AU634652B2 - Process of aftertreating conversion layers - Google Patents
Process of aftertreating conversion layers Download PDFInfo
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- AU634652B2 AU634652B2 AU76180/91A AU7618091A AU634652B2 AU 634652 B2 AU634652 B2 AU 634652B2 AU 76180/91 A AU76180/91 A AU 76180/91A AU 7618091 A AU7618091 A AU 7618091A AU 634652 B2 AU634652 B2 AU 634652B2
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- conversion layers
- aftertreated
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- aluminum
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- 238000000034 method Methods 0.000 title claims description 29
- 238000006243 chemical reaction Methods 0.000 title claims description 26
- 239000000243 solution Substances 0.000 claims description 26
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 8
- 229910000838 Al alloy Inorganic materials 0.000 claims description 7
- -1 hafnium ions Chemical class 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 claims description 2
- 210000002837 heart atrium Anatomy 0.000 claims description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 claims description 2
- 238000010422 painting Methods 0.000 claims description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 claims description 2
- 229960001860 salicylate Drugs 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical compound OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 0.000 claims description 2
- 235000009917 Crataegus X brevipes Nutrition 0.000 claims 1
- 235000013204 Crataegus X haemacarpa Nutrition 0.000 claims 1
- 235000009685 Crataegus X maligna Nutrition 0.000 claims 1
- 235000009444 Crataegus X rubrocarnea Nutrition 0.000 claims 1
- 235000009486 Crataegus bullatus Nutrition 0.000 claims 1
- 235000017181 Crataegus chrysocarpa Nutrition 0.000 claims 1
- 235000009682 Crataegus limnophila Nutrition 0.000 claims 1
- 235000004423 Crataegus monogyna Nutrition 0.000 claims 1
- 240000000171 Crataegus monogyna Species 0.000 claims 1
- 235000002313 Crataegus paludosa Nutrition 0.000 claims 1
- 235000009840 Crataegus x incaedua Nutrition 0.000 claims 1
- 238000010030 laminating Methods 0.000 claims 1
- 239000012487 rinsing solution Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 235000002639 sodium chloride Nutrition 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- 229920001864 tannin Polymers 0.000 description 3
- 239000001648 tannin Substances 0.000 description 3
- 235000018553 tannin Nutrition 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229920001665 Poly-4-vinylphenol Polymers 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000007739 conversion coating Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229920001944 Plastisol Polymers 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical compound [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000003475 lamination 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
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000004999 plastisol Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 235000020681 well water Nutrition 0.000 description 1
- 239000002349 well water Substances 0.000 description 1
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 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
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
- C23C22/361—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing titanium, zirconium or hafnium compounds
-
- 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
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
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)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Laminated Bodies (AREA)
Description
.lr;i -i -ili~. 1IC-~ P/00/011 Regulation 3.2
AUSTRALIA
Patents Act 1990 6 3 4 COMPLETE SPECIFICATION FOR A STANDARD PATENT
ORIGINAL
Application Number: 761 80/90 Lodged: 29.4.91 TO BE COMPLETED BY APPLICANT Name of Applicant: Actual Inventcr(s): METALLGESELLSCHAFT AKTIENGESELLSCHAFT THOMAS KOLBERG, WERNER RAUSCH, PETER SCHUBACH and THOMAS WENDEL Address for Service: c/o WATERMARK ATTORNEYS, The Hawthorn, Victoria PATENT TRADEMARK Atrium, 290 Burwood Road, 3122, Australia.
Invention Title: PROCESS OF AFTERTREATING CONVERSION LAYERS The following statement is a full description of this invention, including the best method of performing it known to me:- PROCESS OF AFTERTREATING CONVERSION LAYERS
DESCRIPTION
This invention relates to a process of post rinsing conversion layers which have been formed on surfaces of aluminum or aluminum alloys by a treatment with solutions based on titanium, zirconium and/or hafnium ions, and to the use of that process for a pretreatment preceding a painting, film lamination or adhesive coating operation.
The production of conversion layers on surfaces of aluminum or aluminum alloys, particularly as a pretreatment before the application of an organic coating, is industrially performed on a large scale. Such conversion layers will prevent or oppose 1 0 the occurrence of corrosion and under an organic coating will improve the bond strength of the coating which has been applied. Whereas said requirements are sufficiently met, as a rule, by the widely employed chromate layers, the productions of chromium-free conversion layers is increasingly preferred for reasons of work place hygiene and environmental protection or because the treated material is intended to be used for specific purposes, for packaging foodstuffs. The treatment solutions for forming chromium-free conversion layers are generally adjusted to an acid pH value and they contain, titanium, fluc de, phosphate and tannin Patent 4,017,334) or zirconium, fluoride and boron Patent 3,964,936). A treating solution which contains hafnium and fluoride has been described in French Patent Specification 2,417,537.
The properties of the conversion layers which have been formed can further be impoved by a succeeding passivating aftertreatment. For the reasons stated, it is preferred to effect the aftertreatment with chromium-free treating solul ins, which contain organic active substances, as a rule. Such an aftertreating solution based on polyvinylphenol has been described in US-A 4,376 000. But that solution will pollute the sewage, particularly because there is a large demand for oxygen required to decompose the organic component.
It is an object of the invention to provide for the passivating post rinsing of chromium-free conversion layers on surfaces of aluminum or aluminum alloys a process 3 0 which does not have the disadvantage of post rinsing solutions that contain organic components as regards the need for a treatment of the waste water but will result in an improvement of the corrosion resistance and the bond strength of paint at least to the same degree.
The object is accomplished in that the process which is of the kind described first 3 5 hereinbefore is carried out in such a manner in accordance with the invention that the ani ~-e~-r~c~Dlra~-c~l~ conversion layers are aftertreated with aqueous solutions which contain aluminum, zirconium and fluoride and have been adjusted to a pH value The process in accordance with the invention can be used for a passivating aftertreatment of conversion layers that have been formbJ on surfaces of aluminum or aluminum alloys, which materials may consist of massive aluminum or massive aluminum alloy or of objects which have been plated therewith, by hot dip coating.
Suitable elements which can be alloyed with aluminum are particularly silicon, manganese, magnesium zinc and copper.
The conversion layers formed on such surfaces by a treatment with solutions based 1 0 on Ti, Zr and/or Hf distinguish in that the thickness of the layer is distinctly below 1 gm, that the layers are amorphous at least in part, and that they do not contain chromium. In addition to titanium, zirconium and/or hafnium ions the treating solutions employed to form the conversion layers contain additional film-forming and/or pickling compon6ns, such as fluorides, phosphates and compounds of boron, and optionally contain passivating 1 5 components, such as tannins. Suitable treating solutions have been described in the patent specifications mentioned hereinbefore.
The surface on which the conversion layer has been formed is suitably rinsed with water.
The post rinsing solution may be applied, by dipping, flooding, spraying or roller coating.
A preferred feature of the invention resides in that the post rinsing solution employed contains aluminum, zirconium and fluoride in a total Al Zr F concentration between 0.1 and 8 g/l, preferably between 0.2 and 5 g/l. The Al :Zr F mole ratios should desirably be adjusted to (0.15 to 8) 1 (5 to 52), particularly to (0.15 to 1 (5 to 16). In a particularly preferred embodiment of the process the Al Zr F ratios in the post rinsing solution are (0.15 to 0.67) 1 (5 to According to a further desirable feature of the invention the pH value is adjusted to 2 to The post rinsing solutions used in the process in accordance with the invention contain, inter alia, acid aluminumrn fluoride zirconates and in case of a surplus of aluminum additionally contain other salts of aluminum, such as fluorides, tetrafluoroborates, nitrates. They may be produced, in that zirconium metal or zirconium carbonate is initially dissolved in aqueous hydrofluoric acid to form complex fluorozirconium acid. Aluminum metal or aluminum hydroxide or an aluminum salt, suc, as the nitrate, fluoride, tetrafluoborate, formr te, acetate, is then added, preferably in dissolved form, and is optionally dissolved. A possible slight cloudiness of the solution will not adversely affect its effectiveness. Whereas the preparation is preferably
,L
C
J1 1 effected on the described route, the solutions may alternatively prepared in a different manner.
The pH value of the solution is preferably adjusted with cations of volatile bases.
These include particularly ammonium, ethanolammonium and di-and triethanolammonium. The adjustment particularly to relatively high pH values in the stated pH range and to relatively high concentrations in the range stated for the total concentration of Al Zr F may result in a cloudiness of the solution but this will not adversely affect the effectiveness of the process.
According to a further desirable feature of the invention the surfaces provided with 1 0 a conversion coating are aftertreated with an aqueous solution which additionally contains at least one of the anions benzoate, caprylate, ethyl hexoate, salicylate, preferably in a total concentration of 0.05 to 0.5 g/l. This will further increase the bare corrosion protection. The anions may be introduced by means of the corresponding acids or their salts.
1 5 According to a further desirable feature of the invention the post rinsing solution is applied for between about 1 and 120 seconds, particularly for between 1 and seconds. The solution may be applied at a temperature between 200C and about 800C.
Temperatures between 20 and 50 0 C are preferred.
Deionized water or low-salt water is preferably used to prepare the post rinsing 2 0 bath. Water having a high salt content is less suitable for the preparation of the bath.
After the passivating aftertreatment the surface may be dried, on the air or in an oven and optionally may be rinsed before with deionized water. According to a preferred embodiment of the invention the surface which has been subjected to the passivating aftertreatment is subjected to an accelerated drying, with hot air or by infrared radiation.
The process in accordance with the invention serves primarily to pretreat surfaces of aluminum or aluminum alloys before they are painted, laminated with a film or coated with an adhesive. Suitable organic coating materials include, Polyesters, silicone-modified polyesters, polyvinylidenefluorides, acrylates, epoxides, epoxyphenol resins, plastisols or organosols of PVC or acrylates).
The advantage afforded by the process in accordance with the invention resides particularly in that the bond strength of the organic films on the metallic substrate is increased, as is reflected, by correspondingly good results achieved in the T-Bend Test (ISO 1519-1973) or in the Feathering Test (bond strength of paint during an opening of can closures). Besides, the corrosion resistance of the organic films to a corrosive action, is also increased, in a test in which an aqueous condensate is formed under constant air conditions (DIN 50 017 KK) or a sterilization test. The process in accordance with the invention also increases the corrosion resistance of the surface which has not been provided with an organic coating, as is reflected, in a test for well water blackening (no blackening in boiling water).
The process in accordance with the invention will be explained .nore in detail and by way of example with reference to the following example.
Example To form a conversion coating on cleaned and degreased aluminum sheets they were dipped for 10 seconds into a solution which was at a temperature of 500C and had the 1 0 following composition: Ti 0.17 g/l F 1.24 g/I
P
2 0s 0.09 g/l
NH
4 0.91 g/l tannin 0.11 g/l Na 0.003 g/l biocide 0.10 g/l Thereafter the sheets were rinsed with water and were then subjected to a passivating aftertreatment. To that end the sheets were dipped into the post rinsing 2 0 solution for 5 seconds and were subsequently squeeged for a removal o f surplus solution.
After a drying at 600C in an oven operated with circulating air for 0.5 minute the sheets were painted with a two-layer coating that is approved for use with foodstuffs. The first layer of said coating consists of an epoxyphenol resin and the second layer consists of an organosol. The coating had a total thickness between 10 and 15 p.m.
Circular blanks 60 mm in diameter were subsequently blanked from the treated sheets, which had a thickness of about 0.25 mm, and the blanks were deep drawn to form cups which were 26 mm in diameter and had a height of 25 mm.
Said cups were subjected to a sterilization test, in which they were exposed in a pressure container to the action of an aqueous solution of 3% common salt, 1% citric acid and 0.5% lactic acid at 121°C for 40 minutes. The defects subsequently detected on the cups (delamination of paint, blisters) were rated with reference to a scale from 1 (delamination of the paint throughout the shell of the cup unusable) to 15 (no paint defect excellent).
To prepare the post rinsing solution to be employed, 1.6 g/l and 3.2 g/I 3 5 respectively of an aqueous concentrate, which contained 0.855% by weight Al and 8.62% -g 1 rr. h. 6 by weight Zr and 10.7% by weight F, was diluted with deionized water to yield post rinsing solution A and post rinsing solution B.
Both solutions were adjusted with ammonia to a pH value of about 3.6.
For comparison, an aftertreatment was effected with a polyvinylphencl solution having a concentration of 0.6 g/l and a pH value of about 5 (post rinsing solution The post rinsing solutions employed in the process in accordance with the invention had the following compositions: Post rinsing solution A: Post rinsing solution B: Al 0.014 g/l Al 0.028 g/l Zr 0.14 g/l Zr 0.28 g/l F 0.17 g/l F 0.34 g/l
NH
4 0.016 g/l NH 4 0.03 g!l Test results obtained in sterilization test (Rating scale: 1 unusable to 15 excellent) Post Rinsing Solution A (invention) B (invention) C (comparison) Rating 11 6 Comparison of the tabulated data reveals that the process in accordance with the invention produces distinctly better results than the comparison example using an post rinsing solution based on polyvinylphenol.
Claims (9)
1. A process of aftertreating conversion layers, said conversion layers having been formed on surfaces of aluminum or aluminum alloys by treatment with solutions based on titanium, zirconium and/or hafnium ions, characterized in that the conversion layers are aftertreated with aqueous solutions which contain aluminum, zirconium and fluoride and have been adjusted to a pH value
2. A process according to claim 1, characterized in that the conversion layers are aftertreated with solutions which contain aluminum, zirconium and fluoride in a total Al Zr F concentration between 0.1 and 8 g/l, preferably between 0.2 and 5 g/l.
3. A process according to claim 1 or 2, characterized in that the conversion layers are aftertreated with solutions in which the Al Zr: F mole ratios have been adjusted to (0.15 to 8) 1 (5 to 52), particularly to (0.15 to 2,0) 1: (5 to 16).
4. A process according to claim 1, 2 or 3, characterized in that the conversion layers are aftertreated with solutions in which the Al Zr: F mole ratios have been adjusted to (0.15 to 0.67) 1 (5 to 7). A process according to any of claims 1 to 4, characterized in that the conversion layers are aftertreated with solutions which have been adjusted to a pH value of 2 to
6. A process according to any of claims 1 to 5, characterized in that the conversion layers are aftertreated with solutions in which the pH value has been adjusted with cations of volatile bases, preferably with ammonium, ethanolammonium, di- or triethanolammonium.
7. A process according to any of claims 1 to 6, characterized in that the conversion layers are aftertreated with solutions which additionally contain at least one of the anions benzoate, caprylate, ethyl hexoate, salicylate in a total concentration of 0.05 to 0.5 g/l.
8. A process according to any of claims 1 to 7, characterized in that the conversion layers S are aftertreated for 1 to 120 seconds, preferably for 1 to 30 seconds. 3_ L-
9. A process according to any of claims 1 to 8, characterized in that the conversion layers are aftertreated with solutions which are at temperatures of 20 to 800C, preferably of 20 to 500C. A process according to any of claims 1 to 9, characterized in that the surface is dried when it has been aftertreated.
11. The use of the process according to any of claims 1 to 10 as a pretreatment before painting, film-laminating or adhesive coating operation. DATED this 29th day of April 1991. METALLGESELLSCHAFT AKTIENGESELLSCHAFT WATERMARK PATENT TRADEMARK ATTORNEYS "THE ATRIUM" 290 BURWOOD ROAD HAWTHORN. VIC. 3122. SKP:JL
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4017187 | 1990-05-29 | ||
| DE4017187A DE4017187A1 (en) | 1990-05-29 | 1990-05-29 | METHOD FOR REFILLING CONVERSION LAYERS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU7618091A AU7618091A (en) | 1991-12-12 |
| AU634652B2 true AU634652B2 (en) | 1993-02-25 |
Family
ID=6407364
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU76180/91A Ceased AU634652B2 (en) | 1990-05-29 | 1991-04-29 | Process of aftertreating conversion layers |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0459550B1 (en) |
| JP (1) | JP3083873B2 (en) |
| AU (1) | AU634652B2 (en) |
| BR (1) | BR9102174A (en) |
| CA (1) | CA2041891C (en) |
| DE (2) | DE4017187A1 (en) |
| ES (1) | ES2047370T3 (en) |
| ZA (1) | ZA914086B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06322287A (en) * | 1993-05-14 | 1994-11-22 | Nippon Parkerizing Co Ltd | Surface-treated composite aluminum powder and method for producing surface-treated composite aluminum flakes using the same |
| DE4317217A1 (en) * | 1993-05-24 | 1994-12-01 | Henkel Kgaa | Chrome-free conversion treatment of aluminum |
| IT1273111B (en) * | 1994-04-07 | 1997-07-04 | Skf Ind Spa | PRE-ASSEMBLY PROCEDURE OF A MULTIPOLAR MAGNETIZED RING, IN PARTICULAR FOR THE APPLICATION IN ROTATION SPEED DETECTION DEVICES, AND RELATED PRODUCT |
| CZ216697A3 (en) * | 1995-01-10 | 1997-12-17 | Circle Prosco | Method of coating metal surfaces with a highly hydrophilic, biologically resistant odorless coating exhibiting high resistance to corrosion |
| US7402214B2 (en) | 2002-04-29 | 2008-07-22 | Ppg Industries Ohio, Inc. | Conversion coatings including alkaline earth metal fluoride complexes |
| US6749694B2 (en) | 2002-04-29 | 2004-06-15 | Ppg Industries Ohio, Inc. | Conversion coatings including alkaline earth metal fluoride complexes |
| JP4612321B2 (en) | 2003-04-04 | 2011-01-12 | 株式会社東芝 | Nonaqueous electrolyte secondary battery |
| DE102016206417A1 (en) | 2016-04-15 | 2017-10-19 | Henkel Ag & Co. Kgaa | PROMOTION TREATMENT FOR SUPPRESSING PLANT-ORIENTED PHOSPHATOR TRANSPORT IN A PROCESS FOR DIVING LACQUER |
| DE102016206418A1 (en) * | 2016-04-15 | 2017-10-19 | Henkel Ag & Co. Kgaa | SUPPRESSION OF PLANT-SPECIFIC PHOSPHATE EXTRACTION IN A PROCESS FOR DIPPING LACQUER |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3912548A (en) * | 1973-07-13 | 1975-10-14 | Amchem Prod | Method for treating metal surfaces with compositions comprising zirconium and a polymer |
| US4370177A (en) * | 1980-07-03 | 1983-01-25 | Amchem Products, Inc. | Coating solution for metal surfaces |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3850732A (en) * | 1970-12-02 | 1974-11-26 | Amchem Prod | Zirconium rinse for phosphate coated metal surfaces |
| US3895970A (en) * | 1973-06-11 | 1975-07-22 | Pennwalt Corp | Sealing rinse for phosphate coatings of metal |
| US4462842A (en) * | 1979-08-13 | 1984-07-31 | Showa Aluminum Corporation | Surface treatment process for imparting hydrophilic properties to aluminum articles |
| US4496404A (en) * | 1984-05-18 | 1985-01-29 | Parker Chemical Company | Composition and process for treatment of ferrous substrates |
| DE3829154A1 (en) * | 1988-08-27 | 1990-03-01 | Collardin Gmbh Gerhard | CHROME-FREE METHOD FOR PRE-TREATING METALLIC SURFACES BEFORE COATING WITH ORGANIC MATERIALS |
| DE3924984A1 (en) * | 1989-07-28 | 1991-01-31 | Metallgesellschaft Ag | METHOD FOR PASSIVATING RINSING OF PHOSPHATE LAYERS |
-
1990
- 1990-05-29 DE DE4017187A patent/DE4017187A1/en not_active Withdrawn
-
1991
- 1991-04-29 ES ES91201021T patent/ES2047370T3/en not_active Expired - Lifetime
- 1991-04-29 DE DE91201021T patent/DE59100650D1/en not_active Expired - Fee Related
- 1991-04-29 EP EP91201021A patent/EP0459550B1/en not_active Expired - Lifetime
- 1991-04-29 AU AU76180/91A patent/AU634652B2/en not_active Ceased
- 1991-05-06 CA CA002041891A patent/CA2041891C/en not_active Expired - Fee Related
- 1991-05-28 BR BR919102174A patent/BR9102174A/en unknown
- 1991-05-28 JP JP03152483A patent/JP3083873B2/en not_active Expired - Fee Related
- 1991-05-29 ZA ZA914086A patent/ZA914086B/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3912548A (en) * | 1973-07-13 | 1975-10-14 | Amchem Prod | Method for treating metal surfaces with compositions comprising zirconium and a polymer |
| US4370177A (en) * | 1980-07-03 | 1983-01-25 | Amchem Products, Inc. | Coating solution for metal surfaces |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3083873B2 (en) | 2000-09-04 |
| JPH04231480A (en) | 1992-08-20 |
| ZA914086B (en) | 1993-01-27 |
| DE59100650D1 (en) | 1994-01-13 |
| AU7618091A (en) | 1991-12-12 |
| DE4017187A1 (en) | 1991-12-05 |
| EP0459550B1 (en) | 1993-12-01 |
| CA2041891A1 (en) | 1991-11-30 |
| EP0459550A1 (en) | 1991-12-04 |
| ES2047370T3 (en) | 1994-02-16 |
| BR9102174A (en) | 1991-12-24 |
| CA2041891C (en) | 2001-07-31 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MK14 | Patent ceased section 143(a) (annual fees not paid) or expired |