EP0060716A1 - Phosphating metal surfaces - Google Patents
Phosphating metal surfaces Download PDFInfo
- Publication number
- EP0060716A1 EP0060716A1 EP82301330A EP82301330A EP0060716A1 EP 0060716 A1 EP0060716 A1 EP 0060716A1 EP 82301330 A EP82301330 A EP 82301330A EP 82301330 A EP82301330 A EP 82301330A EP 0060716 A1 EP0060716 A1 EP 0060716A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ion
- zinc
- process according
- solution
- iron
- 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
- C23C22/73—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
- C23C22/05—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
- C23C22/182—Orthophosphates containing manganese cations 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
- C23C22/07—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
- C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
- C23C22/184—Orthophosphates containing manganese cations containing also zinc cations containing also nickel cations
Definitions
- This invention relates to a process for phosphating metal surfaces, and to a composition suitable for use in that process.
- Japanese Patent Publication (unexamined) No.107784/ 1980 (Nippon Paint Co.Ltd.) concerns a method of phosphating iron-based metal surfaces which is particularly suitable for treating manufactured products having complicated-surfaces, such as -automobile bodies.
- the method is. in use commercially in the automotive-industry for pretreating automobile bodies prior to cationic electrocoating, which is a, coating process now used extensively in this industry.
- the phosphating method is carried-out by first subjecting the metal surface to a dipping treatment with an acidic aqueous solution containing 0.5 to 1.5 g/l of zinc ion, 5 to 30 g/l of phosphate-ion, and 0.01 to 0.2 g/1 of nitrite ion and/or 0.05 to 2 g/1 of m-nitrobenzenesulfonate ion at a bath temperature of 40 to 70°C for 15 seconds or more, followed by spraying with the above solution for 2 seconds or more.
- the present invention provides an improved phosphating method for metal surfaces, which is particularly suitable for treating metal surfaces, such as-those of car bodies, which have both iron-based surfaces and zinc-based surfaces.
- the method is especially advantageous for forming phosphate coating films suitable for electrocoating particularly cationic electrocoating.
- the invention provides a process for phosphating an iron- or zinc-based metal surface comprising subjecting the metal surface to a dipping treatment in an acidic aqueous solution characterised in that the solution contains:
- the invention also provides an acidic aqueous composition for phosphating an iron- or zinc-based metal surface characterised in that the composition is this solution.
- the conversion coating accelerator is preferably at least one of the following:
- the acidic aqueous solution may also contain one or more of the following:
- the metal surface can then be coated with a siccative coating, for example by a known electrocoating process, preferably by the cationic electrocoating process.
- iron- or zinc-based metal surface means iron-based surfaces, iron alloy-based surfaces, zinc-based surfaces, and zinc alloy-based surfaces.
- Zinc- and zinc alloy-based surfaces include, for example, zinc plated steel plate formed by hot dipping, alloyed zinc plated steel plate formed by hot dipping, zinc plated steel plate formed by electroplating and alloyed zinc plated steel plate formed by electroplating.
- An important advantage of the present invention is that surfaces of metal components, such as car bodies, that contain both iron-based surfaces and zinc-based surfaces can be treated by the process of the invention with excellent results.
- the process of the invention produces better conversion coatings than are obtainable with conventional dip treating processes, and the amount of etching of the metal surfaces during the present process is only 2/3 to 4/5 that of conventional processes, so that both the quantity of chemicals used in the process as well as sludget formation is only from 2/3 to 4/5 that of conventional processes.
- the present process is equally applicable to the treatment of a single-metal surface of a type described above.
- a particularly useful method of carrying out the present process is first to degrease the metal surface to be phosphated for example by spraying and/or dipping the metal-surface in a known alkaline-degreasing agent at 50°-60°C for two minutes; washing the metal surface with tap water; spraying and/or dip treating the metal surface with a known surface conditioner at room temperature for 10-30 seconds; dipping the surface into the present acidic aqueous solution at 40°-70°C for at least 15 seconds; and washing the metal surface with tap water followed by deionized water.
- the present acidic aqueous solution has a zinc ion concentration within the range of 0.5 to 1.5 g/1.
- the amount of zinc ion is less than about 0.5 g/l, an even phosphate film is not formed on an iron-based surface, and a partially blue-coloured film is formed.
- the amount of zinc ion exceeds about 1.5 g/1, then though an even phosphate film is formed, the film that forms on an iron-based surface tends to be in the-form of leaf-like crystals, such as those formed in the spray process, which are unsuitable as a substrate for cationic electrocoating.
- the amount of manganese-ion is less than about 0.6 g/l, the manganese content in the film formed on the zinc-based surface is insufficient, resulting in inadequate adhesivity of the coating film to the phosphate substrate after cationic electrocoating.
- the amount of manganese ion exceeds about 3 g/l, no further improvement in the phosphate coating is realized, and hence it is uneconomical to use amounts in excess of about 3 g/l.
- the conversion coating on iron-based surfaces is inadequate, forming yellow rust, etc.
- the amount of the accelerator exceeds the designated higher amount, a blue-coloured uneven film is formed on the iron-based surface.
- a source of zinc ions for use in the practice of the invention, one or more of the following can be employed: zinc oxide, zinc carbonate, and zinc nitrate.
- a source of phosphate ions one or more of the following can be used: sodium phosphate, zinc phosphate, and manganese ⁇ phosphate.
- manganese carbonate manganese nitrate
- manganese chloride manganese phosphate
- a source of conversion coating accelerators one or more of the following can be employed: sodium nitrite, ammonium nitrite, sodium m-nitrobenzenesulfonate, and hydrogen peroxide.
- the addition of the nickel ion results in further improvement in the performance of the phosphate conversion coating, so that the adhesion and the corrosion-resistance of the film produced by cationic electrocoating are also further improved.
- nickel carbonate, nickel nitrate, nickel chloride or nickel phosphate can be used for nickel ions; sodium nitrate, ammonium-nitrate, zinc nitrate, manganese nitrate or nickel nitrate for nitrate ions; and chloric acid, sodium chlorate or ammonium chlorate for chlorate ions.
- the present process is usually carried out at a temperature-in the range of 40° to 70°C, preferably 45° to 60°C.
- a temperature-in the range of 40° to 70°C preferably 45° to 60°C.
- the conversion coating deteriorates, and long periods of treatment time are required to obtain a satisfactory coating.
- the temperature is higher than about 70°C, the conversion coating accelerators begin to decompose at an unacceptable rate, changing the composition of the bath and resulting in an unacceptable conversion coating. Also, precipitates begin to form in the bath.
- the duration that the metal surface contacts the solution in the dip treatment is usually at least 15 seconds, and preferably is from 30 to 120 seconds. When treatment times shorter than about 15 seconds are employed, an adequate phosphate film is not formed.
- the components can advantageously be subjected first to dipping treatments for 15 seconds or more, preferably 30 to 90 seconds, and then to spray treatment with the solution for 2 seconds or more, preferably for 5 to 45 seconds.
- the spray treatment is preferably carried out for as long a period within the above range as the speed of the production line will permit.
- the dipping treatment according to the present invention includes the combination of dipping followed by spraying.
- EXAMPLES I to VIII are Examples of the process and compositions of the invention.
- EXAMPLESIX toXIV are Examples using known compositions, given for comparison purposes.
Landscapes
- Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Chemical Treatment Of Metals (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Chemically Coating (AREA)
- Laminated Bodies (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Glass Compositions (AREA)
- Secondary Cells (AREA)
Abstract
Description
- This invention relates to a process for phosphating metal surfaces, and to a composition suitable for use in that process.
- Japanese Patent Publication (unexamined) No.107784/ 1980 (Nippon Paint Co.Ltd.) concerns a method of phosphating iron-based metal surfaces which is particularly suitable for treating manufactured products having complicated-surfaces, such as -automobile bodies. The method is. in use commercially in the automotive-industry for pretreating automobile bodies prior to cationic electrocoating, which is a, coating process now used extensively in this industry. The phosphating method is carried-out by first subjecting the metal surface to a dipping treatment with an acidic aqueous solution containing 0.5 to 1.5 g/l of zinc ion, 5 to 30 g/l of phosphate-ion, and 0.01 to 0.2 g/1 of nitrite ion and/or 0.05 to 2 g/1 of m-nitrobenzenesulfonate ion at a bath temperature of 40 to 70°C for 15 seconds or more, followed by spraying with the above solution for 2 seconds or more.
- Recently, in the automotive industry, with the aim of improving corrosion-resistance after the application of a siccative coating, steel components which are plated on one surface only with zinc or a zinc alloy have come to be used as materials for automobile bodies. when the process of the above Japanese Patent Publication is applied to such materials (i.e. to metal components having both iron-based metal surfaces and zinc-based metal surfaces), the iron-based surfaces are provided with a phosphate coating film having a low film thickness with uniform and dense cubic crystals, as well as excellent adhesion and corrosion-resistance. Such phosphate coating on the iron-based surface is suitable as a substrate for cationic electrocoating. However, in the case of the phosphate coating film formed on the zinc-based surfaces, the resistance to salt water spraying after the application of a cationic electrocoat thereto is insufficient, and secondary adhesion (tested by immersion of the surface bearing the film with cross-hatched scratches in warm water) after the sequence cationic electrocoating - intermediate coating - top coating is greatly inferior to that on the iron-based surfaces.
- In addition to the Japanese Patent Publication, the following references disclose phosphating compositions for metal surfaces:
- U.S. Patent 3,338,755 (Jenkins et al) discloses a process for phosphating metal surfaces with a phosphating solution containing zinc, manganese, phosphate, nitrate, and nitrite, as essential ingredients, in stated proportions.
- German Patent 29 31 693 (Fosfa-Col) discloses a phosphating process using a solution containing zinc, manganese, phosphate, nitrate, and chlorate ions in stated gram-atom relationships.
- The present invention provides an improved phosphating method for metal surfaces, which is particularly suitable for treating metal surfaces, such as-those of car bodies, which have both iron-based surfaces and zinc-based surfaces. The method is especially advantageous for forming phosphate coating films suitable for electrocoating particularly cationic electrocoating.
- Accordingly, the invention provides a process for phosphating an iron- or zinc-based metal surface comprising subjecting the metal surface to a dipping treatment in an acidic aqueous solution characterised in that the solution contains:
- (a) from 0.5 to 1.5 g/1, preferably 0.7 to 1.2 g/1, of zinc ion;
- (b) from 5 to 30 g/1, preferably 10 to 20 g/l, of phosphate ion;
- (c) from 0.6 to 3 g/1, preferably 0.8 to 2 g/1, of manganese ion; and
- (d) a conversion coating accelerator.
- The invention also provides an acidic aqueous composition for phosphating an iron- or zinc-based metal surface characterised in that the composition is this solution.
- The conversion coating accelerator is preferably at least one of the following:
- (i) from 0.01 to 0.2 g/l, preferably 0.04 to 0.15 g/1, of nitrite ion;
- (ii) from 0.05 to 2 g/1, preferably 0.1 to 1.5 g/l,of m-nitrobenzenesulfonate ion; and
- (iii) . from 0.5 to 5 g/1, preferably 1 to 4 g/l,of hydrogen peroxide (based on 100%. H 2 0 2 )
- Optionally, the acidic aqueous solution may also contain one or more of the following:
- (e) from 0.1 to 4 g/1, preferably 0.3 to 2 g/l, of nickel ion ;
- (f) from 1 to 10 g/l, preferably 2 to 8 g/l, of nitrate ion; and.
- (g) from 0.05 to 2 g/l, preferably 0.2 to 1.5 g/l, of chlorate ion.
- Following the phosphating treatment, the metal surface can then be coated with a siccative coating, for example by a known electrocoating process, preferably by the cationic electrocoating process.
- The term "iron- or zinc-based metal surface" as used herein means iron-based surfaces, iron alloy-based surfaces, zinc-based surfaces, and zinc alloy-based surfaces. Zinc- and zinc alloy-based surfaces include, for example, zinc plated steel plate formed by hot dipping, alloyed zinc plated steel plate formed by hot dipping, zinc plated steel plate formed by electroplating and alloyed zinc plated steel plate formed by electroplating.
- An important advantage of the present invention is that surfaces of metal components, such as car bodies, that contain both iron-based surfaces and zinc-based surfaces can be treated by the process of the invention with excellent results. In fact, the process of the invention produces better conversion coatings than are obtainable with conventional dip treating processes, and the amount of etching of the metal surfaces during the present process is only 2/3 to 4/5 that of conventional processes, so that both the quantity of chemicals used in the process as well as sludget formation is only from 2/3 to 4/5 that of conventional processes. The present process is equally applicable to the treatment of a single-metal surface of a type described above.
- A particularly useful method of carrying out the present process is first to degrease the metal surface to be phosphated for example by spraying and/or dipping the metal-surface in a known alkaline-degreasing agent at 50°-60°C for two minutes; washing the metal surface with tap water; spraying and/or dip treating the metal surface with a known surface conditioner at room temperature for 10-30 seconds; dipping the surface into the present acidic aqueous solution at 40°-70°C for at least 15 seconds; and washing the metal surface with tap water followed by deionized water.
- The present acidic aqueous solution has a zinc ion concentration within the range of 0.5 to 1.5 g/1. When the amount of zinc ion is less than about 0.5 g/l, an even phosphate film is not formed on an iron-based surface, and a partially blue-coloured film is formed. When the amount of zinc ion exceeds about 1.5 g/1, then though an even phosphate film is formed, the film that forms on an iron-based surface tends to be in the-form of leaf-like crystals, such as those formed in the spray process, which are unsuitable as a substrate for cationic electrocoating.
- When the amount of phosphate ion in the solutions is less than about 5 g/l, an uneven film results. When the amount of phosphate ion exceeds about 30 g/l, no further improvement in the phosphate film is realized and hence, while not harmful, use of phosphate ion above about 30 g/1 is uneconomical.
- When the amount of manganese-ion is less than about 0.6 g/l, the manganese content in the film formed on the zinc-based surface is insufficient, resulting in inadequate adhesivity of the coating film to the phosphate substrate after cationic electrocoating. When the amount of manganese ion exceeds about 3 g/l, no further improvement in the phosphate coating is realized, and hence it is uneconomical to use amounts in excess of about 3 g/l.
- With respect to the preferred conversion coating accelerators specified above, when they are present in amount less than the designated lower amount, the conversion coating on iron-based surfaces is inadequate, forming yellow rust, etc. When the amount of the accelerator exceeds the designated higher amount, a blue-coloured uneven film is formed on the iron-based surface.
- As an example of a source of zinc ions for use in the practice of the invention, one or more of the following can be employed: zinc oxide, zinc carbonate, and zinc nitrate.
- As an example-of a source of phosphate ions, one or more of the following can be used: sodium phosphate, zinc phosphate, and manganese · phosphate.
- As an example of a source of manganese ions, one or more of the following can be employed: manganese carbonate, manganese nitrate, manganese chloride, and manganese phosphate.
- As an example of a source of conversion coating accelerators, one or more of the following can be employed: sodium nitrite, ammonium nitrite, sodium m-nitrobenzenesulfonate, and hydrogen peroxide.
- With respect to the optional additional ingredients specified above, the addition of the nickel ion results in further improvement in the performance of the phosphate conversion coating, so that the adhesion and the corrosion-resistance of the film produced by cationic electrocoating are also further improved.
- As examples of sources of the optional ingredients, nickel carbonate, nickel nitrate, nickel chloride or nickel phosphate can be used for nickel ions; sodium nitrate, ammonium-nitrate, zinc nitrate, manganese nitrate or nickel nitrate for nitrate ions; and chloric acid, sodium chlorate or ammonium chlorate for chlorate ions.
- The present process is usually carried out at a temperature-in the range of 40° to 70°C, preferably 45° to 60°C. When temperatures below about 40°C are employed, the conversion coating deteriorates, and long periods of treatment time are required to obtain a satisfactory coating. When the temperature is higher than about 70°C, the conversion coating accelerators begin to decompose at an unacceptable rate, changing the composition of the bath and resulting in an unacceptable conversion coating. Also, precipitates begin to form in the bath.
- The duration that the metal surface contacts the solution in the dip treatment is usually at least 15 seconds, and preferably is from 30 to 120 seconds. When treatment times shorter than about 15 seconds are employed, an adequate phosphate film is not formed. In treating metal components having complicated surface profiles, such as car bodies have, the components can advantageously be subjected first to dipping treatments for 15 seconds or more, preferably 30 to 90 seconds, and then to spray treatment with the solution for 2 seconds or more, preferably for 5 to 45 seconds. In order to wash out the sludge which adheres during dipping, the spray treatment is preferably carried out for as long a period within the above range as the speed of the production line will permit. Accordingly, the dipping treatment according to the present invention includes the combination of dipping followed by spraying.
- The invention is illustrated by the following Examples.
- EXAMPLES I to VIII are Examples of the process and compositions of the invention. EXAMPLESIX toXIV are Examples using known compositions, given for comparison purposes.
- The treating process used, which is common to all the Examples, is given below, with the aqueous coating compositions of each Example being set forth in Table I, while the metal treated and the test results obtained following the phosphate treatment are set forth in Table 2.
- Samples of all four of the metal surfaces specified in Table 2 were treated simultaneously according to the following procedure:
- (a) degreasing, using an alkaline degreasing agent (Nippon Paint Co., "RIDOLINE SD200", 2% by weight) which was sprayed on the metal surfaces at 60°C for 1 minute, followed by dipping in the solution for 2 minutes;
- (b) the metal surfaces were then washed with tap water at room temperature for 15 seconds;
- (c) the metal surfaces were next dipped into a surface conditioner (Nippon Paint Co., "FIXODINE 5N5", 0.1% by weight) at room temperature for 15 seconds;
- (d) the metal surfaces were then dipped into the acidic aqueous solution specified in Table 1 at 52°C for 120 seconds;
- (e) the metal surfaces were washed with tap water at room temperature for 15 seconds;
- (f) the metal surfaces were then dipped into deionized water at room temperature for 15 seconds;
- (g) the surfaces were then dried in hot air at 100°C for 10 minutes. At this stage the appearance and film weight of the treated metal surfaces was determined, with the results set forth in Table 2; and
- (h) a cationic- electrocoating material (Nippon Paint., Power. Top U-30 Dark Gray") was coated to- 20 µ thickness onto the treated metal surfaces (voltage 180V., treatment time 3 minutes); followed by baking at 180°C for 30 minutes. - One sample of each electrocoated plate so obtained was subjected to the brine spray test.
- A second sample of each electrocoated plate so obtained was coated with an intermediate coating material (Nippon Paint Co., "ORGA. T0778 Gray") to= 30µ thickness, followed by baking at l40°C for 20 minutes, and a top coating material (Nippon Paint Co., "ORGA T0626 Margaret White.") in 40µ thickness was then applied, followed by baking as above. Accordingly, coated plates with a total of 3 coatings and 3 bakings were obtained. All the thus coated plates were subjected to the adhesion test, and the thus coated cold rolled steel plate also to the spot rusting test.
- The testing procedures referred to above are described below:
- (A) Brine spraying test (JIS-Z-2871): Cross-cuts were made on an electrocoated plate; 5% brine was sprayed thereon for 500 hours (zinc plated steel plate) or 1000 hours (cold-rolled-steel plate).
- (B) Adhesion test: After dipping a coated plate in deionized water at 50°C for 10 days, grids (100 squares) were made at 1 mm intervals or at 2 mm intervals using a sharp cutter; an adhesive-tape was attached to each surface; and the number of squares of coating film that remained on the plate after the removal of the adhesive tape were counted.
- (C) Spot rusting test: A coated plate was set at a 15 degree angle to the horizontal plane, and an arrow with a cone shaped head with a 90 degree vertical angle, made of alloyed steel (material quality, JIS-G-4404, hardness Hv 700 or higher), weighing 1.00 g and 14.0 mm in total length was dropped repeatedly from a distance of 150 cm, until 25 scratches were made on the coated surface. Subsequently, the coated plate was subjected to 4 cycles of testing, each cycle consisting of first the brine spray test (JIS-Z-2871, 24 hours), second, a moisture test (temperature of 40°C, relative humidity 85%, 120 hours), and third, standing at room temperature (24 hours). After testing, the average value (mm) of the largest diameter of rust spots and blisters was obtained, with the results shown in Table 2.
Claims (11)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT82301330T ATE33684T1 (en) | 1981-03-16 | 1982-03-16 | PHOSPHATION OF METAL SURFACES. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP38411/81 | 1981-03-16 | ||
JP56038411A JPS57152472A (en) | 1981-03-16 | 1981-03-16 | Phosphating method for metallic surface for cation type electrodeposition painting |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0060716A1 true EP0060716A1 (en) | 1982-09-22 |
EP0060716B1 EP0060716B1 (en) | 1988-04-20 |
Family
ID=12524551
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP82301330A Expired EP0060716B1 (en) | 1981-03-16 | 1982-03-16 | Phosphating metal surfaces |
Country Status (10)
Country | Link |
---|---|
EP (1) | EP0060716B1 (en) |
JP (1) | JPS57152472A (en) |
AT (1) | ATE33684T1 (en) |
AU (1) | AU554406B2 (en) |
BR (1) | BR8201400A (en) |
CA (1) | CA1200739A (en) |
CS (1) | CS179582A2 (en) |
DE (1) | DE3278367D1 (en) |
ES (1) | ES8302127A1 (en) |
MX (2) | MX156539A (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0261597A2 (en) * | 1986-09-26 | 1988-03-30 | Ppg Industries, Inc. | Method of applying a zinc-nickel phosphate coating |
WO1995007370A1 (en) * | 1993-09-06 | 1995-03-16 | Henkel Kommanditgesellschaft Auf Aktien | Nickel-free phosphatization process |
EP1012355A4 (en) * | 1996-12-04 | 2000-06-28 | Henkel Corp | Sludge reducing zinc phosphating process and composition |
US6090224A (en) * | 1995-03-29 | 2000-07-18 | Henkel Kommanditgesellschaft Auf Aktien | Phosphating process with a copper-containing re-rinsing stage |
WO2001032953A1 (en) * | 1999-11-04 | 2001-05-10 | Henkel Corporation | Zinc phosphating process and composition with reduced pollution potential |
WO2005051639A1 (en) | 2003-11-28 | 2005-06-09 | Bridgestone Corporation | Support body for run-flat tire and method of manufacturing the same |
Families Citing this family (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0135622B1 (en) * | 1983-08-22 | 1988-12-07 | Nippon Paint Co., Ltd. | Phosphating metal surfaces |
JPS5935681A (en) * | 1982-08-24 | 1984-02-27 | Nippon Paint Co Ltd | Method for phosphating metallic surface for coating by cationic electrodeposition |
DE3315086A1 (en) * | 1983-04-26 | 1984-10-31 | Metallgesellschaft Ag, 6000 Frankfurt | METHOD FOR PHOSPHATING COMPOSITE METALS |
GB8329250D0 (en) * | 1983-11-02 | 1983-12-07 | Pyrene Chemical Services Ltd | Phosphating processes |
WO1985003089A1 (en) * | 1984-01-06 | 1985-07-18 | Ford Motor Company | Alkaline resistance phosphate conversion coatings |
US4595424A (en) * | 1985-08-26 | 1986-06-17 | Parker Chemical Company | Method of forming phosphate coating on zinc |
DE3689442T2 (en) | 1985-08-27 | 1994-06-16 | Nippon Paint Co Ltd | Acidic, aqueous phosphate coating solutions for a process for phosphate coating of metallic surfaces. |
DE3537108A1 (en) * | 1985-10-18 | 1987-04-23 | Collardin Gmbh Gerhard | METHOD FOR PHOSPHATING ELECTROLYTICALLY GALVANIZED METALWARE |
US4941930A (en) * | 1986-09-26 | 1990-07-17 | Chemfil Corporation | Phosphate coating composition and method of applying a zinc-nickel phosphate coating |
US5238506A (en) * | 1986-09-26 | 1993-08-24 | Chemfil Corporation | Phosphate coating composition and method of applying a zinc-nickel-manganese phosphate coating |
AU592671B2 (en) * | 1986-09-26 | 1990-01-18 | Ppg Industries Ohio, Inc. | Phosphate coating composition and method of applying a zinc-nickel phosphate coating |
JPS63227786A (en) * | 1987-03-16 | 1988-09-22 | Nippon Parkerizing Co Ltd | Phosphating method for pretreating steel sheet before coating by electrodeposition |
JPH0819531B2 (en) * | 1989-03-02 | 1996-02-28 | 日本ペイント株式会社 | Zinc phosphate treatment method for metal surface |
DE3913089A1 (en) * | 1989-04-21 | 1990-10-25 | Henkel Kgaa | CHLORATE- AND NITRITE-FREE METHOD FOR THE PRODUCTION OF NICKEL- AND MANGANE-CONTAINING ZINC PHOSPHATE LAYERS |
DE3927131A1 (en) * | 1989-08-17 | 1991-02-21 | Henkel Kgaa | METHOD FOR THE PRODUCTION OF MANGANIZED ZINC PHOSPHATE LAYERS ON GALVANIZED STEEL |
KR100197145B1 (en) * | 1989-12-19 | 1999-06-15 | 후지이 히로시 | Method for phosphating metal surface with zinc phosphate |
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 |
US5268041A (en) * | 1990-04-27 | 1993-12-07 | Metallgesellschaft Ag | Process for phosphating metal surfaces |
JPH04341574A (en) * | 1991-05-18 | 1992-11-27 | Nippon Paint Co Ltd | Treatment of zinc phosphate onto metal surface |
US5328526A (en) * | 1992-04-03 | 1994-07-12 | Nippon Paint Co., Ltd. | Method for zinc-phosphating metal surface |
DE19834796A1 (en) | 1998-08-01 | 2000-02-03 | Henkel Kgaa | Process for phosphating, rinsing and cathodic electrocoating |
JP6075167B2 (en) * | 2012-04-18 | 2017-02-08 | Jfeスチール株式会社 | Method for improving corrosion resistance after painting welded portion of automobile underbody member, automobile underbody member, and manufacturing method of automobile underbody member |
JP6157622B2 (en) | 2012-08-23 | 2017-07-05 | ピールブルグ パンプ テクノロジー ゲゼルシャフト ミット ベシュレンクテル ハフツングPierburg Pump Technology GmbH | Mechanical fluid pump driven by a combustion engine |
WO2014029446A1 (en) | 2012-08-23 | 2014-02-27 | Pierburg Pump Technology Gmbh | Mechanical combustion-engine-driven fluid pump |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2144732A1 (en) * | 1971-07-06 | 1973-02-16 | Parker Ste Continentale | Phosphating metals - by controlling the zinc-phosphate ratio - gives uniform, thin, adhesive coatings |
FR2449135A1 (en) * | 1979-02-13 | 1980-09-12 | Nippon Paint Co Ltd | PROCESS FOR THE PHOSPHATION OF A METAL SURFACE FOR COATING BY ELECTRODEPOSITION |
EP0036689A1 (en) * | 1980-03-21 | 1981-09-30 | Metallgesellschaft Ag | Method of applying phosphate coatings |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5811514B2 (en) * | 1979-05-02 | 1983-03-03 | 日本ペイント株式会社 | How to protect metal surfaces |
-
1981
- 1981-03-16 JP JP56038411A patent/JPS57152472A/en active Granted
-
1982
- 1982-03-15 BR BR8201400A patent/BR8201400A/en not_active IP Right Cessation
- 1982-03-15 AU AU81507/82A patent/AU554406B2/en not_active Expired
- 1982-03-15 MX MX191815A patent/MX156539A/en unknown
- 1982-03-15 CA CA000398352A patent/CA1200739A/en not_active Expired
- 1982-03-15 MX MX011955A patent/MX172180B/en unknown
- 1982-03-16 AT AT82301330T patent/ATE33684T1/en not_active IP Right Cessation
- 1982-03-16 DE DE8282301330T patent/DE3278367D1/en not_active Expired
- 1982-03-16 EP EP82301330A patent/EP0060716B1/en not_active Expired
- 1982-03-16 CS CS821795A patent/CS179582A2/en unknown
- 1982-03-16 ES ES510472A patent/ES8302127A1/en not_active Expired
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2144732A1 (en) * | 1971-07-06 | 1973-02-16 | Parker Ste Continentale | Phosphating metals - by controlling the zinc-phosphate ratio - gives uniform, thin, adhesive coatings |
FR2449135A1 (en) * | 1979-02-13 | 1980-09-12 | Nippon Paint Co Ltd | PROCESS FOR THE PHOSPHATION OF A METAL SURFACE FOR COATING BY ELECTRODEPOSITION |
EP0036689A1 (en) * | 1980-03-21 | 1981-09-30 | Metallgesellschaft Ag | Method of applying phosphate coatings |
Non-Patent Citations (1)
Title |
---|
CHEMICAL ABSTRACTS, vol. 84, 1976, page 283, no. 94280a, Columbus, Ohio, (USA); & JP-A-50 139 039 (MITSU MINING AND SMELTING CO., LTD.) (06-11-1975) * |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0261597A2 (en) * | 1986-09-26 | 1988-03-30 | Ppg Industries, Inc. | Method of applying a zinc-nickel phosphate coating |
EP0261597A3 (en) * | 1986-09-26 | 1988-07-13 | Chemfil Corporation | Phosphate coating composition and method of applying a zinc-nickel phosphate coating |
WO1995007370A1 (en) * | 1993-09-06 | 1995-03-16 | Henkel Kommanditgesellschaft Auf Aktien | Nickel-free phosphatization process |
US5792283A (en) * | 1993-09-06 | 1998-08-11 | Henkel Kommanditgesellschaft Auf Aktien | Nickel-free phosphating process |
CN1041001C (en) * | 1993-09-06 | 1998-12-02 | 汉克尔股份两合公司 | Nickel-free phosphatization process |
US6090224A (en) * | 1995-03-29 | 2000-07-18 | Henkel Kommanditgesellschaft Auf Aktien | Phosphating process with a copper-containing re-rinsing stage |
EP1012355A4 (en) * | 1996-12-04 | 2000-06-28 | Henkel Corp | Sludge reducing zinc phosphating process and composition |
WO2001032953A1 (en) * | 1999-11-04 | 2001-05-10 | Henkel Corporation | Zinc phosphating process and composition with reduced pollution potential |
WO2005051639A1 (en) | 2003-11-28 | 2005-06-09 | Bridgestone Corporation | Support body for run-flat tire and method of manufacturing the same |
EP1693181A1 (en) * | 2003-11-28 | 2006-08-23 | Bridgestone Corporation | Support body for run-flat tire and method of manufacturing the same |
US7531056B2 (en) * | 2003-11-28 | 2009-05-12 | Bridgestone Corporation | Run-flat tire support and manufacturing method for the same |
EP1693181A4 (en) * | 2003-11-28 | 2010-02-10 | Bridgestone Corp | Support body for run-flat tire and method of manufacturing the same |
Also Published As
Publication number | Publication date |
---|---|
JPH0137478B2 (en) | 1989-08-07 |
AU8150782A (en) | 1982-09-23 |
ES510472A0 (en) | 1983-02-01 |
ATE33684T1 (en) | 1988-05-15 |
CS179582A2 (en) | 1984-06-18 |
ES8302127A1 (en) | 1983-02-01 |
EP0060716B1 (en) | 1988-04-20 |
MX172180B (en) | 1993-12-07 |
DE3278367D1 (en) | 1988-05-26 |
JPS57152472A (en) | 1982-09-20 |
BR8201400A (en) | 1983-02-01 |
MX156539A (en) | 1988-09-08 |
CA1200739A (en) | 1986-02-18 |
AU554406B2 (en) | 1986-08-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0060716B1 (en) | Phosphating metal surfaces | |
EP0106459B1 (en) | Phosphate coating metal surfaces | |
US4419199A (en) | Process for phosphatizing metals | |
US4311535A (en) | Composition for forming zinc phosphate coating over metal surface | |
JP2680618B2 (en) | Metal phosphate treatment method | |
US5976272A (en) | No-rinse phosphating process | |
EP0123980A1 (en) | Composition and process for zinc phosphate coating a metal surface and a process for painting the coated surface | |
EP0544650B1 (en) | A process for phosphate-coating metal surfaces | |
JPH04228579A (en) | Method for treating metal surface with phosphate | |
JPH07505445A (en) | Nickel-free phosphate treatment method | |
US4673444A (en) | Process for phosphating metal surfaces | |
CA1308338C (en) | Process of producing phosphate coatings on metal surfaces | |
US5000799A (en) | Zinc-nickel phosphate conversion coating composition and process | |
US4637838A (en) | Process for phosphating metals | |
EP0321059B1 (en) | Process for phosphating metal surfaces | |
JPH08501829A (en) | Method for phosphating steel with zinc coating on one side | |
JPH09501202A (en) | Phosphating Method for Steel Strip Plated on One Side by Zinc | |
EP0061911A1 (en) | Process and composition for treating phosphated metal surfaces | |
EP0135622B1 (en) | Phosphating metal surfaces | |
US5312492A (en) | Process not using chlorate or nitrite for the production of nickel and manganese containing zinc phosphate films | |
KR100496221B1 (en) | Phosphate-treated electrogalvanized steel sheet excellent in corrosion resistance and coating suitability | |
GB2074611A (en) | Phosphating Compositions | |
JPH07173643A (en) | Method for phosphating metal surface and phosphating solution | |
US6342107B1 (en) | Phosphate coatings for metal surfaces | |
US4559087A (en) | Process for phosphating metals |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Designated state(s): AT BE DE FR GB IT NL SE |
|
17P | Request for examination filed |
Effective date: 19830302 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE DE FR GB IT NL SE |
|
REF | Corresponds to: |
Ref document number: 33684 Country of ref document: AT Date of ref document: 19880515 Kind code of ref document: T |
|
REF | Corresponds to: |
Ref document number: 3278367 Country of ref document: DE Date of ref document: 19880526 |
|
ITF | It: translation for a ep patent filed |
Owner name: JACOBACCI & PERANI S.P.A. |
|
ET | Fr: translation filed | ||
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
NLS | Nl: assignments of ep-patents |
Owner name: AMCHEM PRODUCTS INC. TE AMBLER, PENNSYLVANIE, VER. |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: TP |
|
ET1 | Fr: translation filed ** revision of the translation of the patent or the claims | ||
ITPR | It: changes in ownership of a european patent |
Owner name: CESSIONE;HENKEL CORPORATION |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: 732 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: TP |
|
ITTA | It: last paid annual fee | ||
REG | Reference to a national code |
Ref country code: GB Ref legal event code: 732E |
|
EAL | Se: european patent in force in sweden |
Ref document number: 82301330.5 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20010319 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20010323 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20010329 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20010330 Year of fee payment: 20 Ref country code: AT Payment date: 20010330 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20010410 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20010430 Year of fee payment: 20 |
|
BE20 | Be: patent expired |
Free format text: 20020316 *HENKEL CORP. |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20020315 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20020316 Ref country code: AT Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20020316 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020317 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: PE20 Effective date: 20020315 |
|
NLV7 | Nl: ceased due to reaching the maximum lifetime of a patent |
Effective date: 20020316 |
|
EUG | Se: european patent has lapsed |
Ref document number: 82301330.5 |