EP0358338B1 - Method and composition for surface treatment - Google Patents
Method and composition for surface treatment Download PDFInfo
- Publication number
- EP0358338B1 EP0358338B1 EP89308114A EP89308114A EP0358338B1 EP 0358338 B1 EP0358338 B1 EP 0358338B1 EP 89308114 A EP89308114 A EP 89308114A EP 89308114 A EP89308114 A EP 89308114A EP 0358338 B1 EP0358338 B1 EP 0358338B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- sol
- composition
- adhesion promoter
- powder
- concentration
- 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 - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims description 64
- 238000000034 method Methods 0.000 title claims description 29
- 238000004381 surface treatment Methods 0.000 title description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000000843 powder Substances 0.000 claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 37
- 238000000576 coating method Methods 0.000 claims abstract description 30
- 239000002318 adhesion promoter Substances 0.000 claims abstract description 29
- 239000011248 coating agent Substances 0.000 claims abstract description 21
- 239000011253 protective coating Substances 0.000 claims abstract description 21
- 239000007787 solid Substances 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 34
- 239000004411 aluminium Substances 0.000 claims description 22
- 229910052782 aluminium Inorganic materials 0.000 claims description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 21
- 239000012530 fluid Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- 239000000499 gel Substances 0.000 claims description 13
- 150000004706 metal oxides Chemical class 0.000 claims description 13
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 12
- 229910044991 metal oxide Inorganic materials 0.000 claims description 12
- 235000011007 phosphoric acid Nutrition 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 239000007800 oxidant agent Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 10
- -1 nitrilotrismethylene phosphonates Chemical class 0.000 claims description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- 239000011733 molybdenum Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 231100000331 toxic Toxicity 0.000 claims description 8
- 230000002588 toxic effect Effects 0.000 claims description 8
- 239000011164 primary particle Substances 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 235000021317 phosphate Nutrition 0.000 claims description 5
- 150000003016 phosphoric acids Chemical class 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 abstract description 29
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 11
- 229910000077 silane Inorganic materials 0.000 abstract description 11
- 238000011282 treatment Methods 0.000 abstract description 11
- 238000005260 corrosion Methods 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 7
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 239000000853 adhesive Substances 0.000 description 27
- 239000010410 layer Substances 0.000 description 24
- 238000009472 formulation Methods 0.000 description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 239000004922 lacquer Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 239000002253 acid Substances 0.000 description 11
- 239000000758 substrate Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- 238000005189 flocculation Methods 0.000 description 8
- 230000016615 flocculation Effects 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 6
- 239000000470 constituent Substances 0.000 description 6
- 238000001723 curing Methods 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 229910052726 zirconium Inorganic materials 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 5
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 229920006332 epoxy adhesive Polymers 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000012876 topography Methods 0.000 description 5
- 239000002966 varnish Substances 0.000 description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 150000004703 alkoxides Chemical class 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 229910052755 nonmetal Inorganic materials 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 238000007761 roller coating Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 241000894007 species Species 0.000 description 4
- 229910002019 Aerosil® 380 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000008199 coating composition Substances 0.000 description 3
- 238000007739 conversion coating Methods 0.000 description 3
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 description 3
- 239000003349 gelling agent Substances 0.000 description 3
- 229910052735 hafnium Inorganic materials 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- 238000007743 anodising Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001493 electron microscopy Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229920000592 inorganic polymer Polymers 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000000386 microscopy Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910003638 H2SiF6 Inorganic materials 0.000 description 1
- 241000588731 Hafnia Species 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000009924 canning Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229910001651 emery Inorganic materials 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- QQFLQYOOQVLGTQ-UHFFFAOYSA-L magnesium;dihydrogen phosphate Chemical compound [Mg+2].OP(O)([O-])=O.OP(O)([O-])=O QQFLQYOOQVLGTQ-UHFFFAOYSA-L 0.000 description 1
- 229910000401 monomagnesium phosphate Inorganic materials 0.000 description 1
- 235000019785 monomagnesium phosphate Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000001956 neutron scattering Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- ZEFWRWWINDLIIV-UHFFFAOYSA-N tetrafluorosilane;dihydrofluoride Chemical compound F.F.F[Si](F)(F)F ZEFWRWWINDLIIV-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/10—Oxidising
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
- C23C22/74—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process for obtaining burned-in conversion coatings
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1229—Composition of the substrate
- C23C18/1241—Metallic substrates
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1254—Sol or sol-gel processing
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- 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
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- 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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
Definitions
- This invention relates to methods and aqueous compositions for surface treatment.
- One purpose of the treatment is to increase the adhesion of subsequently applied coatings, such as paint, lacquer, varnish or adhesive.
- Another purpose is to decrease adhesion, i.e. to confer non-stick properties on the surface.
- Yet another purpose is to provide protection for the surface from mechanical and chemical damage.
- the invention is of application to solid surfaces generally, it is of major importance in relation to metals generally, and in particular to aluminium.
- Alocrom 100 is the Trade Mark of a commercially available chromium-based pretreatment applied to aluminium before coating with organic finishes such as lacquer on can stock or powder coating on architectural components. Excess chromium solution must be rinsed away before the organic coating is applied. This kind of pretreatment is known as conversion coating. Control of the chromium ions in the rinse water to prevent pollution can be a problem with this formulation.
- Accomet C is the Trade Mark of another commercially available chromium-based pretreatment, as described in US Patent 3706603.
- the composition is applied to a metal workpiece and dried in situ without washing; this is known as a no-rinse pretreatment.
- Accomet C avoids the chromium pollution problems of Alocrom 100, but is not used on can stock for food or beverages because of the danger of toxic chromates leaching out. It is used as a pretreatment for aluminium components that are to be adhesively bonded together, for example as described in British Patent Specification 2139540.
- Alocrom 404 is the Trade Mark of a commercially available pretreatment based on zirconium. This is a conversion coating which requires rinsing, but the absence of chromium reduces pollution problems. The protection is not as good as that provided by Accomet C or by Alocrom 100, but it does find some application in the food industry.
- Patent Specifications which describe metal pretreatment systems based on zirconium, often in the form of fluorozirconate, include US 3964936; 4191596; 4273592; 4339310; 4370177; and EPA 61911. (Some of these mention Ti, Si and Hf as alternatives for Zr.) All these are conversion coatings containing dissolved Zr.
- US Patent 4623591 describes a method of preparing metal surfaces for adhesive bonding by the application of a metal alkoxide solution, which hydrolyses on the surface to form an amorphous hydrated metal oxide layer.
- AI alkoxides are preferably used, though Ti, Zr, Fe and Ni alkoxides are mentioned as alternatives. Because these metal alkoxides hydrolyse in the presence of moisture, it is necessary to use them in solution in organic solvents such as toluene, which solutions have short shelf life and major handling, cost and environmental problems.
- GB 2107215 and 2134008 describe aqueous compositions based on inorganic sols containing refractory oxides for application to refractory substrates followed by firing to produce coatings for catalytic or electronic applications.
- EPA 273698 describes coating compositions to improve adhesion of paints etc, which compositions comprise a silica sol containing a dissolved aluminium or iron salt.
- U.S. Patent 4,271,210 describes forming a clear thin metal oxide layer on a glass substrate by applying a solution of partly hydrolysed aluminium alkoxide.
- Japanese Kokai 52-73138 describes sealing aluminium-plated steel members with an aqueous solution of aluminium biphosphate and/or magnesium biphosphate optionally containing also a silica or alumina sol.
- the invention provides a method which comprises applying to a solid surface an aqueous composition consisting essentially of an inorganic hydrous oxide sol containing an adhesion promoter selected from the class consisting of fluorozirconates, silane coupling agents, nitrilostrismethylene phosphonates, phosphoric acids, phosphate esters and oxidising agents for the surface and optionally also a passenger powder, but not containing toxic hexavalent chromium or molybdenum, and curing the composition to form a protective coating on the surface.
- an adhesion promoter selected from the class consisting of fluorozirconates, silane coupling agents, nitrilostrismethylene phosphonates, phosphoric acids, phosphate esters and oxidising agents for the surface and optionally also a passenger powder, but not containing toxic hexavalent chromium or molybdenum, and curing the composition to form a protective coating on the surface.
- the invention provides a method which comprises applying to a solid surface:
- the method is suitable for the pretreatment of solid surfaces such as non-metals and metals generally, including steel, titanium, copper, zinc and, particularly aluminium, which term is used herein to include the pure metal and its alloys.
- the method can be arranged to improve the adhesion properties of the pretreated surface, by improving the adhesion thereto of a subsequently applied coating such as paint, varnish, lacquer or adhesive.
- the pretreatment may improve either the initial adhesion of the subsequently applied coating to the surface or the maintenance of such adhesive properties in service, or both the initial adhesion and maintenance of adhesives properties.
- the benefits of the invention may be shown mainly not in the initial adhesive strength obtained, but in the maintenance of adhesive strength in hostile or corrosive environments.
- the inorganic sol is a stable, aqueous, colloidal dispersion containing primary particles or aggregates of primary particles, which are smaller than 150 nm.
- sols can be classified into three types; type A, B and C.
- Type A sols consist of basic units which are polynuclear ions which form an 'inorganic polymer' and are formed by hydrolysis and polymerisation of monomeric cations.
- the molecular weight of the polynuclear cations will depend on the degree of hydrolysis but these sols normally have an anion to metal ratio of approximately 1:1.
- the polymeric species are not large enough to scatter light efficiently, so the sol and the resultant gel are optically clear.
- the gel has a high density, low porosity and the x-ray diffraction pattern consists of very broad bands.
- J. D. F. Ramsay “Neutron and Light Scattering Studies of Aqueous Solutions of Polynuclear lons. Water and Aqueous Solutions", 207-218 1986 (ed G. W. Neilson and J. E. Enderby: Bristol. Adam Hilger).
- Type A sols may be formed from the polynuclear ions listed in this paper including those containing AI(III) Fe(III) Zr(IV)
- Type B sols consist of basic units with a definite shape, e.g. spherical, rod or plate-like, and are amorphous or microcrystalline.
- the sol is formed by extensive hydrolysis of a salt and has a low anion to metal atom ratio of approximately 0.3:1.
- the sols can also be prepared by peptization of fresh precipitates.
- the colloidal units are not aggregated and the sol and the resultant gel are both clear.
- Type B sols include (AI(III) Zr(IV) Ce(IV) Ti(IV) Fe(III).
- Preparation of Type B AI(III) sols is described in GB 1,174,648.
- Preparation of Ce Type B sol is described in GB 1,342,893.
- Type B Alumina Sols are available commercially.
- the basic colloidal units are aggregated. They are crystalline and the gels formed by removal of water have a low density. These sols scatter light and are therefore opaque.
- the gels derived from a type C sol are porous and have a density ⁇ 45% of the theoretical density of the oxide.
- the inorganic sol for use in this invention is a hydrous oxide sol, preferably a hydrous metal oxide sol, that is to say a Type A or Type B (but not Type C) sol.
- a hydrous oxide sol preferably a hydrous metal oxide sol, that is to say a Type A or Type B (but not Type C) sol.
- examples are zirconia sols, ceria sols, titania sols, hafnia sols, alumina sols, and iron oxyhydroxide sols.
- Silica sols exemplify non-metal oxide sols.
- Zirconia sols are readily formed by peptising basic zirconium carbonate in mineral acid.
- the constitution of zirconia sols when the associated anion is nitrate or bromide or chloride is discussed in a UKAEA Research Group Report, reference AERE - R5257 (1966) by J.L. Woodhead and J.M. Fletcher.
- Zirconia sols contain extensively hyrolysed inorganic polymers with a primary particle size of less than 10 nm. The polymer is thought to be built up of hydrated oxy-hydroxide species of zirconium. When nitric acid is used, the species is believed to have the formula: where n is thought to be approximately one in dilute sols and greater than one at higher concentrations.
- Ceria and titania and other hydrous metal oxide sols may be formed by peptising the corresponding hydrated metal oxide with a mineral acid.
- a fluid which gels the layer and/or a passenger powder on the surface.
- A1 2 0 3 passenger powder may be gelled on the surface by phosphoric acid.
- This fluid may be in vapour phase, for example a low molecular weight amine such as ethylamine or preferably ammonia, which is applied after the aqueous composition and simply serves to gel and thereby fix the layer on the surface.
- the fluid is a liquid, particularly an aqueous liquid containing a gelling agent for the sol. This liquid may be applied to the surface to deposit the gelling agent thereon, prior to application of the inorganic sol.
- the liquid can be applied to the surface already carrying a layer of the inorganic sol. It is preferred, though not essential, that the layer of inorganic sol be dried prior to application of the gelling fluid. Gelling of the layer causes or may cause shrinkage, and care may need to be taken to prevent cracking of the layer at this stage. Drying may be effected at temperatures below 100°C, conveniently at ambient temperature.
- Either the aqueous composition i) or the fluid ii) may contain an adhesion promoter. These materials may also act as gelling agents for the sol.
- the two step method of this invention allows the incorporation of high concentrations of these reagents into the fluid ii).
- the dissolved adhesion promoting constituent should preferably be substantially non-toxic.
- the constituent promotes adhesion, for example by providing suitable links to the underlying substrate and to the overlying organic layer, or by inhibiting corrosion at the organic coating/substrate interface. It is believed that adhesive bond strength falls on exposure to water or more aggressive agents because of corrosion or hydration at this interface. Inhibition of this corrosion helps to retain adhesive bond strength.
- Adhesion promoters are known and employed to enhance the joint strength, or more commonly to enhance the environmental resistance of the substrate surface/adhesive interface to attack by moisture. Adhesion promoters were described by P.E.Cassidy et al in Ind. Eng. Chem. Prod. Res. Development, Vol 11, No.2 (1972) pages 170-7; and by A.J.Kinlock in J. Mat. Sci., 15 (1980) pages 2141-66 at page 2159. But these articles do not discuss coating compositions.
- the adhesion promoter may comprise fluoride values and one or more of Ti, Si, Hf and Zr values. These can be provided separately. They may conveniently be provided by dissolving fluorozirconic acid H 2 ZrFs, or a soluble fluorozirconate salt, in water; alternatively, a corresponding acid or salt of Ti, Si or Hf, e.g. H 2 TiFs, H 2 SiF 6 or H 2 HfF 6 , may be used.
- Fluorozirconate (or other fluoro complex) is preferably present at a concentration of 0.1 to 200 gl-', particularly from 10 to 100 gl-', of the fluid ii). When provided separately, the fluoride and zirconium (or other) values are preferably sufficient to give a fluorozirconate (or other fluoro complex) concentration in this range.
- the adhesion promoter may comprise phosphate or phosphonate, preferably in a concentration of 0.05 to 200 gl-', particularly 10 to 100 gl -1 , of the fluid.
- Phosphate esters are known to bond well onto aluminium surfaces and to be able to inhibit corrosion.
- organic phosphorus-containing compounds which may be used, examples being amino-phosphates for example nitrilotris (methylene) phosphonic acid (NTMP) or other nitrilo-substituted phosphonic acids or phosphate esters such as bis-(nonyl phenyl ethylene oxide) phosphate.
- the adhesion promoter may comprise one or more silane coupling agents which are organosilanes, for example glycidoxypropyltrimethoxy silane or aminopropyltriethoxy silane, which may act to promote adhesion, preferably in a concentration of 0.05% to 10% by volume on the volume of the fluid.
- silane coupling agents which are organosilanes, for example glycidoxypropyltrimethoxy silane or aminopropyltriethoxy silane, which may act to promote adhesion, preferably in a concentration of 0.05% to 10% by volume on the volume of the fluid.
- organosilanes for example glycidoxypropyltrimethoxy silane or aminopropyltriethoxy silane, which may act to promote adhesion, preferably in a concentration of 0.05% to 10% by volume on the volume of the fluid.
- organosilanes for example glycidoxypropyltrimethoxy silane or aminopropyltrie
- the adhesion promoter may be an oxidizing agent for the surface.
- the Ce 4+ species which may be provided in the form of a hydrated ceria sol or as a dissolved ceric salt, and permanganate.
- the oxidizing agent acts on the aluminium or other metal (e.g. iron or steel) or non-metal surface, improves adhesion of the surface to the protective coating formed by drying the composition, and should be used at a concentration designed to achieve these ends.
- the aqueous composition or the fluid may also contain a passenger powder, which can be used to give the protective coating a desired surface topography.
- the powder is preferably an inert metal oxide such as silica, zirconia, titania or alumina. This may be a type C sol, or a powder produced by comminution, for example. Powder loadings of 1 to 300 gl-', preferably 5 - 150 gl-', more particularly 10 - 75 gl- 1 are appropriate.
- the powder may have an average primary particle size below 250 nm, e.g. in the range 3-150 nm, particularly 4 - 100 nm, and is preferably of substantially uniform particle size.
- the passenger powder is present in the aqueous composition containing the inorganic sol. It is possible to incorporate the passenger powder in the fluid ii), provided that the fluid does not react and/or destabilise the passenger powder, as for example when phosphoric acid is added to an A1 2 0 3 powder. When this fluid brings about gelation of the sol, the powder becomes incorporated in the layer on the metal surface.
- the aqueous composition generally has an acid pH, typically in the range 1 .5 to 7. Sol concentration is chosen to achieve a convenient application viscosity.
- the sol may typically contain from 1 to 200 gl- 1 metal oxide equivalent.
- the adhesion promoting constituent when used in the aqueous composition may be present in conventional concentrations, for example from 0.001 % to 10% by volume.
- a particularly preferred aqueous composition comprises:
- the surface to which the aqueous composition is to be applied may be cleaned by conventional means appropriate to the substrate concerned.
- this may be an acid or alkaline cleaning treatment, using commercially available chemicals such as those sold by ICI under the trade marks Ridolene 124 and 124E.
- the (aluminium or titanium) metal surface may be pre-treated to form thereon an artificially applied oxide layer.
- Such treatments include acid etching (Forest Products Laboratories), and anodizing treatments with sulphuric, chromic or phosphoric acid, the latter being particularly effective in terms of bond strength and durablity. It has been shown by means of transmissions electron microscopy that phosphoric acid anodizing treatment produces fine oxide protrusions of greater length and magnitude than other surface treatments. These whiskers are believed to account for the strength enhancement achieved with joints made using phosphoric acid anodized adherends. Thus, mechanical interlocking by whisker reinforcement of an adhesive appears to play a role in enhancing adhesive bonding.
- the aqueous compositions of this invention can be applied to such profiled surfaces in layers so thin and uniform that the profiled surface topography is substantially maintained. It is believed that the artificially applied oxide layer provides improved initial adhesion for subsequently applied artificial coatings by mechanical interlocking; and that the protective coatings applied according to this invention ensure that the initial excellent adhesion properties are not reduced on prolonged exposure to humid or corrosive environments.
- an adhesion promoter to the sol in a controlled manner, i.e. slowly with stirring, results in a clear, homogenous sol with no apparent flocculation.
- the coating produced by such a pretreatment is therefore smooth and featureless.
- the adhesion promoter can be included in the gelling fluid ii).
- adhesion promoter is added in a less controlled manner, irreversible flocculation occurs and a turbid pretreatment sol is obtained. Consequently, the coating deposited on the surface is more textured.
- silane coupling agents addition of water to the silane (rather than the recommended procedure of adding the silane reagent to water) results in the formation of condensed polysiloxanes which also contribute to surface microtexturing.
- adhesion to non-metal or metal substrate of subsequently applied organic coatings such as paint, lacquer, varnish or adhesive, depends substantially upon the properties of two interfaces:
- the composition may be applied to the substrate surface (optionally carrying an artificially applied oxide layer with a profiled surface) by any convenient technique, such as spin coating, immersion, flow or roller coating, brushing, or by spraying.
- roller coating is likely to be an attractive option.
- the formulation may need to be adjusted to provide a convenient viscosity for application by the desired method.
- the coating on the surface is cured.
- Curing temperatures are from ambient up to 700 ° C, usually (though not always) below those required to fully sinter the particles, and may typically be in the range 50 to 400 ° C. Calcination of the coating at temperatures above 400 ° C is possible but not usually necessary.
- curing temperatures in the range 50 - 100 ° C are preferred.
- curing temperatures in the range 100 ° C to 400 ° C are preferred. Removal of water takes place progressively and is still not complete at 400 ° C.
- the surface preferably carries the coating at a rate of from 0.01 to 5 gm- 2 , preferably between 0.02 and 0.7 gm- 2 , and most preferably from 0.05 to 0.3 gm- 2 .
- Thinner coatings up to 1.5 gm- 2 will normally be preferred when the metal surface has been provided with an underlying artificially applied oxide layer.
- the invention envisages as an additional method step the application to the protective coating of an organic coating such as paint, lacquer, varnish or adhesive.
- an organic coating such as paint, lacquer, varnish or adhesive.
- An example of a commercially available epoxy adhesive suitable for this application is Permabond ESP105.
- thicker coatings e.g. of up to 5 gm- 2 may be preferred and passenger powders with average particle sizes up to 1 ⁇ m or even up to 5 ⁇ m may be used.
- the sol was diluted to 10% or 2% of the original concentration. Further dilution also occurred as a result of mixing the sols with equal volumes of solutions of the adhesion promoters. This mixing was effected by dropwise addition with stirring, thus without significant sol flocculation, and as a result the protective coating had a smooth, glassy appearance under the microscope. Volumes used are summarised in Table 1.
- 300 x 100 panel of 5251 alloy were vapour degreased and then acid cleaned by a 1 minute immersion in Ridolene 124 acid cleaner at a temperature of between 55 and 60 °C. Following cleaning, the samples were thoroughly rinsed in deionised water and pretreated by spin coating. Surfaces were thoroughly wetted with the pretreatment solution prior to spin coating. All pretreatments were dried in an oven at 200 °C for 1 minute. Additional samples of metal pretreated with the additive-free formulations were dried at 100 ° C.
- Samples were cut to a width of 20 mm, stacked (ca 12 samples) and cut to a length of 90 mm.
- a single part epoxy adhesive containing 1% ballotini was applied to one end of two specimens.
- Specimens were mounted in a jig giving 10 mm overlap, clipped together, and subsequently removed from the jig and cured at 180 ° C for a time of 30 minutes, commencing from the time the sample temperature reached 175 ° C. Following curing, excess adhesive was filed off the edges of the sample and, finally the same edges were smoothed with emery cloth.
- Samples for accelerated testing were immersed in deionised water at 60 ° C for 200 hours. All samples were tested on a Zwick tensile tester using a crosshead speed of 2 mm min -1 .
- Pretreated sheets were then cut to form 20mm x 100mm coupons, bent to form L-shaped adherends and bonded, with a standard heat-cure single-part structural epoxy adhesive, to give T-shaped joints with a 60mm long bondline. These were peeled at 5mm/min on an Instron 1115 tensile tester and the steady-state peel load was recorded during the peel event.
- Treatment solutions were prepared and coated as described in Examples 1 to 10 except that dilution with the adhesion promoter was done quickly causing some flocculation of the sol. Coatings produced from the treatments were microtextured.
- Treatment solutions containing silane adhesion promoters were prepared and applied as described in Example 11 except that the silane was diluted to 0.5 volume percentage by adding water to the silane A1110. (The recommended procedure is to add the silane to water.)
- the coatings were microtextured.
- aqueous compositions according to the invention were made up by the general procedure given in Examples 1 to 10. Sample pretreatment and preparation and testing of adhesive joints were also as described in Examples 1 to 10. Details of formulations and peel strengths are set out in Table 3 below.
- the powder was always the last constituent to be added, i.e. it was added to the final sol/adhesion promoter or sol/oxidising agent mixture, with mixing for 1 hour in a Silverson high shear blender to ensure good dispersion.
- Rhone-Poulenc Ceria hydrate (typically 70.9 wt% oxide) was slurried in distilled water. 16ml of conc. HN0 3 in 34ml of water was added to the slurry and stirred thoroughly. The mixture was heated to 70 ° C for 30 minutes allowed to cool and then to settle. The supernate was decanted and water added to the residue to give a final volume of 417ml. The residue immediately disperses to give a stable sol of 425 gl -1 concentration.
- the sol was diluted to 10% or 2% of the original concentration.
- 0.1 M ceric salt, Ce-(S04) 2 was added dropwise to the ceria sol, while stirring rapidly, such that minimal flocculation occured.
- the 1.5% silica was added finally.
- a 5wt% titania sol was prepared by dispersing the gel in deionised water.
- the stock sol was dilute further for use in formulation 5.
- the zirconia sol was diluted to 10% of the original conc. 0.1 M KMn0 4 solution was added dropwise to the sol while stirring rapidly such that minimal flocculation occurred. The 1.5% silica powder was added finally.
- Lacquers were applied to the treated panels and then drawn into standard shaped cans.
- the four lacquer systems applied and the adhesion test conditions used are standard in the field.
- Feathering refers to the degree of detachment of a lacquer film from a surface in a ring-pull-tab configuration.
- the feathering test was carried out by applying an organosol lacquer on the pretreated surface of an aluminium coupon.
- the lacquered coupon was sterilised in water at 130 ° C for 1 hour.
- Parallel lines were scribed on the reverse side of the metal and the metal was then scrolled back along the scribes.
- Feathering was assessed by noting the extent of detachment of lacquer along the metal edge. A score of 0 indicates best performance (i.e. no feathering) and a score of 4 indicates poor performance. Results are set out in Table 4.
- a pretreatment formulation containing 3 components i.e. the sol, the adhesion promoter and the passenger powder
- 3 components i.e. the sol, the adhesion promoter and the passenger powder
- a second formulation containing a higher sol concentration and a lower silane concentration and a series of other formulations containing a range of chemistries were prepared in a similar manner.
- the pretratment formulations were applied on precleaned aluminium by roller coating and dried at 80 ° C for 3 mins.
- concentration of constituents in the respective formulations, the peel strength of resultant adhesive joints (using a modified epoxy adhesive), the tensile adhesive bond strength and bond strength after 200 hours and 1000 hours of immersion in water maintained at 60 °C, are given in Table 5.
- the results are compared with Alocrom 4040, a commercial pretreatment based on fluorozirconic acid and applied by dip coating at 30 for 10 mins. and dried at 120 ° C for 3 mins., as recommended by the supplier (ICI).
- Formulation 3 described in Table 5 was used to prepare single lap adhesive joints which were stressed to 8MPa by means of a calibrated spring arrangement and exposed to condensing humidity of 98-100%, in a test cabinet. The joints remained intact after 100 days of testing. Comparison joints made using Accomet C failed after 87 days.
- CR2 steel was precleaned by degreasing, abrading and degreasing again.
- Single lap adhesive joints were prepared with the pretreated metal and the joints exposed to neutral salt spray (5% NaCI) maintained at 43 ° C.
- the lap shear strength of the joints were measured at various intervals and compared with lap shear strengths of adhesive joints prepared with electrogalvanised steel.
- the sol pretreatment resulted in superior performance. The results are given in Table 6.
- a pretreatment formulation consisting of 1% Zr0 2 sol, 0.8% amino silane and 4% silica prepared as described in Example 22 (formulation 1), was roller coated on aluminium foil, and heated to 200 ° C for 3 mins. The coated foil was immersed in liquid Nitrogen to cause embrittlement of the coating and then bent through 180°. Scanning election microscopy revealed that the pretreatment layer did not delaminate under these conditions. The sol component formed a flexible skin adjacent to the metal surface and deformed with the metal. Cracking was observed in the pretreatment layer when a similar test was carried out on Alocrom 4040 pretreated aluminium.
- a pretreatment consisting of 1% Zr0 2 sol 0.5% aminosilane and 6% alumina (Example 22 formulation 3) was dehydrated by either spray drying or tray drying.
- the tray dried powder was redispersed in water and used to pretreat aluminium.
- the peel strength of the resultant metal:adherend joint was 55N. [The peel strength of a joint prepared with the original formulation, prior to dehydration and reconstitution was 74N].
- a pretreatment formulation consisting of 3.1% Zr0 2 sol and 1% silane [N ( ⁇ -aminoethyl) -y-aminopropyltrimethoxy silane] was roll coated on aluminium metal and dried at 80 ° C for 3 mins. Scanning election microscopy revealed a smooth, featureless coating on the metal surface. The same pretreatment was also roller coated on phosphoric acid anodised metal. Scanning electron microscopy showed that the pretreatment coated the alumina whiskers while maintaining the open, porous topography. A cross section also revealed that the pretreament had penetrated the anodic film and formed a dense layer adjacent to the metal surface.
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Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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GB888819259A GB8819259D0 (en) | 1988-08-12 | 1988-08-12 | Method & composition for metal treatment |
GB8819259 | 1988-08-12 | ||
GB8912424 | 1989-05-31 | ||
GB898912424A GB8912424D0 (en) | 1989-05-31 | 1989-05-31 | Metal treatment method |
Publications (3)
Publication Number | Publication Date |
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EP0358338A2 EP0358338A2 (en) | 1990-03-14 |
EP0358338A3 EP0358338A3 (en) | 1990-04-11 |
EP0358338B1 true EP0358338B1 (en) | 1994-07-27 |
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EP89308114A Expired - Lifetime EP0358338B1 (en) | 1988-08-12 | 1989-08-09 | Method and composition for surface treatment |
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EP (1) | EP0358338B1 (da) |
JP (1) | JPH0285373A (da) |
KR (1) | KR900003403A (da) |
CN (1) | CN1040811A (da) |
AT (1) | ATE109217T1 (da) |
AU (1) | AU625900B2 (da) |
BR (1) | BR8904061A (da) |
CA (1) | CA1337145C (da) |
DE (1) | DE68917059T2 (da) |
DK (1) | DK394089A (da) |
ES (1) | ES2059772T3 (da) |
IN (1) | IN176027B (da) |
MY (1) | MY104467A (da) |
NO (1) | NO893250L (da) |
PT (1) | PT91432B (da) |
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- 1989-08-07 IN IN700DE1989 patent/IN176027B/en unknown
- 1989-08-09 ES ES89308114T patent/ES2059772T3/es not_active Expired - Lifetime
- 1989-08-09 AT AT89308114T patent/ATE109217T1/de not_active IP Right Cessation
- 1989-08-09 EP EP89308114A patent/EP0358338B1/en not_active Expired - Lifetime
- 1989-08-09 DE DE68917059T patent/DE68917059T2/de not_active Expired - Fee Related
- 1989-08-10 MY MYPI89001093A patent/MY104467A/en unknown
- 1989-08-11 AU AU39511/89A patent/AU625900B2/en not_active Ceased
- 1989-08-11 DK DK394089A patent/DK394089A/da not_active Application Discontinuation
- 1989-08-11 BR BR898904061A patent/BR8904061A/pt not_active Application Discontinuation
- 1989-08-11 PT PT91432A patent/PT91432B/pt not_active IP Right Cessation
- 1989-08-11 CA CA000608068A patent/CA1337145C/en not_active Expired - Fee Related
- 1989-08-11 NO NO89893250A patent/NO893250L/no unknown
- 1989-08-12 CN CN89107593A patent/CN1040811A/zh active Pending
- 1989-08-12 KR KR1019890011529A patent/KR900003403A/ko not_active Application Discontinuation
- 1989-08-14 JP JP1210005A patent/JPH0285373A/ja active Pending
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EP0201228A2 (en) * | 1985-04-30 | 1986-11-12 | Allegheny Ludlum Steel Corporation | Grain-oriented silicon steel and stress coating therefor |
EP0348288A1 (en) * | 1988-06-22 | 1989-12-27 | Nisshin Steel Co., Ltd. | Method of preparing zirconia film |
JPH05273138A (ja) * | 1991-11-21 | 1993-10-22 | Hitachi Ltd | 配線パターン検出方法およびその装置 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8609755B2 (en) | 2005-04-07 | 2013-12-17 | Momentive Perfomance Materials Inc. | Storage stable composition of partial and/or complete condensate of hydrolyzable organofunctional silane |
CN100478404C (zh) * | 2005-06-22 | 2009-04-15 | 河南大学 | 一种可在有机介质中分散的纳米二氧化锆微粒及其制备方法 |
DE102007003761A1 (de) | 2007-01-19 | 2008-08-14 | Airbus Deutschland Gmbh | Materialien und Verfahren zur Beschichtung von Substraten mit heterogenen Oberflächeneigenschaften |
US11173518B2 (en) | 2018-08-20 | 2021-11-16 | WilCraft Can, LLC | Process for reusing printed cans |
Also Published As
Publication number | Publication date |
---|---|
PT91432B (pt) | 1995-12-29 |
DK394089D0 (da) | 1989-08-11 |
AU625900B2 (en) | 1992-07-16 |
DE68917059D1 (de) | 1994-09-01 |
CA1337145C (en) | 1995-10-03 |
DK394089A (da) | 1990-02-13 |
BR8904061A (pt) | 1990-03-27 |
DE68917059T2 (de) | 1994-11-17 |
PT91432A (pt) | 1990-03-08 |
NO893250D0 (no) | 1989-08-11 |
JPH0285373A (ja) | 1990-03-26 |
MY104467A (en) | 1994-04-30 |
KR900003403A (ko) | 1990-03-26 |
EP0358338A2 (en) | 1990-03-14 |
EP0358338A3 (en) | 1990-04-11 |
NO893250L (no) | 1990-02-13 |
ES2059772T3 (es) | 1994-11-16 |
IN176027B (da) | 1995-12-23 |
CN1040811A (zh) | 1990-03-28 |
ATE109217T1 (de) | 1994-08-15 |
AU3951189A (en) | 1990-02-15 |
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