CN104372323B - 铝合金无铬水性钝化剂及其制备方法 - Google Patents
铝合金无铬水性钝化剂及其制备方法 Download PDFInfo
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- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 52
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000011651 chromium Substances 0.000 title claims abstract description 39
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims abstract description 36
- -1 siloxanes Chemical class 0.000 claims abstract description 36
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 34
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- 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
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- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 19
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- 238000002454 metastable transfer emission spectrometry Methods 0.000 claims abstract description 16
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- 239000000470 constituent Substances 0.000 claims abstract description 13
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- 239000011609 ammonium molybdate Substances 0.000 claims description 5
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 5
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- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- MUHFRORXWCGZGE-KTKRTIGZSA-N 2-hydroxyethyl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCO MUHFRORXWCGZGE-KTKRTIGZSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 229920003064 carboxyethyl cellulose Polymers 0.000 claims description 4
- 229940095098 glycol oleate Drugs 0.000 claims description 4
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- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
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- 229910052708 sodium Inorganic materials 0.000 claims 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims 1
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- 229910052782 aluminium Inorganic materials 0.000 description 7
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- 229910052751 metal Inorganic materials 0.000 description 7
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
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- CGZZMOTZOONQIA-UHFFFAOYSA-N cycloheptanone Chemical compound O=C1CCCCCC1 CGZZMOTZOONQIA-UHFFFAOYSA-N 0.000 description 2
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- 230000009286 beneficial effect Effects 0.000 description 1
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- 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
- 239000002932 luster Substances 0.000 description 1
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- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
- C23C22/44—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides
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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
本发明公开了一种铝合金无铬水性钝化剂及其制备方法，组分及各组分质量份数如下：钼酸盐5~10份，钨酸盐2~6份，乳酸3~8份，氟钛酸1~3份，磷酸二氢铵2~6份，油酸4~8份，甲基三乙氧基硅烷2~6份，环己酮1~3份，多元醇8~15份，分散剂2~5份，增稠剂1~4份，水10~30份。还包括γ‑氨丙基三乙氧基硅烷1~5份，硅氧烷甲基化钾1~2份。还包括碳酸胺或者三聚氰胺3~8份。钝化剂采用多元醇与水混合作为溶剂配置成无铬水性钝化剂，不含铬，安全无毒，对环境无污染，且能迅速在合金表面形成钝化膜，固化时间短，提高铝合金的耐腐蚀性。生产工艺简单，且对环境友好，无污染。
Description
技术领域
本发明属于金属表面处理化学品技术领域，具体涉及一种铝合金无铬水性钝化剂及其制备方法。
背景技术
铝合金是一种很好的导热和导电金属，机械性能优良并且相对惰性，在电子、交通、仪表、航空和工业等许多领域中应用广泛。纯铝因在空气中能与氧形成一层很薄、很致密的氧化膜，故耐腐蚀性较高，但是铝合金在加入其它的金属元素后，因各金属的电极电位不同及第二相的产生，容易产生原电池效应，引起铝合金的腐蚀。在自然条件下，铝合金容易在表面形成一层自然氧化膜，其厚度仅约4nm，多孔而不均匀，抗蚀性差，不足以抵抗恶劣环境条件下的腐蚀。为了使铝合金免受介质腐蚀，需对其进行表面处理来提高自身的耐蚀性能。由于铝合金自身物理性质的原因，铝合金上电镀、化学镀都比较困难,这是因为铝对氧具有很大的亲合力，极易生成氧化膜；铝是两性物质，在酸性或碱性溶液中都不稳定；铝的电位很负，在电解液中容易发生置换反应；铝的膨胀系数较绝大多数金属的膨胀系数大，镀层易脱落，现今为了在铝合金上实现电镀、化学镀工艺，多采用传统的二次浸锌前处理工艺来实现，这种工艺使用设备多，材料及能源消耗大，操作时间长，工序繁琐，成本高，而且镀件质量难以保证，工序越多，出现镀件质量隐患的几率越高，即便是最好的铝合金化学镀镍磷合金工艺配方，在这样的操作环境下，也难以获得质量好的镀层；阳极氧化是铝合金材料最常见的表面处理方法之一，阳极氧化膜具有良好的力学性能、很好的耐蚀性及耐摩擦性能，阳极氧化膜可以给铝合金提供良好的耐蚀性，但实际上由于阳极氧化工艺成本高，且膜层较厚不导电，对基体材料疲劳性能有较大影响，限制了它的广泛使用；而化学转化膜可以同时提供合格的附着力和合适的耐蚀性，同时化学转化膜层具有良好的导电性，对基体材料疲劳性能也不会产生明显的影响，除此以外，化学氧化具备工艺简单、无需额外电源、对形状复杂工件成膜性较好、可进行局部修补等优点，为此化学转化处理是工业上航空铝合金涂装前表面预处理最常用的手段。
目前铝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铝合金钝化剂。
发明内容
本发明的目的是提供一种铝合金无铬水性钝化剂及其制备方法，钝化剂采用多元醇与水混合作为溶剂配置成无铬水性钝化剂，不含铬，安全无毒，对环境无污染，且能迅速在合金表面形成钝化膜，固化时间短，提高铝合金的耐腐蚀性。生产工艺简单，且对环境友好，无污染。
为了实现上述目的，本发明采用的技术手段为：
一种铝合金无铬水性钝化剂，组分及各组分质量份数如下：钼酸盐 5~10份，钨酸盐 2~6份，乳酸 3~8份，氟钛酸 1~3份，磷酸二氢铵 2~6份，油酸 4~8份，甲基三乙氧基硅烷2~6份，环己酮 1~3份，多元醇 8~15份，分散剂 2~5份，增稠剂 1~4份，水 10~30份。
还包括γ-氨丙基三乙氧基硅烷 1~5份，硅氧烷甲基化钾 1~2份。
还包括碳酸胺或者三聚氰胺 3~8份。
所述分散剂为十二烷基磺酸钠或者聚氧乙二醇油酸酯。
所述增稠剂为聚乙烯醇、羧乙基纤维素或者羧甲基纤维素钠中的一种。
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。
所述多元醇为丙三醇或者乙二醇。
铝合金无铬水性钝化剂，组分及各组分质量份数如下：钼酸盐 6~8份，钨酸盐 4~6份，乳酸 4~7份，氟钛酸 1.6~2.8份，磷酸二氢铵 3.5~4.9份，油酸 5~7份，甲基三乙氧基硅烷 3~5份，环己酮 1.8~2.3份，多元醇 10~12份，分散剂 3~4份，增稠剂 1~3份，水 15~25份，γ-氨丙基三乙氧基硅烷 3~5份，硅氧烷甲基化钾 1~2份，碳酸胺或者三聚氰胺 4~6份。
所述铝合金无铬水性钝化剂的制备方法，将多元醇与水混合均匀作为溶剂，然后将钼酸盐、钨酸盐、磷酸二氢铵、乳酸、氟钛酸、油酸、甲基三乙氧基硅烷和环己酮加入到溶剂中，搅拌，加入分散剂和增稠剂，升温至40~80℃搅拌30~120min，得铝合金无铬水性钝化剂。
升温温度优选为60℃搅拌50min。
有益效果：本发明提供的铝合金无铬水性钝化剂及其制备方法，钝化剂采用多元醇与水混合作为溶剂配置成无铬水性钝化剂，不含铬，安全无毒，对环境无污染，且能迅速在合金表面形成钝化膜，固化时间短，提高铝合金的耐腐蚀性。生产工艺简单，且对环境友好，无污染。
具体实施方式
实施例1
一种铝合金无铬水性钝化剂，组分及各组分质量份数如下：钼酸钠 5份，钨酸钙 2份，乳酸 3份，氟钛酸 1份，磷酸二氢铵 2份，油酸 4份，甲基三乙氧基硅烷 2份，环己酮 1份，丙三醇 8份，分散剂 十二烷基磺酸钠 2份，增稠剂 聚乙烯醇1份，水 10份。
将多元醇与水混合均匀作为溶剂，然后将钼酸盐、钨酸盐、磷酸二氢铵、乳酸、氟钛酸、油酸、甲基三乙氧基硅烷和环己酮加入到溶剂中，搅拌，加入分散剂和增稠剂，升温至80℃搅拌30，得铝合金无铬水性钝化剂。
实施例2
一种铝合金无铬水性钝化剂，组分及各组分质量份数如下：钼酸钠 10份，钨酸钙6份，乳酸 8份，氟钛酸3份，磷酸二氢铵 6份，油酸 8份，甲基三乙氧基硅烷 6份，环己酮 3份，丙三醇 15份，分散剂 十二烷基磺酸钠 5份，增稠剂 聚乙烯醇4份，水 30份。
将多元醇与水混合均匀作为溶剂，然后将钼酸盐、钨酸盐、磷酸二氢铵、乳酸、氟钛酸、油酸、甲基三乙氧基硅烷和环己酮加入到溶剂中，搅拌，加入分散剂和增稠剂，升温至40℃搅拌80min，得铝合金无铬水性钝化剂。
实施例3
一种铝合金无铬水性钝化剂，组分及各组分质量份数如下：钼酸铵 9份，钨酸锌 5份，乳酸 6份，氟钛酸 1份，磷酸二氢铵 3份，油酸 7份，甲基三乙氧基硅烷 4份，环己酮2份，丙三醇 11份，分散剂 聚氧乙二醇油酸酯 3份，增稠剂 羧乙基纤维素2.5份，γ-氨丙基三乙氧基硅烷 3.8份，硅氧烷甲基化钾 1.6份，水 20份。
将多元醇与水混合均匀作为溶剂，然后将钼酸盐、钨酸盐、磷酸二氢铵、乳酸、氟钛酸、油酸、甲基三乙氧基硅烷、γ-氨丙基三乙氧基硅烷、硅氧烷甲基化钾和环己酮加入到溶剂中，搅拌，加入分散剂和增稠剂，升温至60℃搅拌60min，得铝合金无铬水性钝化剂。
实施例4
铝合金无铬水性钝化剂，组分及各组分质量份数如下：钼酸铵 6份，钨酸钠 4份，乳酸 4份，氟钛酸 1.6份，磷酸二氢铵 3.5份，油酸 5份，甲基三乙氧基硅烷 3份，环己酮1.8份，乙二醇 10份，分散剂 聚氧乙二醇油酸酯3份，增稠剂 羧甲基纤维素钠1份，水 15份，γ-氨丙基三乙氧基硅烷 3份，硅氧烷甲基化钾 1份，碳酸胺4份。
将多元醇与水混合均匀作为溶剂，然后将钼酸盐、钨酸盐、磷酸二氢铵、乳酸、氟钛酸、油酸、甲基三乙氧基硅烷、γ-氨丙基三乙氧基硅烷、硅氧烷甲基化钾、碳酸胺和环己酮加入到溶剂中，搅拌，加入分散剂和增稠剂，升温至60℃搅拌60min，得铝合金无铬水性钝化剂。
实施例5
铝合金无铬水性钝化剂，组分及各组分质量份数如下：钼酸钠 8份，钨酸锌6份，乳酸 7份，氟钛酸 2.8份，磷酸二氢铵 4.9份，油酸 7份，甲基三乙氧基硅烷 5份，环己酮 2.3份，乙二醇 12份，分散剂十二烷基磺酸钠 4份，增稠剂 羧乙基纤维素3份，水 25份，γ-氨丙基三乙氧基硅烷 5份，硅氧烷甲基化钾 2份，三聚氰胺 6份。
将多元醇与水混合均匀作为溶剂，然后将钼酸盐、钨酸盐、磷酸二氢铵、乳酸、氟钛酸、油酸、甲基三乙氧基硅烷、γ-氨丙基三乙氧基硅烷、硅氧烷甲基化钾、三聚氰胺和环己酮加入到溶剂中，搅拌，加入分散剂和增稠剂，升温至60℃搅拌60min，得铝合金无铬水性钝化剂。
实施例6
铝合金无铬水性钝化剂，组分及各组分质量份数如下：钼酸铵 7份，钨酸钙 5份，乳酸 6.5份，氟钛酸 1.8份，磷酸二氢铵 4.3份，油酸 6份，甲基三乙氧基硅烷 4份，环己酮2份，乙二醇 11份，分散剂 十二烷基磺酸钠3.5份，增稠剂 聚乙烯醇 1.8份，水 22份，γ-氨丙基三乙氧基硅烷 4份，硅氧烷甲基化钾 1.2份，三聚氰胺 5份。
将多元醇与水混合均匀作为溶剂，然后将钼酸盐、钨酸盐、磷酸二氢铵、乳酸、氟钛酸、油酸、甲基三乙氧基硅烷、γ-氨丙基三乙氧基硅烷、硅氧烷甲基化钾、三聚氰胺和环己酮加入到溶剂中，搅拌，加入分散剂和增稠剂，升温至60℃搅拌60min，得铝合金无铬水性钝化剂。
实施例7
本实施例与实施例5的区别仅在于未添加三聚氰胺，其余组分及各组分质量份数同实施例5。
实施例8
本实施例与实施例4的区别仅在于未添加碳酸胺，其余组分及各组分质量份数同实施例4。
将铝合金用 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，将铝合金采用实施例1~8的铝合金无铬水性钝化剂进行涂覆钝化，涂覆量为5mL/g，然后80℃干燥5min，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铝合金无铬水性钝化剂在铝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 (9)
1.一种铝合金无铬水性钝化剂，其特征在于组分及各组分质量份数如下：钼酸盐 5~10份，钨酸盐 2~6份，乳酸 3~8份，氟钛酸 1~3份，磷酸二氢铵 2~6份，油酸 4~8份，甲基三乙氧基硅烷 2~6份，环己酮 1~3份，多元醇 8~15份，分散剂 2~5份，增稠剂 1~4份，水 10~30份，γ-氨丙基三乙氧基硅烷 1~5份，硅氧烷甲基化钾 1~2份。
2.根据权利要求1所述铝合金无铬水性钝化剂，其特征在于：还包括碳酸胺或者三聚氰胺 3~8份。
3.根据权利要求1所述铝合金无铬水性钝化剂，其特征在于：所述分散剂为十二烷基磺酸钠或者聚氧乙二醇油酸酯。
4.根据权利要求1所述铝合金无铬水性钝化剂，其特征在于：所述增稠剂为聚乙烯醇、羧乙基纤维素或者羧甲基纤维素钠中的一种。
5.根据权利要求1所述铝合金无铬水性钝化剂，其特征在于：所述钼酸盐为钼酸钠或者钼酸铵。
6.根据权利要求1所述铝合金无铬水性钝化剂，其特征在于：所述钨酸盐为钨酸钠、钨酸钙或者钨酸锌。
7.根据权利要求2所述的铝合金无铬水性钝化剂，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 4~6份，乳酸 4~7份，氟钛酸 1.6~2.8份，磷酸二氢铵 3.5~4.9份，油酸 5~7份，甲基三乙氧基硅烷 3~5份，环己酮 1.8~2.3份，多元醇 10~12份，分散剂 3~4份，增稠剂 1~3份，水 15~25份，γ-氨丙基三乙氧基硅烷 3~5份，硅氧烷甲基化钾 1~2份，碳酸胺或者三聚氰胺 4~6份。
8.权利要求1所述铝合金无铬水性钝化剂的制备方法，其特征在于：将多元醇与水混合均匀作为溶剂，然后将钼酸盐、钨酸盐、磷酸二氢铵、乳酸、氟钛酸、油酸、甲基三乙氧基硅烷、环己酮、γ-氨丙基三乙氧基硅烷和硅氧烷甲基化钾加入到溶剂中，搅拌，加入分散剂和增稠剂，升温至40~80℃搅拌30~120min，得铝合金无铬水性钝化剂。
9.根据权利要求8所述的铝合金无铬水性钝化剂的制备方法，其特征在于：升温至60℃搅拌50min。
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