EP0683246A1 - Traitement de nettoyage et de passivation de métaux - Google Patents
Traitement de nettoyage et de passivation de métaux Download PDFInfo
- Publication number
- EP0683246A1 EP0683246A1 EP95301519A EP95301519A EP0683246A1 EP 0683246 A1 EP0683246 A1 EP 0683246A1 EP 95301519 A EP95301519 A EP 95301519A EP 95301519 A EP95301519 A EP 95301519A EP 0683246 A1 EP0683246 A1 EP 0683246A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ion
- molybdate
- treatment solution
- borate ion
- imidazoline
- 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
- 238000011282 treatment Methods 0.000 title claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 17
- 239000002184 metal Substances 0.000 title claims abstract description 17
- 238000004140 cleaning Methods 0.000 title claims abstract description 11
- 238000002161 passivation Methods 0.000 title description 5
- 150000002739 metals Chemical class 0.000 title description 3
- 239000002280 amphoteric surfactant Substances 0.000 claims abstract description 21
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 19
- 229940063013 borate ion Drugs 0.000 claims abstract description 18
- 235000015393 sodium molybdate Nutrition 0.000 claims abstract description 15
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 15
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 15
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 12
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical class CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000001412 amines Chemical class 0.000 claims abstract description 8
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract 2
- 239000010452 phosphate Substances 0.000 claims abstract 2
- SHNJHLWLAGUBOV-UHFFFAOYSA-N sodium;oxido(oxo)borane;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Na+].[O-]B=O SHNJHLWLAGUBOV-UHFFFAOYSA-N 0.000 claims description 8
- 239000002736 nonionic surfactant Substances 0.000 claims description 5
- 239000002518 antifoaming agent Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 description 10
- -1 alkanolamines Chemical class 0.000 description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 8
- 239000013530 defoamer Substances 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Polymers 0.000 description 2
- 239000003139 biocide Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical class OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
-
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/24—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions
Definitions
- the present invention relates to cleaning and passivating treatments for metals. More particularly, the present invention relates to cleaning and passivating treatments for metals which are essentially free of amines, alkanolamines, and phosphates.
- the aqueous treatments of the present invention comprise amphoteric surfactants which were found to provide an excellent passivating film on ferrous surfaces.
- the amphoteric surfactants of the present invention are caprylic acid derivatives of imidazoline compounds.
- In process cleaners are employed in the metal treatment industry to clean and passivate a metal surface. These types of aqueous cleaners are typically based on organic rust-proofing or passivating agents such as combinations of alkanolamines and fatty acids, surfactants, anti-foam agents and/or phosphonates and possibly biocides and builders. In order to passivate a metal surface to prevent rusting during process breaks and storage, appropriate additives are used. Cleaning and passivating agents which inhibit the corrosion of ferrous metal surfaces contain for example alkali nitrites, alkanolamines, soaps and benzoates.
- Clean and passivate treatments are typically employed in applications which require good cleaning and temporary metal passivation. Treated parts may need to remain rust-free, while exposed in the manufacturing plant for from several hours up to 30 days. In order to maintain their rust prevention ability, these cleaners are not rinsed.
- Current commercial cleaners typically employ alkanolamines such as monoethanolamine, diethanolamine or triethanolamine as a passivating agent for ferrous surfaces. The alkanolamine component inhibits flash rusting of ferrous iron parts during line stops or storage.
- Typical cleaners also will include surfactants such as glycol ether compounds and phosphonate compounds which aid in cleaning of the parts.
- U.S. Patent No. 4,578,208 which issued to Geke et al. discloses a cleaning and/or passivating composition and process which employs a phosphoric acid ester, an alkanolamine and a surfactant and optionally builders, non-ferrous metal inhibitors and biocides.
- the present inventors discovered that a specific class of amphoteric surfactants provides excellent passivation of ferrous metals when substituted for alkanolamines.
- the use of amphoteric surfactants in accordance with the present invention obviates the need for amines, alkanolamines, phosphates and other currently environmentally undesirable materials in clean and passivate formulations.
- the inventors found that caprylic acid derivatives of imidazoline compounds provide efficacious passivation of ferrous metal surfaces.
- the treatment solution of the present invention is substantially free of amines, alkanolamines, and phosphates. By substantially free, it is meant that these materials are not intentionally added as active components of the treatment solution.
- the preferred treatment solution also includes small quantities of a borate ion and sodium molybdate. These compounds were found to allow reductions in the concentration of the amphoteric surfactant component without adversely affecting efficacy.
- a defoamer such as a nonionic surfactant may be desirable in spray applications.
- the present inventors discovered a clean and passivate treatment formulation for use in treating ferrous metal surfaces which is substantially free of amines, alkanolamines, and phosphates.
- the clean and passivate formulation of the present invention is an aqueous solution of a caprylic acid derivative of an imidazoline.
- the formulation preferably also includes a borate ion, sodium molybdate and a nonionic surfactant defoamer.
- the inventors found that aqueous solutions of caprylic acid derivatives of an imidazoline provide effective rust protection.
- amphoteric surfactants were used in combination with a borate ion and sodium molybdate significantly lower concentrations of the amphoteric surfactant could be employed with good rust inhibition results.
- the borate ion may be provided by a borate salt or by boric acid.
- the formulation of the present invention includes amphoteric surfactants which are caprylic acid derivatives of an imidazoline compound.
- the surfactants are present in the treatment solution at concentrations of from about 0.05% up to about 5% by weight.
- amphoteric surfactants include Monateric Cy-Na 50%, a sodium salt of 2-caprylic-1 (ethyl beta oxypropanoic acid) imidazoline; Monateric LF-100, a C5 ⁇ 9 methyl alkyl imidazoline; Monateric LF-Na 50, a sodium salt of LF-100 but 50% active; Monateric CYA-50, a capryl ampho-propionate; Monateric 1000, a capryl amphopropionate; and Miranol JAS concentrate which is a carboxylate derivative of capryl imidazoline.
- Miranol is a trademark of Rhone-Poulenc and Monateric is a trademark of Mona Industries.
- Amphopropionate is another name for imidazoline.
- the preferred treatment concentration is about 5% by weight.
- a caprylic acid derivative of an imidazoline is employed in the preferred combination which includes a borate ion (such as sodium metaborate octahydrate) and a molybdate ion (such as sodium molybdate)
- the concentration of the surfactant can be decreased to about 0.1 to 0.3% by weight.
- the preferred concentration of sodium molybdate is from about 0.1 to 0.5% by weight.
- the preferred concentration of sodium metaborate octahydrate is from about 0.1 to 0.5% by weight.
- the ratio of imidazoline to borate ion is from about 1:0.4 to 1.5 and the ratio of molybdate ion to imidazoline and borate ion is more than about 1:4
- the clean and passivate formulation of the present invention is typically supplied in two concentrate packages which are diluted and mixed prior to application.
- the first comprises the caprylic derivative of imidazoline compound; sodium molybdate and sodium metaborate octahydrate in deionized water.
- the second package comprises a nonionic surfactant defoaming agent.
- Efficacy of the treatment solution of the present invention was evaluated in a chip test evaluation.
- the test involved placing 4 g of cast iron chips on a filter paper in a plastic weighing dish, adding 50 ml of the test solution, allowing the solution to stand for 24 hours.
- the filter paper is rinsed with tap water and examined for rust spots. Refer to ASTM D4627-92.
- compositions and methods of the present invention are demonstrated by the following examples which are provided as illustrative and are not intended to limit the scope of the invention as set forth in the claims.
- amphoteric surfactants which are imidazoline compounds were tested in the above manner. Table I summarizes the results.
- Table II shows that efficacious results are obtained at a relatively low treatment concentration with the preferred combination of the present invention.
- Example 3 The presence of Macol LF 110 in the composition of Example 3 is included to inhibit foaming tendencies of the imidazoline surfactant. The presence of the defoamer does not effect the passivating activity of the imidazoline surfactant.
- Table IV summarizes chip testing as described above of a treatment in accordance with the present invention with and without a nonionic polyoxyalkylated aliphatic ether defoamer (Macol LF 110 available from PPG Industries, Inc.). TABLE IV Composition (grams/100 grams) Chip Test Monateric LF Na-50 NaBO2.8H20 Sodium Molybdate Water Macol LF 110 1. 0.075 0.37 0.075 99.48 ----- no rust spots 2. 0.075 0.37 0.075 99.44 0.04 no rust spots 3. 0.10 0.50 0.10 99.30 ----- no rust spots 4. 0.10 0.50 0.10 99.26 0.04 no rust spots
- the treatment solution of the present invention is preferably supplied as a concentrate which is diluted with deionized water to form a working bath.
- a preferred concentrate comprises 12.5% sodium metaborate octahydrate, 2.5% sodium molybdate, 5.0% Monateric LF-Na 50 and 80% deionized water.
- the Macol LF 110 defoamer is supplied separately.
- a 4% v/v dilution of the preferred concentrate with 0.04% v/v of Macol LF 110 results in the treatment solution described in Example 3. This preferred treatment solution has been found to be effective when diluted with DI, soft or hard water.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Detergent Compositions (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US24655094A | 1994-05-20 | 1994-05-20 | |
| US246550 | 1994-05-20 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0683246A1 true EP0683246A1 (fr) | 1995-11-22 |
| EP0683246B1 EP0683246B1 (fr) | 2000-07-19 |
Family
ID=22931164
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP95301519A Expired - Lifetime EP0683246B1 (fr) | 1994-05-20 | 1995-03-08 | Traitement de nettoyage et de passivation de métaux |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0683246B1 (fr) |
| AT (1) | ATE194858T1 (fr) |
| CA (1) | CA2143471A1 (fr) |
| DE (1) | DE69518036T2 (fr) |
| ES (1) | ES2148433T3 (fr) |
| PT (1) | PT683246E (fr) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102797004A (zh) * | 2012-08-23 | 2012-11-28 | 李征 | 环保型有色金属表面处理剂及制备方法 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1133385A (en) * | 1966-03-18 | 1968-11-13 | Fuji Iron & Steel Company Ltd | Storage of corrodible metals |
| US4450088A (en) * | 1983-05-19 | 1984-05-22 | Basf Wyandotte Corporation | Corrosion inhibited alcohol compositions |
| EP0124851A2 (fr) * | 1983-05-07 | 1984-11-14 | Henkel Kommanditgesellschaft auf Aktien | Composition et procédé pour le nettoyage et la passivation de métaux par pulvérisation |
| EP0229440A1 (fr) * | 1985-12-27 | 1987-07-22 | Texaco Development Corporation | Inhibiteur de corrosion pour antigel à base d'acide/sel monobasique/dibasique |
| EP0328872A1 (fr) * | 1988-02-22 | 1989-08-23 | Pacific Gas and Electric Company | Inhibition de la corrosion de circuits clos secondaires d'eau de refroidissement dans les centrales nucléaires |
| EP0552988A1 (fr) * | 1992-01-21 | 1993-07-28 | BP Chemicals Limited | Composition antigel |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4759847A (en) * | 1983-12-05 | 1988-07-26 | Medbury Seward J | Filter for the sorption of a petroleum product from a liquid |
-
1995
- 1995-02-27 CA CA002143471A patent/CA2143471A1/fr not_active Abandoned
- 1995-03-08 EP EP95301519A patent/EP0683246B1/fr not_active Expired - Lifetime
- 1995-03-08 DE DE69518036T patent/DE69518036T2/de not_active Expired - Fee Related
- 1995-03-08 PT PT95301519T patent/PT683246E/pt unknown
- 1995-03-08 ES ES95301519T patent/ES2148433T3/es not_active Expired - Lifetime
- 1995-03-08 AT AT95301519T patent/ATE194858T1/de not_active IP Right Cessation
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1133385A (en) * | 1966-03-18 | 1968-11-13 | Fuji Iron & Steel Company Ltd | Storage of corrodible metals |
| EP0124851A2 (fr) * | 1983-05-07 | 1984-11-14 | Henkel Kommanditgesellschaft auf Aktien | Composition et procédé pour le nettoyage et la passivation de métaux par pulvérisation |
| US4578208A (en) * | 1983-05-07 | 1986-03-25 | Henkel Kommanditgesellschaft Auf Aktien | Compositions and processes for cleaning and passivating metals |
| US4450088A (en) * | 1983-05-19 | 1984-05-22 | Basf Wyandotte Corporation | Corrosion inhibited alcohol compositions |
| EP0229440A1 (fr) * | 1985-12-27 | 1987-07-22 | Texaco Development Corporation | Inhibiteur de corrosion pour antigel à base d'acide/sel monobasique/dibasique |
| EP0328872A1 (fr) * | 1988-02-22 | 1989-08-23 | Pacific Gas and Electric Company | Inhibition de la corrosion de circuits clos secondaires d'eau de refroidissement dans les centrales nucléaires |
| EP0552988A1 (fr) * | 1992-01-21 | 1993-07-28 | BP Chemicals Limited | Composition antigel |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102797004A (zh) * | 2012-08-23 | 2012-11-28 | 李征 | 环保型有色金属表面处理剂及制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| PT683246E (pt) | 2000-11-30 |
| DE69518036D1 (de) | 2000-08-24 |
| EP0683246B1 (fr) | 2000-07-19 |
| ATE194858T1 (de) | 2000-08-15 |
| CA2143471A1 (fr) | 1995-11-21 |
| DE69518036T2 (de) | 2001-03-22 |
| ES2148433T3 (es) | 2000-10-16 |
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