
EP2767615A1 (fr) * | 2005-12-09 | 2014-08-20 | Henkel AG&Co. KGAA | Procédé au trempé et solution acide sans chrome destinés au traitement anticorrosion de surfaces en aciers |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3828676A1 (de) * | 1988-08-24 | 1990-03-01 | Metallgesellschaft Ag | Phosphatierverfahren |
DE4131382A1 (de) * | 1990-09-21 | 1992-03-26 | Kobe Steel Ltd | Oberflaechenbehandeltes aluminiumlegierungsblech fuer den automobilbau und verfahren zu dessen herstellung |
US5144611A (en) * | 1990-10-01 | 1992-09-01 | International Business Machines Corporation | Optical disk drive cleaner cartridge |
JPH05306497A (ja) | 1992-04-30 | 1993-11-19 | Nippondenso Co Ltd | リン酸塩化成処理方法 |
US6413588B1 (en) | 1999-01-11 | 2002-07-02 | E. I. Du Pont De Nemours And Company | Method of producing durable layered coatings |
JP4658339B2 (ja) * | 2001-01-17 | 2011-03-23 | 日本ペイント株式会社 | 金属表面処理方法 |
JP5119864B2 (ja) * | 2006-10-31 | 2013-01-16 | Jfeスチール株式会社 | リン酸塩処理亜鉛系めっき鋼板及びその製造方法 |
SG176435A1 (en) | 2006-10-31 | 2011-12-29 | Jfe Steel Corp | Phosphate-treated galvanized steel sheet and method for making the same |
JP4992385B2 (ja) * | 2006-10-31 | 2012-08-08 | Jfeスチール株式会社 | 有機樹脂被覆リン酸塩処理亜鉛系めっき鋼板及びその製造方法 |
JP2007314888A (ja) * | 2007-07-17 | 2007-12-06 | Toyota Motor Corp | 多層塗膜構造 |
ES2397997B1 (es) * | 2010-03-22 | 2014-01-17 | Roberto Ruiz Sanz | Depósito by pass para aire comprimido. |
KR101830508B1 (ko) * | 2016-06-24 | 2018-02-21 | 주식회사 포스코 | 내변색성 및 필름 접착성이 우수한 인산염 처리 아연계 도금강판 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2049350A1 (de) * | 1969-10-08 | 1971-04-15 | Lubrizol Corp | Phosphatierungslosungen und ihre Verwendung zum Korrosionsschutz von Eisen metall und Zinkoberflachen |
FR2111665A1 (fr) * | 1970-10-16 | 1972-06-09 | Lubrizol Corp | |
FR2231775A1 (en) * | 1973-05-29 | 1974-12-27 | Parker Ste Continentale | Phosphate-coating solns. - free from formation of water-soluble salts during neutralization |
WO1985003089A1 (fr) * | 1984-01-06 | 1985-07-18 | Ford Motor Company | Revetement de conversion de phosphate a resistance alcaline |
EP0258922A1 (fr) * | 1986-09-05 | 1988-03-09 | Metallgesellschaft Ag | Procédé pour produire des revêtements de phosphate et leur utilisation |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB648888A (en) * | 1947-04-25 | 1951-01-17 | Walterisation Company Ltd | Improvements in the production of phosphate coatings on metal surfaces |
JPS5165041A (en) * | 1974-12-04 | 1976-06-05 | Nippon Packaging Kk | Kinzokuno rinsanenhimakukeiseihoho |
US4529451A (en) * | 1983-01-03 | 1985-07-16 | Detrex Chemical Industries, Inc. | Zinc phosphate coated metal and process of producing same |
DE3311738A1 (de) * | 1983-03-31 | 1984-10-04 | Metallgesellschaft Ag, 6000 Frankfurt | Verfahren zur phosphatierung von metalloberflaechen |
DE3408577A1 (de) * | 1984-03-09 | 1985-09-12 | Metallgesellschaft Ag, 6000 Frankfurt | Verfahren zur phosphatierung von metallen |
US4595424A (en) * | 1985-08-26 | 1986-06-17 | Parker Chemical Company | Method of forming phosphate coating on zinc |
-
1988
- 1988-07-26 EP EP88201613A patent/EP0304108B1/fr not_active Expired - Lifetime
- 1988-07-26 DE DE8888201613T patent/DE3871031D1/de not_active Expired - Lifetime
- 1988-07-26 ES ES198888201613T patent/ES2036666T3/es not_active Expired - Lifetime
- 1988-08-09 CA CA000574254A patent/CA1333147C/fr not_active Expired - Fee Related
- 1988-08-12 JP JP63200322A patent/JP2680618B2/ja not_active Expired - Lifetime
- 1988-08-19 GB GB8819791A patent/GB2208876B/en not_active Expired - Lifetime
- 1988-08-19 ZA ZA886167A patent/ZA886167B/xx unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2049350A1 (de) * | 1969-10-08 | 1971-04-15 | Lubrizol Corp | Phosphatierungslosungen und ihre Verwendung zum Korrosionsschutz von Eisen metall und Zinkoberflachen |
FR2111665A1 (fr) * | 1970-10-16 | 1972-06-09 | Lubrizol Corp | |
FR2231775A1 (en) * | 1973-05-29 | 1974-12-27 | Parker Ste Continentale | Phosphate-coating solns. - free from formation of water-soluble salts during neutralization |
WO1985003089A1 (fr) * | 1984-01-06 | 1985-07-18 | Ford Motor Company | Revetement de conversion de phosphate a resistance alcaline |
EP0258922A1 (fr) * | 1986-09-05 | 1988-03-09 | Metallgesellschaft Ag | Procédé pour produire des revêtements de phosphate et leur utilisation |
Cited By (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1991004354A1 (fr) * | 1989-09-21 | 1991-04-04 | Henkel Corporation | Articles a surfaces zinciferes presentant une resistance a la corrosion avant peinture amelioree, et leurs procedes de fabrication et d'utilisation |
EP0434358A2 (fr) * | 1989-12-19 | 1991-06-26 | Nippon Paint Co., Ltd. | Procédé de phosphatation au phosphate de zinc de surfaces métalliques |
EP0434358A3 (en) * | 1989-12-19 | 1992-10-28 | Nippon Paint Co., Ltd. | Method for phosphating metal surface with zinc phosphate |
US5399208A (en) * | 1989-12-19 | 1995-03-21 | Nippon Paint Co., Ltd. | Method for phosphating metal surface with zinc phosphate |
EP0452638A1 (fr) * | 1990-03-16 | 1991-10-23 | Mazda Motor Corporation | Méthode de traitement pour la phosphatation de surfaces métalliques |
WO1993014241A1 (fr) * | 1992-01-13 | 1993-07-22 | Henkel Corporation | Procede de traitement par conversion acide d'un metal contenant de l'aluminium |
US5454882A (en) * | 1992-01-13 | 1995-10-03 | Henkel Corporation | Process for controlling a fluoride containing conversion coating forming composition during its use for conversion coating aluminum containing metal |
EP0613964A1 (fr) * | 1993-03-02 | 1994-09-07 | Metallgesellschaft Aktiengesellschaft | Procédé facilitant la déformation à froid |
US5415701A (en) * | 1993-03-02 | 1995-05-16 | Metallgesellschaft Aktiengesellschaft | Process for facilitating cold-working operations |
CN1040779C (zh) * | 1993-03-02 | 1998-11-18 | 金属股份公司 | 便于冷加工操作的方法 |
US5536336A (en) * | 1993-12-21 | 1996-07-16 | Nippon Paint Co., Ltd. | Method of phosphating metal surfaces and treatment solution |
EP0659906A1 (fr) * | 1993-12-21 | 1995-06-28 | Mazda Motor Corporation | Procédé et solution de phosphatation de surfaces métalliques |
EP0728851B1 (fr) * | 1994-12-27 | 2000-03-15 | Sermatech International Inc. | Composition de revêtement respectant l'environnement |
WO1997021850A1 (fr) * | 1995-12-14 | 1997-06-19 | Ppg Industries, Inc. | Compositions pour revetement de conversion en phosphate de zinc et procede afferent |
US5797987A (en) * | 1995-12-14 | 1998-08-25 | Ppg Industries, Inc. | Zinc phosphate conversion coating compositions and process |
US5868874A (en) * | 1995-12-14 | 1999-02-09 | Ppg Industries, Inc. | Zinc phosphate conversion coating compositions and process |
WO1997030189A1 (fr) * | 1996-02-19 | 1997-08-21 | Henkel Kommanditgesellschaft Auf Aktien | Procede de phosphatisation au zinc a l'aide de faibles teneurs en nickel et/ou en cobalt |
WO2000068154A1 (fr) * | 1999-05-07 | 2000-11-16 | Henkel Kommanditgesellschaft Auf Aktien | Procede de phosphatation au zinc au moyen d'une solution a faible teneur en nickel et traitement consecutif des eaux usees |
EP2767615A1 (fr) * | 2005-12-09 | 2014-08-20 | Henkel AG&Co. KGAA | Procédé au trempé et solution acide sans chrome destinés au traitement anticorrosion de surfaces en aciers |
CN102430506A (zh) * | 2011-12-15 | 2012-05-02 | 江苏腾奇电力设备科技有限公司 | 用于散热器铸件的涂漆工艺 |
Also Published As
Publication number | Publication date |
---|---|
ES2036666T3 (es) | 1993-06-01 |
CA1333147C (fr) | 1994-11-22 |
ZA886167B (en) | 1990-04-25 |
GB8819791D0 (en) | 1988-09-21 |
EP0304108B1 (fr) | 1992-05-13 |
JPS6468481A (en) | 1989-03-14 |
GB2208876B (en) | 1991-08-14 |
JP2680618B2 (ja) | 1997-11-19 |
GB2208876A (en) | 1989-04-19 |
DE3871031D1 (de) | 1992-06-17 |
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