EP0180523B1 - Procédé perfectionné de phosphatation au zinc, bain d'activation et d'affinage mis en oeuvre dans ce procédé et concentré correspondant - Google Patents
Procédé perfectionné de phosphatation au zinc, bain d'activation et d'affinage mis en oeuvre dans ce procédé et concentré correspondant Download PDFInfo
- Publication number
- EP0180523B1 EP0180523B1 EP85402096A EP85402096A EP0180523B1 EP 0180523 B1 EP0180523 B1 EP 0180523B1 EP 85402096 A EP85402096 A EP 85402096A EP 85402096 A EP85402096 A EP 85402096A EP 0180523 B1 EP0180523 B1 EP 0180523B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- bath
- fact
- ppm
- activating
- 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.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000007670 refining Methods 0.000 title claims abstract description 27
- 239000012141 concentrate Substances 0.000 title claims description 12
- 230000004913 activation Effects 0.000 title description 22
- 239000011248 coating agent Substances 0.000 title description 3
- 238000000576 coating method Methods 0.000 title description 3
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 title description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 title description 2
- 150000003839 salts Chemical class 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011701 zinc Substances 0.000 claims abstract description 20
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 20
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000203 mixture Chemical class 0.000 claims abstract description 15
- 230000003213 activating effect Effects 0.000 claims abstract description 13
- 239000010936 titanium Substances 0.000 claims abstract description 10
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 238000005238 degreasing Methods 0.000 claims abstract description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000001447 alkali salts Chemical class 0.000 claims abstract description 6
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 6
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical class [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000470 constituent Substances 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 239000000956 alloy Substances 0.000 claims abstract description 3
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 3
- 239000011651 chromium Substances 0.000 claims abstract description 3
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 239000000758 substrate Substances 0.000 claims abstract 2
- 238000007654 immersion Methods 0.000 claims description 17
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- 239000001488 sodium phosphate Substances 0.000 claims description 8
- 150000003009 phosphonic acids Chemical class 0.000 claims description 7
- 159000000000 sodium salts Chemical class 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims description 4
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 4
- 239000008235 industrial water Substances 0.000 claims description 4
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 4
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 4
- -1 alkyl radical Chemical class 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 150000005840 aryl radicals Chemical class 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- SZHQPBJEOCHCKM-UHFFFAOYSA-N 2-phosphonobutane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CCC(P(O)(O)=O)(C(O)=O)CC(O)=O SZHQPBJEOCHCKM-UHFFFAOYSA-N 0.000 claims 4
- 238000002360 preparation method Methods 0.000 claims 1
- 229910019142 PO4 Inorganic materials 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 235000021317 phosphate Nutrition 0.000 description 8
- 239000008399 tap water Substances 0.000 description 8
- 235000020679 tap water Nutrition 0.000 description 8
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 7
- 239000010452 phosphate Substances 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical class [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920000388 Polyphosphate Polymers 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
- 235000011176 polyphosphates Nutrition 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- UOKRBSXOBUKDGE-UHFFFAOYSA-N butylphosphonic acid Chemical compound CCCCP(O)(O)=O UOKRBSXOBUKDGE-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- DKPHLYCEFBDQKM-UHFFFAOYSA-H hexapotassium;1-phosphonato-n,n-bis(phosphonatomethyl)methanamine Chemical compound [K+].[K+].[K+].[K+].[K+].[K+].[O-]P([O-])(=O)CN(CP([O-])([O-])=O)CP([O-])([O-])=O DKPHLYCEFBDQKM-UHFFFAOYSA-H 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003892 tartrate salts Chemical class 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- 229940006486 zinc cation Drugs 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
- 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
- step (3) can be omitted, the activating constituents then being introduced directly into the bath used for the step of alkaline degreasing.
- step (3) becomes essential in order to obtain a sufficiently fine and dense phosphating.
- the baths intended for covering the zinc phosphating stage can comprise, in addition to the zinc cation, other metals such as nickel, manganese, calcium or possibly iron, as widely described in the scientific literature.
- the refining agents used at the time of the activation and refining step or which can be used at the time of the alkaline degreasing step in the case of processes carried out entirely by jet are constituted by compounds of titanium, in particular colloidal titanium salts known under the name of Jernstedt salts; these salts are described in particular in US Pat. No. 2,456,947.
- Such a Jernstedt salt can be obtained by mixing 95 parts of disodium phosphate with 5 parts of potassium fluotitanate in an amount of water sufficient to dissolve the ingredients. The water is then removed from the mixture by evaporation at a temperature of 80 to 100 ° C.
- titanium can be used for the production of Jernstedt salt, such as for example titanium sulfate or titanium oxide.
- Polyphosphates can also be added to the Jernstedt salts, in particular in a proportion of 1 to 300 parts by weight of? 2 0 7 .
- Jernstedt salts are commonly found on the market and are in particular marketed by the Applicant Company under the trademark “FIXODINE 5”.
- the object of the invention is, above all, to remedy these drawbacks and to ensure that, in the phosphating methods of the genus in question, the activation and refining step can be carried out with industrial water without overflow and supply of refining salts proportional to the quantities of water added while providing a refining and stability effect comparable to that obtained with demineralized water.
- R representing an alkyl radical or a ra dical aryl optionally substituted with at least one of the substituents of the group comprising the hydroxyl radical, other phosphonic groups and the amino groups of formula in which R 2 and R 3 which may be identical or different from each other, each represent a hydrogen atom or have the meaning of R 1 .
- the salts of the acids of formula (I) and of 2-phosphono-butane-1,2,4-tricarboxylic acid which can be used are those obtained by partial or total neutralization with alkaline ions such as Na + and K + or by the NH 4 + ion .
- the bath used in the above process is also referred to as a new industrial product.
- constituents of the refining bath used in accordance with the invention may be pyrophosphates or alkali citrates.
- these baths are prepared from concentrates containing the acid of formula (1) or 2-phosphono-butane-1,2,4-tricarboxylic acid or their salt and Jernstedt salt in such proportions that mixing it with an appropriate quantity of water provides the activation and refining bath used in accordance with the invention.
- the activation and refining step according to the invention is carried out at a temperature of 20 to 50 ° C.
- the stability of the bath used is sufficient for it to be able to operate under normal conditions without regeneration, that is to say without the addition of additional amounts of concentrate other than the normal amounts to be provided by consumption of the product, for approximately 5 15 days.
- the aim is to study the influence of different activation baths on the morphology of the zinc phosphate crystals deposited in the phosphating step.
- This morphology is examined using a scanning electron microscope at a magnification of 1500.
- Two examinations are carried out, the first of which is carried out after treatment in a new bath, 10 minutes after assembly, and the second of which is carried out after treatment in the same bath, 6 days after assembly thereof.
- the activation bath comprises 2 g / l of Jernstedt salt (FIXODINE 5) in demineralized water corresponding to 20 ppm of titanium.
- FIXODINE 5 Jernstedt salt
- the other ingredients are sodium phosphates.
- the pH is 7.
- Example 2 Same composition and same pH as in Example 1, but the water consists of tap water.
- the pH 7.9.
- the bath is identical to that of Example 3, except that the phosphonic acid is present at the rate of 100 ppm.
- the bath is identical to that of Example 4, but the pH is brought to 9 with trisodium phosphate.
- the bath is identical to that of Example 6 in the except that the sodium salt of phosphonic acid is present at 200 ppm.
- the bath is identical to that of Example 7, except that the phosphonic acid is present at the rate of 100 ppm and the pH is then 7.
- test pieces thus treated are examined under the electron microscope, as indicated above.
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Detergent Compositions (AREA)
- Manufacture And Refinement Of Metals (AREA)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT85402096T ATE44051T1 (de) | 1984-10-31 | 1985-10-30 | Verfahren zur beschichtung mit zinkphosphaten, aktivierungs- und schichtverfeinerungsbad fuer dieses verfahren und konzentrat dafuer. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8416725A FR2572422B1 (fr) | 1984-10-31 | 1984-10-31 | Bain d'activation et d'affinage perfectionne pour procede de phosphatation au zinc et concentre correspondant |
| FR8416725 | 1984-10-31 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0180523A1 EP0180523A1 (fr) | 1986-05-07 |
| EP0180523B1 true EP0180523B1 (fr) | 1989-06-14 |
Family
ID=9309205
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP85402096A Expired EP0180523B1 (fr) | 1984-10-31 | 1985-10-30 | Procédé perfectionné de phosphatation au zinc, bain d'activation et d'affinage mis en oeuvre dans ce procédé et concentré correspondant |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4678519A (ja) |
| EP (1) | EP0180523B1 (ja) |
| JP (1) | JPS61124582A (ja) |
| AT (1) | ATE44051T1 (ja) |
| CA (1) | CA1260809A (ja) |
| DE (1) | DE3571050D1 (ja) |
| FR (1) | FR2572422B1 (ja) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4793867A (en) * | 1986-09-26 | 1988-12-27 | 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 |
| CA1309315C (en) * | 1987-07-14 | 1992-10-27 | Toan Manh Ngo | Compositions and process for metal treatment |
| DE3814287A1 (de) * | 1988-04-28 | 1989-11-09 | Henkel Kgaa | Polymere titanphosphate, verfahren zu ihrer herstellung und ihre verwendung zur aktivierung von metalloberflaechen vor einer zinkphosphatierung |
| DE3814363A1 (de) * | 1988-04-28 | 1989-11-09 | Henkel Kgaa | Titanfreie aktivierungsmittel, verfahren zu ihrer herstellung und ihre verwendung zur aktivierung von metalloberflaechen vor einer zinkphosphatierung |
| US5003986A (en) * | 1988-11-17 | 1991-04-02 | Kenneth D. Pool, Jr. | Hierarchial analysis for processing brain stem signals to define a prominent wave |
| US4917737A (en) * | 1989-03-13 | 1990-04-17 | Betz Laboratories, Inc. | Sealing composition and method for iron and zinc phosphating process |
| DE4131950A1 (de) * | 1991-09-25 | 1993-04-01 | Boehme Chem Fab Kg | Produkte als flussmittel und umschmelzfluessigkeiten bei der herstellung von leiterplatten |
| FR2686622B1 (fr) * | 1992-01-29 | 1995-02-24 | Francais Prod Ind Cfpi | Concentre pour bain d'activation et d'affinage et bain obtenu a partir de ce concentre. |
| US5628838A (en) * | 1992-01-29 | 1997-05-13 | C.F.P.I Societe Anonyme | Concentrate for activating and defining bath and bath obtained from this concentrate |
| US5326408A (en) * | 1993-06-15 | 1994-07-05 | Henkel Corporation | Rapidly dissolving and storage stable titanium phosphate containing activating composition |
| US5494504A (en) * | 1994-09-12 | 1996-02-27 | Ppg Industries, Inc. | Liquid rinse conditioner for phosphate conversion coatings |
| US20050268991A1 (en) * | 2004-06-03 | 2005-12-08 | Enthone Inc. | Corrosion resistance enhancement of tin surfaces |
| CN111534815A (zh) * | 2020-05-22 | 2020-08-14 | 山东大学 | 可在金属表面形成可水洗本色转化膜的前处理液及其制备方法 |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3864139A (en) * | 1970-12-04 | 1975-02-04 | Amchem Prod | Pretreatment compositions and use thereof in treating metal surfaces |
| DE2951600A1 (de) * | 1979-12-21 | 1981-07-02 | Gerhard Collardin GmbH, 5000 Köln | Verfahren zur vorbehandlung von metalloberflaechen vor dem phosphatieren |
| US4427459A (en) * | 1982-01-25 | 1984-01-24 | Pennwalt Corporation | Phosphate conversion coatings for metals with reduced coating weights and crystal sizes |
| DE3213649A1 (de) * | 1982-04-14 | 1983-10-27 | Gerhard Collardin GmbH, 5000 Köln | Verfahren zum reinigen und entfetten sowie aktivieren von metalloberflaechen |
| DE3217145A1 (de) * | 1982-05-07 | 1983-11-10 | Gerhard Collardin GmbH, 5000 Köln | Verfahren zum reinigen, entfetten sowie aktivieren von metalloberflaechen |
| US4497667A (en) * | 1983-07-11 | 1985-02-05 | Amchem Products, Inc. | Pretreatment compositions for metals |
-
1984
- 1984-10-31 FR FR8416725A patent/FR2572422B1/fr not_active Expired - Fee Related
-
1985
- 1985-10-30 CA CA000494250A patent/CA1260809A/en not_active Expired
- 1985-10-30 DE DE8585402096T patent/DE3571050D1/de not_active Expired
- 1985-10-30 EP EP85402096A patent/EP0180523B1/fr not_active Expired
- 1985-10-30 AT AT85402096T patent/ATE44051T1/de not_active IP Right Cessation
- 1985-10-31 JP JP60243024A patent/JPS61124582A/ja active Granted
- 1985-10-31 US US06/793,346 patent/US4678519A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0568552B2 (ja) | 1993-09-29 |
| JPS61124582A (ja) | 1986-06-12 |
| US4678519A (en) | 1987-07-07 |
| ATE44051T1 (de) | 1989-06-15 |
| FR2572422B1 (fr) | 1993-03-05 |
| FR2572422A1 (fr) | 1986-05-02 |
| DE3571050D1 (en) | 1989-07-20 |
| EP0180523A1 (fr) | 1986-05-07 |
| CA1260809A (en) | 1989-09-26 |
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