CN101713069A - Method for preparing additive homogeneous phase modified solution of silane and application thereof - Google Patents
Method for preparing additive homogeneous phase modified solution of silane and application thereof Download PDFInfo
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- CN101713069A CN101713069A CN200910153862A CN200910153862A CN101713069A CN 101713069 A CN101713069 A CN 101713069A CN 200910153862 A CN200910153862 A CN 200910153862A CN 200910153862 A CN200910153862 A CN 200910153862A CN 101713069 A CN101713069 A CN 101713069A
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- silane
- solution
- organic solvent
- butyl
- water
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- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 63
- 239000000654 additive Substances 0.000 title claims abstract description 18
- 230000000996 additive effect Effects 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims description 22
- 239000011159 matrix material Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 150000004756 silanes Chemical class 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 230000001681 protective effect Effects 0.000 claims abstract description 9
- 238000007865 diluting Methods 0.000 claims abstract description 4
- -1 sec.-propyl Chemical group 0.000 claims description 22
- 239000011248 coating agent Substances 0.000 claims description 17
- 238000000576 coating method Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 230000007062 hydrolysis Effects 0.000 claims description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 6
- 125000005907 alkyl ester group Chemical group 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 239000010959 steel Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- BKFAZDGHFACXKY-UHFFFAOYSA-N cobalt(II) bis(acetylacetonate) Chemical compound [Co+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O BKFAZDGHFACXKY-UHFFFAOYSA-N 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- JBAKCAZIROEXGK-LNKPDPKZSA-N copper;(z)-4-hydroxypent-3-en-2-one Chemical compound [Cu].C\C(O)=C\C(C)=O JBAKCAZIROEXGK-LNKPDPKZSA-N 0.000 claims description 3
- 238000003618 dip coating Methods 0.000 claims description 3
- 230000005518 electrochemistry Effects 0.000 claims description 3
- 239000008397 galvanized steel Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229940046892 lead acetate Drugs 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 238000004528 spin coating Methods 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 abstract description 9
- 238000005260 corrosion Methods 0.000 abstract description 9
- 239000000758 substrate Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 58
- 238000012360 testing method Methods 0.000 description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 238000002444 silanisation Methods 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 10
- 239000010935 stainless steel Substances 0.000 description 10
- 238000012986 modification Methods 0.000 description 9
- 230000004048 modification Effects 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 238000002203 pretreatment Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 229910000838 Al alloy Inorganic materials 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000007739 conversion coating Methods 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 229910000737 Duralumin Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004532 chromating Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229920006334 epoxy coating Polymers 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
Images
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
- 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
Landscapes
- Chemical Treatment Of Metals (AREA)
Abstract
本发明公开了一种均相改性硅烷溶液的制备方法及其用途。它是将硅烷加入到水和水溶性有机溶剂的混合体系中不断搅拌条件下缓慢加入同一有机溶剂稀释后的不同含量的添加剂，硅烷∶水∶有机溶剂的体积比为m∶n∶(100-m-n)，其中m/n为0.1-1，硅烷∶添加剂的摩尔比为10∶1-10000∶1，充分搅拌均匀后，将配置好的溶液静置、恒温水解0.1-48小时。硅烷溶液用于金属基体表面的防护性处理。本发明通过一种溶胶-凝胶体系均相改性另一种溶胶-凝胶体系，其中所提供的添加剂种类较多，成本较低，且与未改性的硅烷溶液相比，金属基体经改性过的硅烷溶处理后，耐蚀性能显著提高。The invention discloses a preparation method and application of a homogeneously modified silane solution. It is to add silane to the mixed system of water and water-soluble organic solvent under the condition of constant stirring and slowly add additives of different contents after diluting the same organic solvent. The volume ratio of silane: water: organic solvent is m: n: (100- m-n), wherein m/n is 0.1-1, and the molar ratio of silane:additive is 10:1-10000:1. After fully stirring, the prepared solution is left to stand and hydrolyzed at constant temperature for 0.1-48 hours. Silane solutions are used for the protective treatment of metal substrate surfaces. The present invention homogeneously modifies another sol-gel system through a sol-gel system, wherein the types of additives provided are more, the cost is lower, and compared with the unmodified silane solution, the metal matrix is After the modified silane is dissolved, the corrosion resistance is significantly improved.
Description
Technical field
The present invention relates to a kind of preparation method and its usage of homogeneous phase modified silane solution.
Background technology
As everyone knows, most of metals corrode under field conditions (factors) easily, it is carried out the surfacecti proteon processing after, the speed of the metallic corrosion of can slowing down greatly.In various treatment processs, traditional technology has chromating, phosphate conversion processing and rare-earth conversion coatings processing etc., yet preceding two kinds of technologies exist than the serious environmental pollution problem, as the high valence chrome ion very strong toxicity and carinogenicity are arranged, phosphoric acid salt then is one of main arch-criminal of body eutrophication; And rare-earth conversion coatings technical matters more complicated.In recent years, along with the raising of various countries' environmental requirement, development of new green metal process for treating surface has become the focus of this area research.Wherein, the organic-silylation processing is pollution-free because of it, processing part corrosion resisting property is good and preparation technology simply enjoys favor.
The metallic surface silanization treatment technology is to utilize silane reagent (with single silane is example, and its general formula is X-Si (OR)
3, wherein X represents functional group, one or more in alkyl or alkenyl, methoxyl group, oxyethyl group or the benzyl that replaces for alkyl, thiazolinyl, by at least one amino, epoxy group(ing) or sulfydryl; R is an alkyl, is generally methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl or ethanoyl etc.) hydrolysis generation silanol (X-Si (OH)
n(OR)
3-n), silanol by combine with metal (Me) surface hydroxyl and silanol between after the self-crosslinking condensation, form one deck compact protective film in the metallic surface, thus the barrier propterty of providing.
A large amount of experiments show that the hydrolyzed solution after the simple silane dilution of ordinary method preparation is handled part surface filming very thin thickness, is generally tens to hundreds of nanometers, and the rete not even compact that distributes, and the corrosion resisting property of metal are improved can not reach good effect.The compactness that how to increase thickness, raising surface film improves new direction, the fresh target that metal corrosion resisting property this purpose becomes the investigator to reach.So far, the technology that obtains better effect has: double-deck silane film technique, the polynary compound silane membrane technique of disposable deposition and add the inertia nano particle (as SiO in solution
2, ZnO
2, Al
2O
3), add rare earths salt (as Ce (NO
3)
3) out-phase improvement technology etc.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of preparation method and its usage of homogeneous phase modified silane solution is provided.
The objective of the invention is to be achieved through the following technical solutions:
The preparation method of modified silane solution joins in the mixed system of water and water-miscible organic solvent constantly the additive that agitation condition slowly adds the different content behind the same organic solvent diluting down with silane, silane: water: volume of organic solvent is than being m: n: (100-m-n), wherein m/n is 0.1-1, silane: the mol ratio of additive is 10: 1-10000: 1, after stirring, with the solution left standstill, the constant temperature hydrolysis that configure 0.1-48 hour.
Described silane is single silane and two silane, and single silane structure general formula is:
Wherein, R is methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl or ethanoyl, and X is one or more in alkyl, thiazolinyl or the alkyl or alkenyl, methoxyl group, oxyethyl group or the benzyl that are replaced by at least one amino, epoxy group(ing) or sulfydryl.
Two silane structure general formulas are:
Wherein, R is methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl or ethanoyl, and Y is CH
2CH
2, (CH
2)
3-NH-(CH
2)
3Or (CH
2)
3-S
4-(CH
2)
3
Described organic solvent is methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, ethyl acetate or tetrahydrofuran (THF).Described additive is zirconic acid alkyl ester, alkyl titanate, stannic acid alkyl ester, lead acetate, Co (acac)
2, Cu (acac)
2Or Zn (acac)
2
Solution of silane is used for the protective of metal base surface to be handled.
Described metallic matrix is an iron and steel, galvanized steel, aluminium, zinc, magnesium, copper, tin and alloy thereof.The protective treatment process of described metal base surface is spread coating, dip coating, spin-coating method or electrochemistry assistant depositing method.
Homogeneous phase modified silane formulations prepared from solutions technology provided by the invention is simple, and cost is lower.Compare with the simple solution of silane of ordinary method preparation, silane hydrolyzate rapidly, the condensation film forming is easier on the processing part carries out, handle the part corrosion resisting property under the same hydrolysis time and obviously improve, and in certain additive concentration scope with under the long period, hydrolyzed silane solution has good stability.The present invention can be used for the protective pre-treatment of multiple metal and alloy.
Description of drawings
Fig. 1 is plunderred the corner reflection infrared spectrum for methyltrimethoxy silane modification pre-process and post-process part (stainless steel) electrode surface, illustrates that solution of silane increases the infrared absorption peak intensity enhancing through tetra-n-butyl titanate modification aftertreatment part silane film layer thickness;
Fig. 2 be methyltrimethoxy silane modification pre-process and post-process part (stainless steel) electrode in NaCl aqueous solution middle impedance mould value, illustrate that the electrode impedance value is significantly improved after the solution of silane of tetra-n-butyl titanate modification is handled.
Embodiment
The preparation method of modified silane solution joins in the mixed system of water and water-miscible organic solvent constantly the additive that agitation condition slowly adds the different content behind the same organic solvent diluting down with silane, silane: water: volume of organic solvent is than being m: n: (100-m-n), wherein m/n is 0.1-1, silane: the mol ratio of additive is 10: 1-10000: 1, after stirring, with the solution left standstill, the constant temperature hydrolysis that configure 0.1-48 hour.
Described silane is single silane and two silane, and single silane structure general formula is:
Wherein, R is methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl or ethanoyl, and X is one or more in alkyl, thiazolinyl or the alkyl or alkenyl, methoxyl group, oxyethyl group or the benzyl that are replaced by at least one amino, epoxy group(ing) or sulfydryl.
Two silane structure general formulas are:
Wherein, R is methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl or ethanoyl, and Y is CH
2CH
2, (CH
2)
3-NH-(CH
2)
3Or (CH
2)
3-S
4-(CH
2)
3
Described organic solvent is methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, ethyl acetate or tetrahydrofuran (THF).Described additive is zirconic acid alkyl ester, alkyl titanate, stannic acid alkyl ester, lead acetate, Co (acac)
2, Cu (acac)
2Or Zn (acac)
2
Solution of silane is used for the protective of metal base surface to be handled.
Described metallic matrix is an iron and steel, galvanized steel, aluminium, zinc, magnesium, copper, tin and alloy thereof.The protective treatment process of described metal base surface is spread coating, dip coating, spin-coating method or electrochemistry assistant depositing method.
Get methyltrimethoxy silane (MTMS) solution 5mL and join in ethanol (50mL)-water (5mL) mixed solution system, stir the back and add about 0.035mL Glacial acetic acid (solution A); Getting 0,1,10,100,1000 μ L tetra-n-butyl titanates respectively joins in the 40mL ethanolic soln and stir (solution B).A, B two solution are mixed, obtain tetra-n-butyl titanate concentration and be respectively 0,2.9 * 10
-5, 2.9 * 10
-4, 2.9 * 10
-3And 2.9 * 10
-2The series modified solution of silane of M, wherein pH value of solution is～4.5, silane concentration is～0.35M.It is stand-by that solution is put into 35 ℃ of Water Tank with Temp.-controlled hydrolysis 48 hours.
Matrix is handled: stainless steel base is successively after 400,600, No. 800 abrasive paper for metallograph polishings, putting into degreasing fluid descended ultrasonic 15 minutes in 45 ℃, wash away the residual alkali lye of electrode surface with tap water, dry up behind the deionized water rinsing electrode surface and place moisture eliminator stand-by.
Matrix silanization: matrix is immersed 200s in the good solution of silane of hydrolysis, blow away behind the unnecessary solution of silane in surface promptly in 100 ℃ of drying in oven 1 hour with high pressure nitrogen.
The stainless steel that solution coats before and after modification is handled the typical infrared spectrum of part silane surface rete and is seen accompanying drawing 1.As seen from the figure, solution of silane modification aftertreatment part silane film layer thickness increases, the infrared absorption peak intensity enhancing.786cm wherein
-1Corresponding to the absorption of Si-C stretching vibration, 923cm
-1Corresponding to the absorption of Si-OH, 1158cm
-1Corresponding to the absorption of Si-O-Si key, 1276cm
-1Corresponding to-CH
3Formation vibration absorb.
Adopt electrochemical impedance spectroscopy test evaluation silanization to handle, see accompanying drawing 2 the stainless steel effect on corrosion.Show among the figure that after silanization was handled, the resistance value of stainless steel in NaCl solution was greatly improved, the resistance value of system is further enhanced after the solution of silane of tetra-n-butyl titanate modification is handled simultaneously, for example, compare, add 2.3 * 10 with pure 0.35M solution of silane
-2A small amount of tetra-n-butyl titanate of M can make the barrier propterty of silane film improve 1 most magnitude.Concrete modulus of impedance value (| Z|
10mHz, promptly get the data under the 10mHZ) list in the following table 1.
Table 1 different additive consumption experimental result (stainless steel is that matrix, used silane are that MTMS, additive are tetra-n-butyl titanate)
| Sample | ??|Z| 10mHz |
| Stainless steel is untreated | ??4.81E5 |
| Only contain 2.3 * 10 -2The solution of silane of M tetra-n-butyl titanate is handled part | ??4.88E5 |
| Pure silane solution-treated part | ??4.22E6 |
| Add 2.3 * 10 -5The solution of silane of M tetra-n-butyl titanate is handled part | ??6.82E6 |
| Add 2.3 * 10 -4The solution of silane of M tetra-n-butyl titanate is handled part | ??8.95E6 |
| Add 2.3 * 10 -3The solution of silane of M tetra-n-butyl titanate is handled part | ??2.25E8 |
| Add 2.3 * 10 -2The solution of silane of M tetra-n-butyl titanate is handled part | ??2.32E8 |
The step preparation interpolation content that repeats embodiment 1 is 2.3 * 10
-2The methyltrimethoxy silane solution of M tetra-n-butyl titanate is used to handle cold-rolled steel sheet, steel plate galvanized and LY12 duralumin etc., with the suitability of explanation to multiple matrix.The pre-treatment of cold-rolled steel sheet is identical with stainless steel, and steel plate galvanized and alloy matrix aluminum adopt the alkali-free degreasing fluid to wash the removal oil stain before use, and wherein aluminium alloy need carry out mechanical grinding before cleaning.According to the difference of body material, adopt different corrosion evaluation methods to handling sample.Immersion test adopts the NaCl aqueous solution of 0.1M, observation sample surface appearance; Testing impedance carries out in 3.5 (wt) %NaCl aqueous solution.The results are shown in Table 2.
The experimental result of table 2 different matrix (solution of silane: 0.35M MTMS/2.3 * 10
-2The M titanium
Embodiment 3
Matrix is handled: the stainless steel base pre-treatment is with reference to embodiment 1, and the pre-treatment of steel plate galvanized is with reference to embodiment 2.
Matrix silanization: matrix is immersed 200s in the good solution of silane of hydrolysis, blow away behind the unnecessary solution of silane in surface promptly in 100 ℃ of drying in oven 1 hour with high pressure nitrogen.The evaluation result of treatment samples sees Table the experimental result (solution of silane: 0.19M MTEOS/1.38 * 10 that 3. table 3 additives are zirconic acid four n-propyls
-2M zirconic acid four n-propyls)
Embodiment 4
Matrix is handled: the pre-treatment of aluminium alloy is with reference to embodiment 2.
The matrix silanization: get the good modified silane drips of solution of 200 μ L hydrolysis in aluminium alloy matrix surface, rotating speed is that 3000r/min films solution rotating to be deposited on the back, surface 100 ℃ of drying in oven 1 hour.
Silanization is handled the back matrix surface and is brushed organic coating: Resins, epoxy/polymeric amide (1: 0.8/v: v), coat-thickness 40 μ m, simultaneously with the non-modified silanization handle matrix and not silanization to handle matrix brushing coating be contrast.
The performance evaluation of coating adopts the method for accelerated test, and used experiment is Machu test and boiling water Soak Test.The Machu test: the back side and the side of coating to be measured are sealed with paraffin wax, drawn two dark metallic matrix, mutually perpendicular two cuts of reaching with blade on coating, cut length all is 4cm, and corrosive medium is 5%NaCl+0.6%H
2O
2Solution after soaking 24 hours under 37 ℃, upgrades etchant solution, soaks 24 hours again.Take out sample, along the cut release coating, observe coating shedding degree and cut situation with adhesive tape.Boiling water test: coating/metal system is placed the ebullient deionized water, after 4 hours, stop to soak, take out sample, observe the layering and the foaming phenomenon of coating.The evaluation result of treatment samples sees Table 4.
The test result of table 4 aluminum alloy surface coating performance after the pre-treatment of Different Silicon alkanisation
| Sample | The Machu test | The boiling water test |
| The pure epoxy coating of brushing is handled on the surface without silanization | Coating almost integral body is peeled off, and undercut corrosion is serious | 4-5 bubble |
| The epoxy coat that brush after γ-APS handles on the surface | Near coating wide the peeling off of 1 cm of the having an appointment cut, cut obviously corrodes | 2 bubbles |
| The epoxy coat that brush after modification γ-APS handles on the surface | Near coating wide the peeling off of 0.6cm of the having an appointment cut, cut slightly corrodes | 1 bubble |
The foregoing description is used for the present invention that explains, rather than limits the invention, and in the protection domain of spirit of the present invention and claim, any modification and change to the present invention makes all fall into protection scope of the present invention.
Claims (7)
1. the preparation method of a homogeneous phase modified silane solution, it is characterized in that silane is joined in the mixed system of water and water-miscible organic solvent constantly the additive that agitation condition slowly adds the different content behind the same organic solvent diluting down, silane: water: volume of organic solvent is than being m: n: (100-m-n), wherein m/n is 0.1-1, silane: the mol ratio of additive is 10: 1-10000: 1, after stirring, with the solution left standstill, the constant temperature hydrolysis that configure 0.1-48 hour.
2. preparation method according to claim 1 is characterized in that, described silane is single silane and two silane, and single silane structure general formula is:
Wherein, R is methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl or ethanoyl, and X is one or more in alkyl, thiazolinyl or the alkyl or alkenyl, methoxyl group, oxyethyl group or the benzyl that are replaced by at least one amino, epoxy group(ing) or sulfydryl.
Two silane structure general formulas are:
Wherein, R is methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl or ethanoyl, and Y is CH
2CH
2, (CH
2)
3-NH-(CH
2)
3Or (CH
2)
3-S
4-(CH
2)
3
3. preparation method according to claim 1 is characterized in that, described organic solvent is methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, ethyl acetate or tetrahydrofuran (THF).
4. preparation method according to claim 1 is characterized in that, described additive is zirconic acid alkyl ester, alkyl titanate, stannic acid alkyl ester, lead acetate, Co (acac)
2, Cu (acac)
2Or Zn (acac)
2
5. purposes of the modified silane solution of method preparation according to claim 1 is characterized in that the protective that solution of silane is used for metal base surface handles.
6. purposes according to claim 5 is characterized in that, described metallic matrix is an iron and steel, galvanized steel, aluminium, zinc, magnesium, copper, tin and alloy thereof.
7. purposes according to claim 5 is characterized in that, the protective treatment process of described metal base surface is spread coating, dip coating, spin-coating method or electrochemistry assistant depositing method.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898946A (en) * | 2012-08-15 | 2013-01-30 | 中国科学院宁波材料技术与工程研究所 | Preservative solution use for copper and copper alloy surface, preparation method and application |
| CN103060791A (en) * | 2012-12-18 | 2013-04-24 | 芜湖恒坤汽车部件有限公司 | Metal surface silicane treating agent containing tetraisopropyl titanate and preparing method thereof |
| CN105585734A (en) * | 2015-12-16 | 2016-05-18 | 东莞兆舜有机硅科技股份有限公司 | 1,2-ditrialkoxy silane crosslinking agent and preparation method and application thereof |
| CN105970138A (en) * | 2016-05-20 | 2016-09-28 | 国网山东省电力公司高唐县供电公司 | Long-lasting corrosion prevention method of transmission line tower |
| CN106633112A (en) * | 2016-12-29 | 2017-05-10 | 中国人民大学 | Super-oleophilicity hydrophobic material and preparation method and application thereof |
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2009
- 2009-11-16 CN CN2009101538627A patent/CN101713069B/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898946A (en) * | 2012-08-15 | 2013-01-30 | 中国科学院宁波材料技术与工程研究所 | Preservative solution use for copper and copper alloy surface, preparation method and application |
| CN102898946B (en) * | 2012-08-15 | 2014-12-31 | 中国科学院宁波材料技术与工程研究所 | Preservative solution use for copper and copper alloy surface, preparation method and application |
| CN103060791A (en) * | 2012-12-18 | 2013-04-24 | 芜湖恒坤汽车部件有限公司 | Metal surface silicane treating agent containing tetraisopropyl titanate and preparing method thereof |
| CN105585734A (en) * | 2015-12-16 | 2016-05-18 | 东莞兆舜有机硅科技股份有限公司 | 1,2-ditrialkoxy silane crosslinking agent and preparation method and application thereof |
| CN105970138A (en) * | 2016-05-20 | 2016-09-28 | 国网山东省电力公司高唐县供电公司 | Long-lasting corrosion prevention method of transmission line tower |
| CN106633112A (en) * | 2016-12-29 | 2017-05-10 | 中国人民大学 | Super-oleophilicity hydrophobic material and preparation method and application thereof |
| CN106633112B (en) * | 2016-12-29 | 2018-12-25 | 中国人民大学 | A kind of super oleophilic drainage material and the preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN101713069B (en) | 2011-05-04 |
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