CN104357817A - 镁合金复合型无铬钝化剂及其制备方法 - Google Patents
镁合金复合型无铬钝化剂及其制备方法 Download PDFInfo
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- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002131 composite material Substances 0.000 title abstract description 5
- 238000002161 passivation Methods 0.000 claims abstract description 32
- -1 siloxane methylated potassium Chemical class 0.000 claims abstract description 31
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 20
- 239000010452 phosphate Substances 0.000 claims abstract description 20
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 19
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 19
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 19
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000005642 Oleic acid Substances 0.000 claims abstract description 19
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 19
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 19
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 19
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims abstract description 19
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical group [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims abstract description 18
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 10
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical group [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001488 sodium phosphate Substances 0.000 claims abstract description 9
- 229910000162 sodium phosphate Inorganic materials 0.000 claims abstract description 9
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical group [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims abstract description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 7
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims abstract description 7
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 7
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 7
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 7
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical group [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011701 zinc Substances 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011575 calcium Substances 0.000 claims abstract description 5
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 34
- 150000001875 compounds Chemical class 0.000 claims description 34
- SRWKSFRBHIWJSD-UHFFFAOYSA-N 6-cyclohexylhexan-1-ol Chemical compound OCCCCCCC1CCCCC1 SRWKSFRBHIWJSD-UHFFFAOYSA-N 0.000 claims description 18
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 claims description 18
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 12
- 239000011591 potassium Substances 0.000 claims description 12
- 229910052700 potassium Inorganic materials 0.000 claims description 12
- 239000000470 constituent Substances 0.000 claims description 11
- 150000003016 phosphoric acids Chemical class 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 14
- 230000007797 corrosion Effects 0.000 abstract description 13
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000956 alloy Substances 0.000 abstract description 5
- 231100000252 nontoxic Toxicity 0.000 abstract description 5
- 230000003000 nontoxic effect Effects 0.000 abstract description 5
- 229910045601 alloy Inorganic materials 0.000 abstract description 4
- 229910052804 chromium Inorganic materials 0.000 abstract description 3
- 239000011651 chromium Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract 1
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 abstract 1
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 abstract 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 229940068041 phytic acid Drugs 0.000 abstract 1
- 235000015393 sodium molybdate Nutrition 0.000 abstract 1
- 239000011684 sodium molybdate Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000009849 deactivation Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 229910000714 At alloy Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000004532 chromating Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 206010010071 Coma Diseases 0.000 description 1
- 208000007217 Esophageal Stenosis Diseases 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
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- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000000399 orthopedic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
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- 206010039083 rhinitis Diseases 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 231100000019 skin ulcer Toxicity 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
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Classifications
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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
- C23C22/02—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 non-aqueous solutions
-
- 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
- C23C22/02—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 non-aqueous solutions
- C23C22/03—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 non-aqueous solutions containing phosphorus compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
本发明公开了一种镁合金复合型无铬钝化剂及其制备方法，组分及各组分质量份数如下：钼酸盐4~10份，钨酸盐2~6份，高锰酸钾1~3份，氟钛酸铵2~5份，环己六醇六磷酸酯6~15份，油酸5~15份，甲基三乙氧基硅烷1~5份，正硅酸乙酯1~5份。还包括磷酸盐3~8份，硝酸盐1~5份。还包括硅氧烷甲基化钾1~2份。所述钼酸盐为钼酸钠或者钼酸铵。所述钨酸盐为钨酸钠、钨酸钙或者钨酸锌。所述磷酸盐为磷酸钠，所述硝酸盐为硝酸钙。钝化剂采用有机类钝化物质与无机类钝化物质按比例配合形成复合无铬钝化剂，不含铬，安全无毒，对环境无污染，能在合金表面形成钝化膜，提高镁合金的耐腐蚀性。
Description
技术领域
本发明属于金属表面处理化学品技术领域，具体涉及一种镁合金复合型无铬钝化剂及其制备方法。
背景技术
镁元素在地球上的分布极其广泛，而且储量巨大，镁合金具有很多特性，主要有：1、是目前所有系列合金里最轻的金属结构材料；2、电磁屏蔽性好，是优质导体；3、比强度和比刚度均优于钢铁及铝合金，稍逊于最好的纤维增强塑料；4、加工性能极佳，且成本低廉；5、吸收震动性能优秀，有利于减小震动和噪声所带来的影响；6、高导热性，优于铝合金；7、无毒、可回收性能高，符合可持续发展和环保的要求。因此镁合金广泛应用于各行各业中。
在公路交通工具领域中，镁合金的应用主要包括自行车工业、汽车工业和摩托车工业等。镁合金在综合性能上具有极大的技术优越性，从上世纪九十年代起，韩国、日本及欧美的各大机动车生产商都逐渐把镁合金零部件引入到生产线上，多用于制造驾驶盘、仪表盘、座椅框架等部件。
在军事工业及航空航天领域中，镁合金得到了大量的应用，其质轻、减震和降噪等特点，可非常好地满足该领域对制造材料的要求。当前主要应用于火箭、导弹、飞机、卫星的零部件生产和制造。具有高比强度、高比模量和良好热稳定性的碳或石墨纤维增强的镁金属基复合材料，是航天领域理想的结构材料，用于人造卫星无线骨架、支撑架、反射镜和空间站构架等，结构效率最高。
在医学医疗领域中，不锈钢因其优异的机械及耐蚀性能被广泛地应用于整形外科用的骨骼固定、人工关节和骨骼及食道狭窄部位的扩张支架等，但在身体恢复健康后需要进行二次手术将其摘除，给身体带来又一次创伤。镁合金本身有着良好的机械性能，且镁元素是人体必须的宏量元素之一，对生体内新陈代谢的顺利进行有着不可替代的积极作用。随着镁合金研究的不断深入和新型加工技术快速发展，为医用材料的研究和临床实践带来了新的机遇，可降解镁合金材料已成为当前材料科学和生物医学材料领域备受关注的重点和热点，具有广阔的应用前景和商业潜力。
在电器电子制造领域，镁合金不仅具有轻质、价低、优异的力学机械性能、良好散热性和可回收利用性，同时具有优秀的电磁屏蔽性，在消除手机电磁波对人体健康影响上有着积极意义，也符合 3C 产品对新型产品的开发需求。
镁合金具有很多优异的性能，但耐腐蚀性能却成为其诸多性能中的一个短板，限制了其广泛应用。镁合金的腐蚀主要发生在其与介质环境接触的表面上，腐蚀速度主要由合金的表面和介质所决定，因此，镁合金的腐蚀防护技术一般都是围绕着介质环境与合金界面进行的。镁合金的表面防护处理对于其能得到广泛工业化应用和延长使用寿命具有重要的意义。同时，表面处理又是提高镁合金耐蚀性诸多方法中成本低廉、操作简单又行之有效的手段。目前 镁合金腐蚀防护处理中应用最简单有效的是金属表面钝化处理技术，铬酸盐钝化作为优秀的腐蚀
制剂被广泛应用于金属表面处理。铬酸盐钝化工艺十分成熟，但是由于六价铬具有致癌性，会对生物和人体产生致命的威胁。同时六价铬是一种毒性很大的物质，它严重污染环境，长期接触会引起人头痛、昏迷、鼻炎、鼻穿孔、皮肤溃疡和引发各种癌变等症状，对环境和人体健康危害极大。因此，急需开发安全无毒无污染的新型镁合金钝化剂。
发明内容
本发明的目的是提供一种镁合金复合型无铬钝化剂及其制备方法，钝化剂采用有机类钝化物质与无机类钝化物质按比例配合形成复合无铬钝化剂，不含铬，安全无毒，对环境无污染，能在合金表面形成钝化膜，提高镁合金的耐腐蚀性。
为了实现上述目的，本发明采用的技术手段为：
一种镁合金复合型无铬钝化剂，组分及各组分质量份数如下：钼酸盐 4~10份，钨酸盐 2~6份，高锰酸钾 1~3份，氟钛酸铵 2~5份，环己六醇六磷酸酯 6~15份，油酸 5~15份，甲基三乙氧基硅烷 1~5份，正硅酸乙酯 1~5份。
还包括磷酸盐 3~8份，硝酸盐 1~5份。
还包括硅氧烷甲基化钾 1~2份。
所述钼酸盐为钼酸钠或者钼酸铵。
所述钨酸盐为钨酸钠、钨酸钙或者钨酸锌。
所述磷酸盐为磷酸钠，所述硝酸盐为硝酸钙。
镁合金复合型无铬钝化剂，组分及各组分质量份数如下：钼酸盐 6~8份，钨酸盐 3~5份，高锰酸钾 2份，氟钛酸铵 2.5~4.2份，磷酸盐 4~6份，硝酸盐 2~4份，环己六醇六磷酸酯 8~12份，油酸 8~12份，甲基三乙氧基硅烷 2~4份，正硅酸乙酯 2~4份，硅氧烷甲基化钾 1.8份。
镁合金复合型无铬钝化剂，组分及各组分质量份数如下：钼酸盐 7份，钨酸盐 4份，高锰酸钾 2份，氟钛酸铵 3.6份，磷酸盐 5份，硝酸盐 3份，环己六醇六磷酸酯 10份，油酸 10份，甲基三乙氧基硅烷 3份，正硅酸乙酯 3份，硅氧烷甲基化钾 1.8份。
镁合金复合型无铬钝化剂的制备方法，将钼酸盐、钨酸盐、高锰酸钾、氟钛酸铵混合均匀，得无机钝化物；将环己六醇六磷酸酯、油酸 、甲基三乙氧基硅烷、正硅酸乙酯混合均匀，得有机钝化物；然后在使用前将无机钝化物加入到有机钝化物中，加热至30~80℃，搅拌均匀，得复合型无铬钝化剂。
加热温度优选为45℃。
有益效果：本发明提供的镁合金复合型无铬钝化剂及其制备方法，钝化剂采用有机类钝化物质与无机类钝化物质按比例配合形成复合无铬钝化剂，不含铬，安全无毒，对环境无污染，能在合金表面形成钝化膜，提高镁合金的耐腐蚀性。
具体实施方式
实施例1
一种镁合金复合型无铬钝化剂，组分及各组分质量份数如下：钼酸钠 4份，钨酸锌 2份，高锰酸钾 1份，氟钛酸铵 2份，环己六醇六磷酸酯 6份，油酸 5份，甲基三乙氧基硅烷 1份，正硅酸乙酯 1份。
将钼酸钠、钨酸锌、高锰酸钾、氟钛酸铵混合均匀，得无机钝化物；将环己六醇六磷酸酯、油酸 、甲基三乙氧基硅烷、正硅酸乙酯混合均匀，得有机钝化物；然后在使用前将无机钝化物加入到有机钝化物中，加热至40℃，搅拌均匀，得复合型无铬钝化剂。
实施例2
一种镁合金复合型无铬钝化剂，组分及各组分质量份数如下：钼酸钠10份，钨酸锌6份，高锰酸钾3份，氟钛酸铵5份，环己六醇六磷酸酯15份，油酸15份，甲基三乙氧基硅烷5份，正硅酸乙酯5份。
将钼酸钠、钨酸锌、高锰酸钾、氟钛酸铵混合均匀，得无机钝化物；将环己六醇六磷酸酯、油酸 、甲基三乙氧基硅烷、正硅酸乙酯混合均匀，得有机钝化物；然后在使用前将无机钝化物加入到有机钝化物中，加热至40℃，搅拌均匀，得复合型无铬钝化剂。
实施例3
镁合金复合型无铬钝化剂，组分及各组分质量份数如下：钼酸铵 6份，钨酸钠 3份，高锰酸钾 2份，氟钛酸铵 2.5份，磷酸钠 4份，硝酸钙 2份，环己六醇六磷酸酯 8份，油酸 8份，甲基三乙氧基硅烷 2份，正硅酸乙酯 2~4份，硅氧烷甲基化钾 1.8份。
将钼酸铵、钨酸钠、高锰酸钾、氟钛酸铵、磷酸钠、硝酸钙混合均匀，得无机钝化物；将环己六醇六磷酸酯、油酸 、甲基三乙氧基硅烷、正硅酸乙酯、硅氧烷甲基化钾混合均匀，得有机钝化物；然后在使用前将无机钝化物加入到有机钝化物中，加热至50℃，搅拌均匀，得复合型无铬钝化剂。
实施例4
镁合金复合型无铬钝化剂，组分及各组分质量份数如下：钼酸铵8份，钨酸钠5份，高锰酸钾 2份，氟钛酸铵4.2份，磷酸钠6份，硝酸钙4份，环己六醇六磷酸酯12份，油酸12份，甲基三乙氧基硅烷 2~4份，正硅酸乙酯4份，硅氧烷甲基化钾 1.8份。
将钼酸铵、钨酸钠、高锰酸钾、氟钛酸铵、磷酸钠、硝酸钙混合均匀，得无机钝化物；将环己六醇六磷酸酯、油酸 、甲基三乙氧基硅烷、正硅酸乙酯、硅氧烷甲基化钾混合均匀，得有机钝化物；然后在使用前将无机钝化物加入到有机钝化物中，加热至50℃，搅拌均匀，得复合型无铬钝化剂。
实施例5
镁合金复合型无铬钝化剂，组分及各组分质量份数如下：钼酸钠 7份，钨酸钙 4份，高锰酸钾 2份，氟钛酸铵 3.6份，磷酸钠 5份，硝酸钙 3份，环己六醇六磷酸酯 10份，油酸 10份，甲基三乙氧基硅烷 3份，正硅酸乙酯 3份，硅氧烷甲基化钾 1.8份。
将钼酸钠、钨酸钙、高锰酸钾、氟钛酸铵、磷酸钠和硝酸钙混合均匀，得无机钝化物；将环己六醇六磷酸酯、油酸 、甲基三乙氧基硅烷、正硅酸乙酯和硅氧烷甲基化钾混合均匀，得有机钝化物；然后在使用前将无机钝化物加入到有机钝化物中，加热至30~80℃，搅拌均匀，得复合型无铬钝化剂。
将镁合金用 DK7732 型电火花数控线切割机床加工成规格为13mm×13mm×5mm 的小片，打磨，直到表面露出金属光泽、平整且无划痕即可，作为测试样品，将镁合金采用实施例1~5的复合型无铬钝化剂进行涂覆钝化，涂覆量为5mL/g，然后80℃干燥20min，然后进行性能测试，结果见表1。
参照机械行业标准 JB/T 6073-1992，采用全浸腐蚀试验测定复合型无铬钝化剂在镁合金表面形成涂层的耐蚀性能：取样品浸入 5% NaCl 溶液中浸泡，试样用塑料绳悬挂，上端距液面大于 2cm，溶液 pH 值为 6.5，每隔六天更换一次盐水，敞口放置，温度 25±2℃，记录每个样品出现第一个红锈的时间，耐蚀时间作为耐蚀性评价结果。
中性盐雾试验：
试验箱内的温度保持在35℃，压缩空气要预热到45℃之间并调节到足够的压力。氯化纳溶液的质量浓度为5%±1%，冷凝后溶液的pH值在6.5-7.2之间。在盐雾试验过程中，降雾量应控制在如下范围:每80cm2水平面内，每小时收集的降雾量平均为1.0~2.0ml之间，将试样放置在试验箱中进行连续喷雾72小时，测定平面部腐蚀程度。
涂膜附着力实验：
在试验片的涂膜上间隔1mm刻画横竖垂直的线，根据断开处裂痕扩展的大小判定涂膜的脆性及对本材质的附着性能是否良好。
表1：
Claims (10)
1.一种镁合金复合型无铬钝化剂，其特征在于组分及各组分质量份数如下：钼酸盐 4~10份，钨酸盐 2~6份，高锰酸钾 1~3份，氟钛酸铵 2~5份，环己六醇六磷酸酯 6~15份，油酸 5~15份，甲基三乙氧基硅烷 1~5份，正硅酸乙酯 1~5份。
2.根据权利要求1所述镁合金复合型无铬钝化剂，其特征在于：还包括磷酸盐 3~8份，硝酸盐 1~5份。
3.根据权利要求2所述镁合金复合型无铬钝化剂，其特征在于：还包括硅氧烷甲基化钾 1~2份。
4.根据权利要求1所述镁合金复合型无铬钝化剂，其特征在于：所述钼酸盐为钼酸钠或者钼酸铵。
5.根据权利要求1所述镁合金复合型无铬钝化剂，其特征在于：所述钨酸盐为钨酸钠、钨酸钙或者钨酸锌。
6.根据权利要求2所述镁合金复合型无铬钝化剂，其特征在于：所述磷酸盐为磷酸钠，所述硝酸盐为硝酸钙。
7.根据权利要求3所述的镁合金复合型无铬钝化剂，其特征在于组分及各组分质量份数如下：钼酸盐 6~8份，钨酸盐 3~5份，高锰酸钾 2份，氟钛酸铵 2.5~4.2份，磷酸盐 4~6份，硝酸盐 2~4份，环己六醇六磷酸酯 8~12份，油酸 8~12份，甲基三乙氧基硅烷 2~4份，正硅酸乙酯 2~4份，硅氧烷甲基化钾 1.8份。
8.根据权利要求7所述的镁合金复合型无铬钝化剂，其特征在于组分及各组分质量份数如下：钼酸盐 7份，钨酸盐 4份，高锰酸钾 2份，氟钛酸铵 3.6份，磷酸盐 5份，硝酸盐 3份，环己六醇六磷酸酯 10份，油酸 10份，甲基三乙氧基硅烷 3份，正硅酸乙酯 3份，硅氧烷甲基化钾 1.8份。
9.权利要求1~8中任意一项所述镁合金复合型无铬钝化剂的制备方法，其特征在于：将钼酸盐、钨酸盐、高锰酸钾、氟钛酸铵混合均匀，得无机钝化物；将环己六醇六磷酸酯、油酸 、甲基三乙氧基硅烷、正硅酸乙酯混合均匀，得有机钝化物；然后在使用前将无机钝化物加入到有机钝化物中，加热至30~80℃，搅拌均匀，得复合型无铬钝化剂。
10.根据权利要求9所述的镁合金复合型无铬钝化剂的制备方法，其特征在于：加热温度为45℃。
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