US3101277A - Metal surface such as aluminum - Google Patents
Metal surface such as aluminum Download PDFInfo
- Publication number
- US3101277A US3101277A US3101277DA US3101277A US 3101277 A US3101277 A US 3101277A US 3101277D A US3101277D A US 3101277DA US 3101277 A US3101277 A US 3101277A
- Authority
- US
- United States
- Prior art keywords
- metal
- silane
- aluminum
- silanes
- coated
- 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
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- 229910052782 aluminium Inorganic materials 0.000 title claims description 32
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 32
- 229910052751 metal Inorganic materials 0.000 title description 78
- 239000002184 metal Substances 0.000 title description 78
- 238000000576 coating method Methods 0.000 claims description 26
- 238000005260 corrosion Methods 0.000 claims description 26
- 239000011248 coating agent Substances 0.000 claims description 24
- 229910052802 copper Inorganic materials 0.000 claims description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 14
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 14
- 229910052749 magnesium Inorganic materials 0.000 claims description 14
- 239000011777 magnesium Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N iso-propanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 28
- 150000004756 silanes Chemical class 0.000 description 26
- 150000003961 organosilicon compounds Chemical class 0.000 description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 20
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 18
- 239000003960 organic solvent Substances 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- 239000004215 Carbon black (E152) Substances 0.000 description 12
- 125000001931 aliphatic group Chemical group 0.000 description 12
- -1 anthracyl Chemical group 0.000 description 12
- 238000009833 condensation Methods 0.000 description 12
- 230000005494 condensation Effects 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 238000006460 hydrolysis reaction Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- BLRPTPMANUNPDV-UHFFFAOYSA-N silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 12
- 229910000077 silane Inorganic materials 0.000 description 12
- 239000002253 acid Substances 0.000 description 10
- 239000003513 alkali Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 description 10
- 150000002739 metals Chemical class 0.000 description 10
- 229910052759 nickel Inorganic materials 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000002844 melting Methods 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 235000011007 phosphoric acid Nutrition 0.000 description 6
- 238000009877 rendering Methods 0.000 description 6
- 239000008257 shaving cream Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 6
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- YOBOXHGSEJBUPB-MTOQALJVSA-N (Z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N Methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 4
- UJTMLNARSPORHR-UHFFFAOYSA-N OC2H5 Chemical compound C=C=[O+] UJTMLNARSPORHR-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 239000004922 lacquer Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000008164 mustard oil Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000011253 protective coating Substances 0.000 description 4
- 150000004819 silanols Chemical class 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- KOPOQZFJUQMUML-UHFFFAOYSA-N Chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 2
- 239000005046 Chlorosilane Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N Cumene Chemical group CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 210000003298 Dental Enamel Anatomy 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K Iron(III) chloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- BQFPQJVSYUPUQE-UHFFFAOYSA-N O[SiH](O)CC1=CC=CC=C1 Chemical compound O[SiH](O)CC1=CC=CC=C1 BQFPQJVSYUPUQE-UHFFFAOYSA-N 0.000 description 2
- 101700061961 SKOR Proteins 0.000 description 2
- 241000282887 Suidae Species 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J Titanic acid Chemical class O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- JJLKTTCRRLHVGL-UHFFFAOYSA-L [acetyloxy(dibutyl)stannyl] acetate Chemical compound CC([O-])=O.CC([O-])=O.CCCC[Sn+2]CCCC JJLKTTCRRLHVGL-UHFFFAOYSA-L 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N acetic acid ethyl ester Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- 238000006136 alcoholysis reaction Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- MEWFSXFFGFDHGV-UHFFFAOYSA-N cyclohexyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C1CCCCC1 MEWFSXFFGFDHGV-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 description 2
- DNMBXNBDPPLUIT-UHFFFAOYSA-N diethoxy-hydroxy-methylsilane Chemical compound CCO[Si](C)(O)OCC DNMBXNBDPPLUIT-UHFFFAOYSA-N 0.000 description 2
- WWDSCWXXCRBQLK-UHFFFAOYSA-N dihydroxy(methyl)silane Chemical compound C[SiH](O)O WWDSCWXXCRBQLK-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- GVUGIFZLJMQKGZ-UHFFFAOYSA-N ethyl-hydroxy-dimethoxysilane Chemical compound CC[Si](O)(OC)OC GVUGIFZLJMQKGZ-UHFFFAOYSA-N 0.000 description 2
- KCWYOFZQRFCIIE-UHFFFAOYSA-N ethylsilane Chemical class CC[SiH3] KCWYOFZQRFCIIE-UHFFFAOYSA-N 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 150000002611 lead compounds Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- ZJBHFQKJEBGFNL-UHFFFAOYSA-N methylsilanetriol Chemical compound C[Si](O)(O)O ZJBHFQKJEBGFNL-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 230000001264 neutralization Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 125000004430 oxygen atoms Chemical group O* 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000000717 retained Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005488 sandblasting Methods 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 235000015096 spirit Nutrition 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000010301 surface-oxidation reaction Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N tin hydride Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- GYZQBXUDWTVJDF-UHFFFAOYSA-N tributoxy(methyl)silane Chemical compound CCCCO[Si](C)(OCCCC)OCCCC GYZQBXUDWTVJDF-UHFFFAOYSA-N 0.000 description 2
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 150000003755 zirconium compounds Chemical class 0.000 description 2
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- 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
- C23C18/122—Inorganic polymers, e.g. silanes, polysilazanes, polysiloxanes
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S62/00—Refrigeration
- Y10S62/20—Materials used to prevent corrosion in refrigeration system
Definitions
- the metal is coated as described above and is subsequently heated to a temperature of at least 350 C. but below the melting point of the metal.
- This heating step imparts a permanence and additional resistance to alkali and acid to the protective coating. It is often desirable to allow some or all of the solvent to evaporate from the coating film prior to heating.
- the metal may be dipped in a tank containing a solution of organosilicon compound in an organic solvent, removed and airdried, then redipped if desired and again air-dried, then heated to above 350 C.
- the resultant coating is clear and hard.
- the coating can only be removed by extreme measures such as sandblasting or other abrasion means removing a surface layer from the metal itself.
- the coated metal can be used without further treatment or it can be coated with lacquers, enamels, and so forth.
- Aluminum tubes employed for packaging shaving cream were coated by dipping in a 10% by weight solution of methyltriethoxy silane in xylene. The xylene was allowed to evaporate ofi the metal and the tubes were then heated to between 500 and 600 C. for above five minutes. The treated tubes were then filled with shaving cream having a pH of about 9.8. No reaction between shaving cream and tube could be discovered and the tube remained free of corrosion and deterioration after four months storage at 50 C. i
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Description
Aug. 20, 193 H. EDER ETAL 3,101,277 METHOD OF RENDERING METALLIC SURFACES CORROSION RESISTANT Filed April 27, 1959 METAL SURFACE sucn AS ALUMINUM 1 METAL SURFACE DEGREASED AND CLEANED OPTIONAL COATED WlT|-| LIQUID FUNCTIONAL MONOORGANOSILICON MATERIAL COATING AIR-DRIED r 1 SURFACE RECOATED AND AIR-DRIED I OPTIONAL TREATED METAL HEATED TO AT LEAST 350C F' '"l 1 I TREATED METAL FURTHER COATED WITH A oPnoML PAINT OR VARNlSl-I A T TORNE' Y United States Patent 3,101,277 METHOD OF RENDERING METALLIC SURFACES CORROSION RESISTANT Heinz Eder, Gauting, near Munich, and Siegfried Bloeclt, Furth, Bavaria, Germany, assign'ors to Wacker-Chemie G.m.b.H., Munich, Bavaria, Germany Filed Apr. 27, 1959, Ser. No. 808,899 Claims priority, application Germany Apr. 30, 1958 9 Claims. (Cl, 117-132),
This invention relates to a method of imparting corrosion resistance to metallic surfaces by treating the surface with an organosilicon compound.
The flow diagram shown in the drawing illustrates the process of coating a metal surface with a monoorganosilicone material.
The problem of the corrosion of metal surfaces resulting from oxidation, acid attack and alkali attack of the surface has plagued producer and consumer alike. The use of protective coatings such as paints, lacquers, varnishes and the like has been a partial answer to this problem, but such materials are of limited effectiveness at high and low temperatures and against acid or alkali attack. Furthermore the mechanical integrity of such cured films is not satisfactory in that the film breaks under mechanical stresses such as bending, pulling and striking the metal and the cured films have not had satisfactory resistance to solvents and chemical agents in general.
In some cases, carefully produced oxide films are employed to protect aluminum, copper, magnesium and other metals from further corrosion. However the metallic surface must be substantially free of grease and other foreign matter or the metal must be pretreated prior to the surface oxidation to achieve a satisfactory degree of protection.
It is an object of this invention to introduce a simple, economical method of imparting corrosion resistance to metal surfaces. Another object is to produce acid resistant and alkali resistant sheets, foils and other forms of aluminum, copper, nickel and magnesium. Other objects and advantages are apparent or will be detailed in the disclosure and claims which follow.
This invention is a method of rendering metal surfaces corrosion resistant by coating the metal with a functional monoorganosilicon compound and thereafter heating the coated metal to a temperature below its melting point to cure the organosilicon composition.
The organosilicon compounds which are operable in this invention include silanes and siloxanes. The operable organosilicon compounds have an organic substituent to silicon ratio of from .9/1 to 1.2/1 and preferably about 1/1. The balance of the .substituents attached to silicon in these compounds are selected from oxygen atoms, hydroxy radicals and'alkoxy radicals. The operable silanes would be of the general formula where each R is a monovalent hydrocarbon radical free of aliphatic unsaturation or halogenatedv monovalent hydrocarbon radical free of aliphatic unsaturation, each R is hydrogen or alkyl, m has an average value of 0 to 1 inclusive, and n has an average value of .9 t 0.1.2 inclusive, preferably about 1.0. The organic radicals represented by R include alkyl radicals such as methyl, ethyl, butyl and octadecyl, aryl radicals such as phenyl and anthracyl, alkaryl radicals such as tolyl and methylnaphthyl, aralkyl radicals such as benzyl and phenylethyl, and cycloaliphatic such as cyclohexyl and cyclobutyl. The preferred and most common silanes are methy1-, phenyl-, and ethyl-silanes.
The silanes can contain hydrogen substituents. There can be up to 1 hydrogen atom per silicon atom in such 3 ,101,277 Patented Aug. 20, 1963 lCe hydroxy and alkoxy radicals are present on the silanes.
wherein each R is an alkyl radical. Specific examples of operable silanes include methyltriethoxy silane, methyltributoxy silane, methyldiethoxy silane, methyltrihydroxy silane, methylhydroxydiethoxy silane, methyldihydroxy silane, phenyltrimethoxy silane, ethyltriethoxy silane, tolyldiethoxy silane, benzyldihydroxy silane, and cyclohexyltrimethoxy silane. It is apparent that R can be the same or different in each operable silane. The silane employed can be a single specie or it can be mixtures of silanes. Limited amounts of diorganosilanes and SiO units can be tolerated in the mixture, but the closer the silane approximates an R/ Si ratio of about 1, the better the results achieved.
The organosilicon compounds employed can be siloxanes. The operable siloxanes are polymeric materials obtained by partial hydrolysis and condensation or by complete hydrolysis and partial condensation or by partial hydrolysis and partial condensation of silanes. I The silanes described above can be employed as starting materials in the production of the operable siloxanes. The silanes R I-l Si(OR') as defined above can be partiallyv hydrolyzed by conventional techniques to produce silanols such as R l-l SKOR) (OH) These silanols can then be condensed to siloxanes such as an m (OR, 4nmx x/ 2 and n m K 4-n-m-y( x-y y/Z Another method involved complete hydrolysis of the silane to produce siloxanes of the unit formula and the partial condensate R H Si(OH) O Alcoholysis of the chlorosilanes produces alkoxy silanes from which the operable siloxanes can be prepared as noted above.
The organosilicon compounds employed are liquids soluble in organic solvents. They are usually relatively low molecular weight materials having viscosities of 1 to 10,000 cs. at 25 C. but they can be high viscosity materials of 1,000,000 cs. or more at 25 C.
The organosilicon compound is applied to the metal surface from a solvent solution, from an aqueous disper sion in an organic solvent, or from an emulsion. The solvent employed can be any organic solvent in which the particular organosilicon compound is soluble. Commonly employed as solvents are xylene, benzene, isopropyl, alcohol, acetic acid ethyl ester, Stoddard solvent, neutral minerals spirits, naphthas and other petroleum v solvents, and so forth.
The metal is coated by any desired means. Such varied coatingmethods asbrushing, spraying, dipping, flowing, and so forth are operable. It is desirable to form an unbroken film on the metal surface to secure even protection for the entire surface of the metal piece.
The metals can be in the fonm of sheets, bricks or pigs, foils or even completed parts such as gears, fenders for automobiles, flexible tubes for use as ducts, packing cases arena 7 Q.) and the like. While this invention is applicable to metals generally, it is of particular importance and usefulness with aluminum, nickel, copper, and magnesium as well as with alloys containing such rnetals.
The metal is coated as described above and is subsequently heated to a temperature of at least 350 C. but below the melting point of the metal. This heating step imparts a permanence and additional resistance to alkali and acid to the protective coating. It is often desirable to allow some or all of the solvent to evaporate from the coating film prior to heating. Thus the metal may be dipped in a tank containing a solution of organosilicon compound in an organic solvent, removed and airdried, then redipped if desired and again air-dried, then heated to above 350 C. The resultant coating is clear and hard. The coating can only be removed by extreme measures such as sandblasting or other abrasion means removing a surface layer from the metal itself.
The coated metal can be used without further treatment or it can be coated with lacquers, enamels, and so forth.
Aluminum tubes employed for packaging shaving cream were coated by dipping in a 10% by weight solution of methyltriethoxy silane in xylene. The xylene was allowed to evaporate ofi the metal and the tubes were then heated to between 500 and 600 C. for above five minutes. The treated tubes were then filled with shaving cream having a pH of about 9.8. No reaction between shaving cream and tube could be discovered and the tube remained free of corrosion and deterioration after four months storage at 50 C. i
A mustard oil food product having a pH of 3.94 packed in tubes treated as above was stored for four months at 50 C. At the end of this storage period the tubes were opened. The mustard-oil product was unchanged in taste and remained completely usable as a foodstufi. The tubes were uncorroded and retained their orginal surface characteristics of brightness and smoothness.
A series of aluminum panels of 10 mils thickness were dipped in a 10 percent by weight solution of m-ethyltrimethoxy silane in benzene. The panels were air-dried. The coated panels and some uncoated control panels were placed in an air circulating oven and heated to about 500 C. for 30 minutes. The coated panels and control panels were then immersed in concentrated hydrochloric acid for several hours. The coated panels showed substantially no attack at the end of the test but the untreated control panels were gradually and progressively corroded and fell apart before the end of the test.
The foregoing are exemplary of the excellent results achieved through this invention. Similar results are achieved with copper, nickel and magnesium similarly coated. When phenyltrimethoxy silane, ethyldi methoxyhydroxy silane and methylhydrogenmethoxy siloxanes of the average unit formula CH H Si(OMe) O- where a has an average value of 0.25 and b has an average value of 0.75 are substituted for the silanes employed in the rforegoing examples, similar corrosion resistance is imparted to the metals.
Corrosion resistance will be considerably increased when conventional catalysts are addedwhich facilitate the hydrolysis of alkoxy silanes and accelerate the condensation of silicon organic compounds.
Substances facilitating hydrolysis include phosphoric acid and ferric chloride. Substances which accelerate condensation are all organometal compounds which in silicone chemistry areuseful as condensation catalysts. Such substances include metal salts of carboxylic acids, alcoholates of heavy metals, metal chelates and the like, [for example titanic acid esters, and organic Zinc, tin, aluminum, lead, and zirconium compounds such as tetrabutyl titanate, dibutyl tin diacetate and dimaleinate, zirconium acetyl acetonate.
The aluminum surfaces are treated as described above.
Table Amount Treatment of aluminum of H, Time (1) No treatment 1 1'30 2 1'45 3 1'54" (2) 10% GH3SKOC2H5 3 in isopropyl alcohol 1 4:30;:
2 5 30 3 an" (3) 10% (GH3)iSi(OCzH5)z in isopropyl alcohol. 1 2:20
2 2 40 3 2'50 (4) 10% OH Si(OH) in isopropyl alcohol 1 1047 2 ll 51 3 1232" (5) 10% CH Sl(OC2H5)3 3% dibutyl tin dilaurate in isopropyl alcohol 1 630 2 7'19 3 7'50" (6) 10% ClI3Sl(OC2H5)3 3% zirconium acetyl acetonate in isopropyl alcohol 1 7'49 2 823 3 8 47 (7) 10% OH3Si OO2H5 3 3% phosphoric acid (89%) in isopropyl alcohol 1 1O051 2 1 3 1130 (8) 6.6% CI-I3Si(OOQH5) 2.4% (CHs flSi(O 0 11 2 1% butyl titanate in isopropyl alcohol 1 1507 (This solution had been stored 18 months). 2 1647 3 1737 (9) 10% OH3Si(OH) 3% H3PO4 (89%) 3 2040 (10) 10% (OHS)Z l(OOZH5)Z 3% buty1titanate 3'40 3 4'18 (11) 10% OH3Si(OH)a 3% butyl tltanate 1 1218 2 13/55 3 1449 That which is claimed is:
l. The method of imparting corrosion resistance to metallic surfaces selected from the group consisting of aluminum, copper, nickel and magnesium consisting essentially of coating the surface of the metal with an organosilicon composition selected from the group consisting of at least one silane of the formula n m )i n m and siloxanes of the unit formula n m (OR, 4-nm-x x 2 wherein each R is selected from the group consisting of monovalent hydrocarbon radicals free of aliphatic unsaturation and halogenated monovalent hydrocarbon radicals free of aliphatic unsaturation, each R is selected from the group consisting of hydrogen atom and alkyl radicals, m has an average value of 0 to 1 inclusive, n has an average value of .9 to 1.2 inclusive and x has an average value of from 1 to 2 inclusive, the sum of n-l-m-l-x being less than 4-, and thereafter heating the coated metal to a temperature of 350 C. to 600 C. until the organosilicon coating is cured.
2. The method of claim 1 wherein the organosilicon compound is applied to the metal surface from a solution in an organic solvent.
3. The method of claim 2 wherein aluminum is coated with a mixture of methyltrimethoxy silane and phenyltrimethoxy silane.
4. 'lhe method of claim 2 wherein the organosilicon compound is methyltrimethoxy silane.
5, The method 'of claim} wherein the organosilicon compound is methyltriethoxy silane.
6. The method of imparting corrosion resistance to metals selected from the group consisting of copper, nickel, aluminum, and magnesium, consisting essentially:
of coating the metal with at least one 'monoorganosilicon compound selected from the group consisting of silanes of the general formula R H Si(OR') wherein each R is selected from the group consisting of monovalent hydrocarbon radicals free o f aliphatic unsaturation and halogenated monovalent hydrocarbon radicals free of aliphatic unsaturation, each R, .is selected from the group consisting of the hydrogen atom and alkyl radicals, m 'has an average value of from 0 to l inclusive, n has an average value of [from .9 to 1.2 inclusive, and partial hydrolyzates of such 'silanes, and heating the metal to the range above 350 C. and below the melting point of the metal until the organosilicon coating is cured.
compound isapplied to the-metal surface from a solution in an'organic solvent.
8. Amethod of'impartingfresistance to alkali and, acid 20 7. The method of claim 6 wherein the or'gan'osilicone to aluminum consisting essentially of coating the aluminum with a monoorganosilan-e of the formula n n mnn where each R is an alkyl radical, each R is an alkyl radical and n has an average valueof .9 to 1.2 inclusive and heating the coated metal to a temperature in the range 350 to 600 C. until the silarre is cured.
9. The method of claim 8 wherein the organosilicon compound is applied to the metal surface from a solution in an organic solvent.
'Reierences Cited in the file of this patent- UNITED STATES PATENTS 650,131 Great Britain Feb. 14, 1951 Rochow ou. 7, 194,1
Claims (1)
1. THE METHOD OF IMPARTING CORROSION RESISTANCE TO METALLIC SURFACES SELECTED FROM THE GROUP CONSISTING OF ALUMINUM, COPPER, NICKEL AND MAGNESIUM CONSISTING ESSENTIALLY OF COATING THE SURFACE OF THE METAL WITH AN ORGANOSILICON COMPOSITION SELECTED FROM THE GROUP CONSISTING OF AT LEAST ONE SILANE OF THE FORMULA
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3201632A (en) * | 1960-02-04 | 1965-08-17 | Philips Corp | Electroluminescent element employing a chrome iron base plate with matching glass enamels |
| US3232065A (en) * | 1963-04-27 | 1966-02-01 | British Oxygen Co Ltd | Method and apparatus for storing ozone/oxygen mixtures |
| US3346405A (en) * | 1964-12-14 | 1967-10-10 | Gen Electric | Metal protectant |
| US3364246A (en) * | 1962-06-30 | 1968-01-16 | Th Goldsmidt A G | Process for preparing aqueous solutions of silanols and siloxanols by hydrolysis of alkoxy silanes and siloxanes in an aqueous emulsion |
| US3373137A (en) * | 1962-05-18 | 1968-03-12 | Dow Corning | Nitrogen-containing organosilicon compounds and their preparation |
| US3450736A (en) * | 1963-09-12 | 1969-06-17 | Mobil Oil Corp | Modified siloxane polymers and compositions containing same |
| US3971388A (en) * | 1974-11-29 | 1976-07-27 | Telectronics Pty. Limited | Titanium covered cardiac pacemaker with elastomer coating and method of applying same |
| US3987530A (en) * | 1975-04-11 | 1976-10-26 | International Business Machines Corporation | Heat fuser roll and method of manufacture |
| US4133921A (en) * | 1974-08-12 | 1979-01-09 | Very Important Products, Inc. | Rubber and polymer preservative method |
| US4311738A (en) * | 1980-05-27 | 1982-01-19 | Dow Corning Corporation | Method for rendering non-ferrous metals corrosion resistant |
| US4912934A (en) * | 1987-10-05 | 1990-04-03 | Hitachi, Ltd. | Hermetically closed circulation type, vapor absorption refrigerator |
| US5053081A (en) * | 1990-04-02 | 1991-10-01 | Oakite Products, Inc. | Composition and method for treatment of conversion coated metal surfaces with an aqueous solution of 3-aminopropyltriethoxy silane and titanium chelate |
| US5162460A (en) * | 1991-10-17 | 1992-11-10 | Dow Corning Corporation | Moisture-curable silicone corrosion resistant coatings |
| US5342578A (en) * | 1993-02-23 | 1994-08-30 | Gas Research Institute | Corrosion inhibition of ammonia-water absorption chillers |
| US20030140671A1 (en) * | 2002-01-25 | 2003-07-31 | L&L Products, Inc. | Method and apparatus for applying flowable materials |
| US20100317796A1 (en) * | 2009-05-01 | 2010-12-16 | Misty Huang | Moisture Curable Silylated Polymer Compositions Containing Reactive Modifiers |
| US20130245194A1 (en) * | 2009-05-01 | 2013-09-19 | Momentive Performance Materials Inc. | Moisture curable silylated polymer compositions containing reactive modifiers |
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| US2258218A (en) * | 1939-08-01 | 1941-10-07 | Gen Electric | Methyl silicones and related products |
| GB563995A (en) * | 1941-06-10 | 1944-09-08 | Corning Glass Works | Organo silicon polymer condensation products and methods of making them |
| US2386466A (en) * | 1940-02-10 | 1945-10-09 | Corning Glass Works | Insulated conductor and insulation therefor |
| GB650131A (en) * | 1948-06-29 | 1951-02-14 | Dow Corning | A method of rendering materials water-repellent |
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| US2643964A (en) * | 1950-10-14 | 1953-06-30 | Gen Electric | Method for improving the adhesion of organopolysiloxanes to solid surfaces |
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| US2258218A (en) * | 1939-08-01 | 1941-10-07 | Gen Electric | Methyl silicones and related products |
| US2386466A (en) * | 1940-02-10 | 1945-10-09 | Corning Glass Works | Insulated conductor and insulation therefor |
| GB563995A (en) * | 1941-06-10 | 1944-09-08 | Corning Glass Works | Organo silicon polymer condensation products and methods of making them |
| GB650131A (en) * | 1948-06-29 | 1951-02-14 | Dow Corning | A method of rendering materials water-repellent |
| US2643964A (en) * | 1950-10-14 | 1953-06-30 | Gen Electric | Method for improving the adhesion of organopolysiloxanes to solid surfaces |
| DE855817C (en) * | 1956-12-10 | 1952-11-17 | Dow Corning | Process for protecting objects made of magnesium and its alloys against tarnishing in air |
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Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3201632A (en) * | 1960-02-04 | 1965-08-17 | Philips Corp | Electroluminescent element employing a chrome iron base plate with matching glass enamels |
| US3373137A (en) * | 1962-05-18 | 1968-03-12 | Dow Corning | Nitrogen-containing organosilicon compounds and their preparation |
| US3364246A (en) * | 1962-06-30 | 1968-01-16 | Th Goldsmidt A G | Process for preparing aqueous solutions of silanols and siloxanols by hydrolysis of alkoxy silanes and siloxanes in an aqueous emulsion |
| US3232065A (en) * | 1963-04-27 | 1966-02-01 | British Oxygen Co Ltd | Method and apparatus for storing ozone/oxygen mixtures |
| US3450736A (en) * | 1963-09-12 | 1969-06-17 | Mobil Oil Corp | Modified siloxane polymers and compositions containing same |
| US3346405A (en) * | 1964-12-14 | 1967-10-10 | Gen Electric | Metal protectant |
| US4133921A (en) * | 1974-08-12 | 1979-01-09 | Very Important Products, Inc. | Rubber and polymer preservative method |
| US3971388A (en) * | 1974-11-29 | 1976-07-27 | Telectronics Pty. Limited | Titanium covered cardiac pacemaker with elastomer coating and method of applying same |
| US3987530A (en) * | 1975-04-11 | 1976-10-26 | International Business Machines Corporation | Heat fuser roll and method of manufacture |
| US4311738A (en) * | 1980-05-27 | 1982-01-19 | Dow Corning Corporation | Method for rendering non-ferrous metals corrosion resistant |
| US4912934A (en) * | 1987-10-05 | 1990-04-03 | Hitachi, Ltd. | Hermetically closed circulation type, vapor absorption refrigerator |
| US5053081A (en) * | 1990-04-02 | 1991-10-01 | Oakite Products, Inc. | Composition and method for treatment of conversion coated metal surfaces with an aqueous solution of 3-aminopropyltriethoxy silane and titanium chelate |
| US5162460A (en) * | 1991-10-17 | 1992-11-10 | Dow Corning Corporation | Moisture-curable silicone corrosion resistant coatings |
| US5342578A (en) * | 1993-02-23 | 1994-08-30 | Gas Research Institute | Corrosion inhibition of ammonia-water absorption chillers |
| US20030140671A1 (en) * | 2002-01-25 | 2003-07-31 | L&L Products, Inc. | Method and apparatus for applying flowable materials |
| US7043815B2 (en) * | 2002-01-25 | 2006-05-16 | L & L Products, Inc. | Method for applying flowable materials |
| US20100317796A1 (en) * | 2009-05-01 | 2010-12-16 | Misty Huang | Moisture Curable Silylated Polymer Compositions Containing Reactive Modifiers |
| CN102459487A (en) * | 2009-05-01 | 2012-05-16 | 莫门蒂夫性能材料股份有限公司 | Moisture curable silylated polymer compositions containing reactive modifiers |
| US20130245194A1 (en) * | 2009-05-01 | 2013-09-19 | Momentive Performance Materials Inc. | Moisture curable silylated polymer compositions containing reactive modifiers |
| US8809479B2 (en) * | 2009-05-01 | 2014-08-19 | Momentive Performance Materials Inc. | Moisture curable silylated polymer compositions containing reactive modifiers |
| US9714315B2 (en) | 2009-05-01 | 2017-07-25 | Momentive Performance Materials Inc. | Moisture curable silylated polymer compositions containing reactive modifiers |
| US9932437B2 (en) * | 2009-05-01 | 2018-04-03 | Momentive Performance Materials Inc. | Moisture curable silylated polymer compositions containing reactive modifiers |
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