EP0056675A2 - Pretreatment composition for phosphatising ferrous metals, and method of preparing the same - Google Patents
Pretreatment composition for phosphatising ferrous metals, and method of preparing the same Download PDFInfo
- Publication number
- EP0056675A2 EP0056675A2 EP82200062A EP82200062A EP0056675A2 EP 0056675 A2 EP0056675 A2 EP 0056675A2 EP 82200062 A EP82200062 A EP 82200062A EP 82200062 A EP82200062 A EP 82200062A EP 0056675 A2 EP0056675 A2 EP 0056675A2
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- EP
- European Patent Office
- Prior art keywords
- weight
- measured
- amount
- composition
- titanium
- 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.)
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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
- C23C22/78—Pretreatment of the material to be coated
- C23C22/80—Pretreatment of the material to be coated with solutions containing titanium or zirconium compounds
Definitions
- This invention relates to an aqueous solution for the treatment of ferrous metal surfaces, to the treatment of ferrous metal surfaces with this aqueous solution, to a solid composition suitable for preparing the aqueous solution and to the production of the solid composition.
- the usual treatment steps include the following in order:
- this composition does not provide the desired microcrystalline coating in the zinc phosphate conversion coating treatment.
- the present invention relates to surface preparation compositions for the treatment of ferrous metal surfaces that do not suffer from the disadvantages of the prior art composition discussed above.
- the surface preparation compositions of the present invention can be used for long periods of time and such use results in a uniform and dense zinc phosphate coating when a zinc phosphate conversion coating composition is applied to the surface so treated.
- the surface preparation compositions of the invention can be used to pretreat any ferrous metal surface, such as steel or other alloys of iron where the alloy consists predominantly of iron.
- composition for the treatment of ferrous metal surfaces which composition is an aqueous solution comprising:
- a rust-inhibiting quantity of nitrite ion e.g. in the form of its alkali metal salt, such as the sodium or potassium salt, may be added to the solution, provided the quantity added is not so large as to interfere with the effectiveness of the compositions. Additional carbonate and/or acid carbonate may then also be added, if necessary, to keep the pH in the above range.
- various compounds may be employed. Examples of such compounds include titanium sulphate or titanium oxide as a source of (a); phosphoric acid, a primary alkali metal salt (e.g. Na or K salt) or primary ammonium salt of phosphoric acid, a secondary alkali metal salt (e.g. Na or K salt) or secondary ammonium salt of phosphoric acid, or a tertiary alkali metal salt (e.g. Na or K salt) or tertiary ammonium salt of phosphoric acid as a source of (b); pyrophosphoric acid or an alkali metal salt (e.g.
- Na or K salt or ammonium salt of pyrophosphoric acid as a source of (c); and carbonic acid, an alkali metal salt (e.g. Na or K salt) or ammonium salt of carbonic acid, alkali metal hydrogen carbonate (e.g. Na or K salt) or ammonium hydrogen carbonate as a source of (d).
- an alkali metal salt e.g. Na or K salt
- ammonium salt of carbonic acid e.g. Na or K salt
- alkali metal hydrogen carbonate e.g. Na or K salt
- ammonium hydrogen carbonate e.g. Na or K salt
- the present invention also relates to solid compositions (conveniently in powder form) that can be added to water to form the aqueous pretreatment compositions of the invention.
- solid compositions comprise:
- a small quantity of nitrite ion can also be present to provide a rust-inhibiting quantity of nitrite ion when the solid compositions are diluted with a sufficient quantity of water to give the aqueous pretreatment compositions of the invention.
- the solid compositions can be prepared by (A) mixing the sources of titanium compound, phosphate and/or acid phosphate, and pyrophosphate together with water in the above proportions; (B) heating the resulting mixture, e.g. at a temperature in the range of from 100° to 120 0 C until the water content is substantially removed, e.g. to a level of 1.5% by weight or less; and (C) mixing, which should be even mixing, the resulting solid residue with the source of carbonate and/or acid carbonate added in the above proportion.
- a titanium phosphate colloid adheres thereto, which serves to accelerate the formation of a zinc phosphate conversion coating by providing crystal nuclei around which the zinc phosphate coating can form.
- the resulting zinc phosphate coating has excellent characteristics as a base for siccative coatings such as paint.
- the titanium compound concentration is lower than the amount specified, the colloid which becomes the crystal nuclei for the zinc phosphate coating is formed in too small a quantity.
- the titanium compound concentration is higher than the amount specified, no enhanced effect is obtained.
- the phosphate and/or acid phosphate concentration specified is also present for the same purpose, i.e. to provide an adequate quantity of titanium phosphate colloid on the ferrous metal surface.
- the pyrophosphate has the beneficial effect of micronizing the zinc phosphate conversion coating.
- concentration of pyrophosphate is below the range specified, adequate micronizing is not achieved.
- concentration is above the range specified, the pyrophosphate tends to react with the iron in the ferrous metal surface, resulting in the inhibition of formation of a zinc phosphate conversion coating.
- the pH buffer effect is not obtained, i.e. when the pH of the present aqueous pretreatment composition is lower than the required values, the pyrophosphate ion tends to react with the ferrous metal surface, resulting in the inhibition of the subsequent zinc phosphate conversion coating formation.
- too high a pH value does not give a preferred conversion coating for pretreatmentsof electro coating.
- aqueous surface preparation compositions When the present aqueous surface preparation compositions are used in the pretreatment of ferrous metal surfaces, such compositions can be used for long periods of time, and provide a base for uniform, dense zinc phosphate conversion coatings.
- the surface preparation compositions of the present invention are especially effective for preparing ferrous metal surfaces for zinc phosphate treatment for electro coating.
- the long-term stability of the instant surface preparation compositions is particularly advantageous in the dipping type treatment of metals in which a large quantity of surface preparation composition is employed.
- An aqueous surface treatment composition was prepared using the following quantities of ingredients:
- An aqueous surface treatment composition was prepared using the following quantities of ingredients:
- a solid mixture was formed in accordance with the process of EXAMPLE I, and the mixture was added to sufficient water to give a solution of 0.1% concentration.
- aqueous surface treatment composition was prepared from the following ingredients using the procedure of EXAMPLE I, except that the solid mixture formed was diluted with water to form a . 0.05% aqueous solution:
- Each of three degreased commercial cold rolled steel plates was treated with one of the new aqueous compositions of EXAMPLES I, II and III, i.e. one plate was treated with the composition of EXAMPLE I, a second plate with the composition of EXAMPLE II, etc.
- the plates were treated by dipping them for 1 minute in the aqueous composition, allowing excess liquid to drip off, and immediately dipping them into a zinc phosphate conversion coating bath (Nippon Paint Co. "GRANODINE SD 2000”) for 2 minutes at a bath temperature of 50 0 C.
- An aqueous surface treatment composition was prepared from the following ingredients:
- a solid mixture was formed from the above ingredients in accordance with the procedure of EXAMPLE I (except that all of the above ingredients were mixed together and heated to form the solid mixture).
- a 0.05% aqueous solution was formed according to the procedure of EXAMPLE I.
- An aqueous surface treatment composition was prepared from the following ingredients in accordance with the procedure of EXAMPLE V except that the solid mixture was diluted with water to form a 0.1% aqueous solution.
- An aqueous surface treatment composition was prepared from the following ingredients in accordance with the procedure of EXAMPLE V except that the solid mixture was diluted with water to form a 0.07% aqueous solution.
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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)
Abstract
- (a) titanium compound in amount from 1 to 100 parts per million by weight, measured as titanium;
- (b) phosphate and/or acid phosphate in amount totalling from 50 to 1500 parts per million by weight, measured as PO4;
- (c) pyrophosphate in amount from 10 to 300 parts per million by weight, measured as P2O7; and
- (d) carbonate and/or acid carbonate in amount totalling 20 to 1500 parts per million by weight, measured as C03;
the solution having a pH from 8.5 to 9.5.
Description
- This invention relates to an aqueous solution for the treatment of ferrous metal surfaces, to the treatment of ferrous metal surfaces with this aqueous solution, to a solid composition suitable for preparing the aqueous solution and to the production of the solid composition.
- In the surface treatment of ferrous metals such as steel and other alloys of iron, the usual treatment steps include the following in order:
- (1) degreasing; (2) washing with water;
- (3) surface preparation; (4) conversion coating;
- (5) washing with water; (6) drying; and
- (7) siccative coating. With respect to the surface preparation step, various proposals have hitherto been made. For example, Japanese Patent Publication Number 7125/1964 discloses the use of a surface preparation composition which is produced by dissolving a titanium -oxide with an excess quantity of sulphuric acid, adding thereto phosphoric acid or an alkali metal salt thereof, and/or pyrophosphoric acid or its alkali metal salt to form a slurry at pH of 1 or lower, followed by ageing the slurry at a pH of from 6.5 to 8.5. This surface preparation composition is reported to contribute to the precipitation of the zinc phosphate coating in the conversion coating step which follows. However, when the pH of said composition is about 8.5 or lower, pyrophosphate ion in the composition reacts with the ferrous metal surface to form an iron pyrophosphate coating on the surface thereof, which inhibits the formation of the zinc phosphate coating, thus causing unevenness in treatment. Also, the pH of the surface preparation composition decreases with the passage of time for some unknown reason, and as a result, iron pyrophosphate forms on the surface of the ferrous metals treated with the composition. Furthermore even where the pH of the composition is adjusted to a pH, e.g. about 9, where iron pyrophosphate does not precipitate, such as by the addition of caustic soda, caustic potash, etc., the pH still decreases after a short period of time, causing the problem of iron pyrophosphate coating on the surface of the metals being treated. Accordingly, pH control of this prior art composition is difficult, and satisfactory surface preparations cannot be carried out with the compositions over long periods of time. Frequent replacements of the compositions must be made, with attendant expense and down time, particularly since the usual dipping process involves the use of large quantities of the surface preparation compositions.
- In addition to the above problem with the prior art surface preparation composition, this composition does not provide the desired microcrystalline coating in the zinc phosphate conversion coating treatment.
- The present invention relates to surface preparation compositions for the treatment of ferrous metal surfaces that do not suffer from the disadvantages of the prior art composition discussed above. The surface preparation compositions of the present invention can be used for long periods of time and such use results in a uniform and dense zinc phosphate coating when a zinc phosphate conversion coating composition is applied to the surface so treated.
- The surface preparation compositions of the invention can be used to pretreat any ferrous metal surface, such as steel or other alloys of iron where the alloy consists predominantly of iron.
- The invention provides a composition for the treatment of ferrous metal surfaces, which composition is an aqueous solution comprising:
- (a) titanium compound in amount from 1 to 100 parts per million by weight, measured as titanium;
- (b) phosphate and/or acid phosphate in amount totalling from 50 to 1500 parts per million by weight, measured as PO4;
- (c) pyrophosphate in amount from 10 to 300 parts per million by weight, measured as P207; and
- (d) carbonate and/or acid carbonate in amount totalling 20 to 1500 parts per million by weight, measured as Co3;
- Optionally, a rust-inhibiting quantity of nitrite ion, e.g. in the form of its alkali metal salt, such as the sodium or potassium salt, may be added to the solution, provided the quantity added is not so large as to interfere with the effectiveness of the compositions. Additional carbonate and/or acid carbonate may then also be added, if necessary, to keep the pH in the above range.
- As sources for the essential ingredients, various compounds may be employed. Examples of such compounds include titanium sulphate or titanium oxide as a source of (a); phosphoric acid, a primary alkali metal salt (e.g. Na or K salt) or primary ammonium salt of phosphoric acid, a secondary alkali metal salt (e.g. Na or K salt) or secondary ammonium salt of phosphoric acid, or a tertiary alkali metal salt (e.g. Na or K salt) or tertiary ammonium salt of phosphoric acid as a source of (b); pyrophosphoric acid or an alkali metal salt (e.g. Na or K salt) or ammonium salt of pyrophosphoric acid as a source of (c); and carbonic acid, an alkali metal salt (e.g. Na or K salt) or ammonium salt of carbonic acid, alkali metal hydrogen carbonate (e.g. Na or K salt) or ammonium hydrogen carbonate as a source of (d).
- The present invention also relates to solid compositions (conveniently in powder form) that can be added to water to form the aqueous pretreatment compositions of the invention. Such solid compositions comprise:
- (a) titanium compound in amount from 1 to 100 parts by weight, measured as titanium;
- (b) phosphate and/or acid phosphate in amount totalling from 50 to 1500 parts by weight, measured as PO4;
- (c) pyrophosphate in amount from 10 to 300 parts by weight, measured as P207; and
- (d) carbonate and/or acid carbonate in amount totalling 20 to 1500 parts by weight, measured as C03.
- Optionally, a small quantity of nitrite ion can also be present to provide a rust-inhibiting quantity of nitrite ion when the solid compositions are diluted with a sufficient quantity of water to give the aqueous pretreatment compositions of the invention.
- The solid compositions can be prepared by (A) mixing the sources of titanium compound, phosphate and/or acid phosphate, and pyrophosphate together with water in the above proportions; (B) heating the resulting mixture, e.g. at a temperature in the range of from 100° to 1200C until the water content is substantially removed, e.g. to a level of 1.5% by weight or less; and (C) mixing, which should be even mixing, the resulting solid residue with the source of carbonate and/or acid carbonate added in the above proportion.
- When ferrous metal surfaces are treated with the aqueous compositions of the invention, a titanium phosphate colloid adheres thereto, which serves to accelerate the formation of a zinc phosphate conversion coating by providing crystal nuclei around which the zinc phosphate coating can form. The resulting zinc phosphate coating has excellent characteristics as a base for siccative coatings such as paint. When the titanium compound concentration is lower than the amount specified, the colloid which becomes the crystal nuclei for the zinc phosphate coating is formed in too small a quantity. When the titanium compound concentration is higher than the amount specified, no enhanced effect is obtained. The phosphate and/or acid phosphate concentration specified is also present for the same purpose, i.e. to provide an adequate quantity of titanium phosphate colloid on the ferrous metal surface.
- The pyrophosphate has the beneficial effect of micronizing the zinc phosphate conversion coating. When the concentration of pyrophosphate is below the range specified, adequate micronizing is not achieved. When its concentration is above the range specified, the pyrophosphate tends to react with the iron in the ferrous metal surface, resulting in the inhibition of formation of a zinc phosphate conversion coating.
- When the carbonate and/or acid carbonate is employed in a quantity lower than that specified, the pH buffer effect is not obtained, i.e. when the pH of the present aqueous pretreatment composition is lower than the required values, the pyrophosphate ion tends to react with the ferrous metal surface, resulting in the inhibition of the subsequent zinc phosphate conversion coating formation. On the other hand, too high a pH value does not give a preferred conversion coating for pretreatmentsof electro coating.
- When the present aqueous surface preparation compositions are used in the pretreatment of ferrous metal surfaces, such compositions can be used for long periods of time, and provide a base for uniform, dense zinc phosphate conversion coatings. The surface preparation compositions of the present invention are especially effective for preparing ferrous metal surfaces for zinc phosphate treatment for electro coating. The long-term stability of the instant surface preparation compositions is particularly advantageous in the dipping type treatment of metals in which a large quantity of surface preparation composition is employed.
- The invention is illustrated by the following Examples, in which the term refers to percent by weight.
-
- The above ingredients, except for the sodium bicarbonate, were heated at a temperature maintained in the range of 100° to 120°C with stirring until the water content was reduced to 1.5% or lower (about 2 hours). To the powder so obtained, the sodium bicarbonate was added and evenly mixed together.
- The above solid mixture was then diluted with sufficient water to give a solution having a concentration of 0.07% of the mixture.
-
- A solid mixture was formed in accordance with the process of EXAMPLE I, and the mixture was added to sufficient water to give a solution of 0.1% concentration.
-
- Each of three degreased commercial cold rolled steel plates was treated with one of the new aqueous compositions of EXAMPLES I, II and III, i.e. one plate was treated with the composition of EXAMPLE I, a second plate with the composition of EXAMPLE II, etc. The plates were treated by dipping them for 1 minute in the aqueous composition, allowing excess liquid to drip off, and immediately dipping them into a zinc phosphate conversion coating bath (Nippon Paint Co. "GRANODINE SD 2000") for 2 minutes at a bath temperature of 500C. The plates were then washed with water, dried, and evaluated; in addition, the above procedure was repeated with an additional three steel plates after the aqueous compositions of EXAMPLES I, II and III had stood for 10 days. The results obtained are given in the Table below EXAMPLE VIII, together with the pH values of the pretreatment compositions.
- The following Examples are given for comparison purposes, using aqueous surface treatment compositions in accordance with the teachings of the prior art.
-
- A solid mixture was formed from the above ingredients in accordance with the procedure of EXAMPLE I (except that all of the above ingredients were mixed together and heated to form the solid mixture). A 0.05% aqueous solution was formed according to the procedure of EXAMPLE I.
-
-
-
the solution having a pH from 8.5 to 9.5.
Claims (13)
the solution having a pH from 8.5 to 9.5.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT82200062T ATE10513T1 (en) | 1981-01-19 | 1982-01-19 | PRETREATMENT COMPOSITION FOR THE PHOSPHATION OF FERROUS METALS AND PROCESS FOR THE PRODUCTION THEREOF. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP56007028A JPS5855229B2 (en) | 1981-01-19 | 1981-01-19 | Surface conditioner for zinc phosphate treatment |
JP7028/81 | 1981-01-19 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0056675A2 true EP0056675A2 (en) | 1982-07-28 |
EP0056675A3 EP0056675A3 (en) | 1982-08-04 |
EP0056675B1 EP0056675B1 (en) | 1984-11-28 |
Family
ID=11654577
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP82200062A Expired EP0056675B1 (en) | 1981-01-19 | 1982-01-19 | Pretreatment composition for phosphatising ferrous metals, and method of preparing the same |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0056675B1 (en) |
JP (1) | JPS5855229B2 (en) |
AT (1) | ATE10513T1 (en) |
DE (1) | DE3261311D1 (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0201841A2 (en) * | 1985-05-10 | 1986-11-20 | Nihon Parkerizing Co., Ltd. | Process for phosphating metal surfaces |
WO1991003582A1 (en) * | 1989-09-04 | 1991-03-21 | Henkel Corporation | Method of conditioning surfaces before phosphating |
US5026423A (en) * | 1989-02-22 | 1991-06-25 | Monsanto Chemical Company | Compositions and process for metal treatment |
US5039362A (en) * | 1988-04-28 | 1991-08-13 | Henkel Kommanditgesellschaft Auf Aktien | Titanium free composition and process for activating metal surfaces prior to zinc phosphating |
US5112395A (en) * | 1989-02-22 | 1992-05-12 | Monsanto Company | Compositions and process for metal treatment |
WO2004011231A1 (en) * | 2002-07-31 | 2004-02-05 | Nippon Steel Corporation | Resin-lined steel pipe and method for production thereof |
US11518960B2 (en) | 2016-08-24 | 2022-12-06 | Ppg Industries Ohio, Inc. | Alkaline molybdenum cation and phosphonate-containing cleaning composition |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6343039U (en) * | 1986-09-06 | 1988-03-22 | ||
DE3823716C2 (en) * | 1987-07-14 | 2001-09-27 | Astaris Llc St Louis | Process for the preparation of compositions for the treatment of metals |
WO2017078832A1 (en) * | 2015-11-04 | 2017-05-11 | Illinois Tool Works Inc. | Corrosion inhibitor and water conditioning agent |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2490062A (en) * | 1949-01-21 | 1949-12-06 | Westinghouse Electric Corp | Cleaning and activating compositions and use thereof in producing protective phosphate coatings on metal surfaces |
DE885638C (en) * | 1945-02-27 | 1953-08-06 | Metallgesellschaft Ag | Process for the production of a pre-wash solution for phosphating |
GB774667A (en) * | 1955-12-01 | 1957-05-15 | John Arthur Kemp | Improvements in or relating to the phosphate coating of metal surfaces |
FR1291347A (en) * | 1961-06-06 | 1962-04-20 | Parker Ste Continentale | Iron and steel spray phosphating process |
FR2093664A5 (en) * | 1970-05-25 | 1972-01-28 | Balm Paints Ltd | |
FR2154796A1 (en) * | 1971-09-30 | 1973-05-11 | Amchem Prod |
-
1981
- 1981-01-19 JP JP56007028A patent/JPS5855229B2/en not_active Expired
-
1982
- 1982-01-19 AT AT82200062T patent/ATE10513T1/en not_active IP Right Cessation
- 1982-01-19 DE DE8282200062T patent/DE3261311D1/en not_active Expired
- 1982-01-19 EP EP82200062A patent/EP0056675B1/en not_active Expired
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE885638C (en) * | 1945-02-27 | 1953-08-06 | Metallgesellschaft Ag | Process for the production of a pre-wash solution for phosphating |
US2490062A (en) * | 1949-01-21 | 1949-12-06 | Westinghouse Electric Corp | Cleaning and activating compositions and use thereof in producing protective phosphate coatings on metal surfaces |
GB774667A (en) * | 1955-12-01 | 1957-05-15 | John Arthur Kemp | Improvements in or relating to the phosphate coating of metal surfaces |
FR1291347A (en) * | 1961-06-06 | 1962-04-20 | Parker Ste Continentale | Iron and steel spray phosphating process |
FR2093664A5 (en) * | 1970-05-25 | 1972-01-28 | Balm Paints Ltd | |
FR2154796A1 (en) * | 1971-09-30 | 1973-05-11 | Amchem Prod |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0201841A2 (en) * | 1985-05-10 | 1986-11-20 | Nihon Parkerizing Co., Ltd. | Process for phosphating metal surfaces |
EP0201841A3 (en) * | 1985-05-10 | 1988-08-10 | Nihon Parkerizing Co., Ltd. | Process for phosphating metal surfaces |
US5039362A (en) * | 1988-04-28 | 1991-08-13 | Henkel Kommanditgesellschaft Auf Aktien | Titanium free composition and process for activating metal surfaces prior to zinc phosphating |
US5112414A (en) * | 1988-04-28 | 1992-05-12 | Henkel Kommanditgesellschaft Auf Aktien | Titanium free composition and process for activating metal surfaces prior to zinc phosphating |
US5026423A (en) * | 1989-02-22 | 1991-06-25 | Monsanto Chemical Company | Compositions and process for metal treatment |
US5112395A (en) * | 1989-02-22 | 1992-05-12 | Monsanto Company | Compositions and process for metal treatment |
WO1991003582A1 (en) * | 1989-09-04 | 1991-03-21 | Henkel Corporation | Method of conditioning surfaces before phosphating |
WO2004011231A1 (en) * | 2002-07-31 | 2004-02-05 | Nippon Steel Corporation | Resin-lined steel pipe and method for production thereof |
US11518960B2 (en) | 2016-08-24 | 2022-12-06 | Ppg Industries Ohio, Inc. | Alkaline molybdenum cation and phosphonate-containing cleaning composition |
Also Published As
Publication number | Publication date |
---|---|
JPS5855229B2 (en) | 1983-12-08 |
EP0056675B1 (en) | 1984-11-28 |
ATE10513T1 (en) | 1984-12-15 |
EP0056675A3 (en) | 1982-08-04 |
DE3261311D1 (en) | 1985-01-10 |
JPS57120678A (en) | 1982-07-27 |
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