CN102443794B - 船用铝合金抗划伤、耐指纹无铬化学转化液及转化膜制备 - Google Patents
船用铝合金抗划伤、耐指纹无铬化学转化液及转化膜制备 Download PDFInfo
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- CN102443794B CN102443794B CN2011103993648A CN201110399364A CN102443794B CN 102443794 B CN102443794 B CN 102443794B CN 2011103993648 A CN2011103993648 A CN 2011103993648A CN 201110399364 A CN201110399364 A CN 201110399364A CN 102443794 B CN102443794 B CN 102443794B
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- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Chemical class O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
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- 230000001681 protective effect Effects 0.000 description 1
- 235000011067 sorbitan monolaureate Nutrition 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- JPJZHBHNQJPGSG-UHFFFAOYSA-N titanium;zirconium;tetrahydrate Chemical compound O.O.O.O.[Ti].[Zr] JPJZHBHNQJPGSG-UHFFFAOYSA-N 0.000 description 1
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- 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
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- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
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- Chemical Treatment Of Metals (AREA)
Abstract
本发明涉及船用铝合金装饰与防护涂层领域，具体为一种船用铝合金环保型抗划伤、耐指纹无铬化学转化液及其在化学转化膜中的应用。该化学转化液包含钛盐、锆盐、硅化合物、加速剂、表面活性剂，其余为水；其中：钛盐在无铬化学转化液中的浓度范围为0.02～10g/L，锆盐在无铬化学转化液中的浓度范围为0.1～10g/L，硅化合物在无铬化学转化液中的浓度范围为2～25g/L，加速剂在无铬化学转化液中的浓度范围为0.5～12g/L，表面活性剂在化学转化液中的浓度范围为0.1～10g/L。采用浸渍、刷涂、辊涂或喷淋方式在5xxx或6xxx系列铝合金表面形成化学转化膜，化学转化膜具有良好的耐腐蚀性、抗划伤性及耐指纹性，可用作船用铝合金表面装饰与防护涂层。
Description
技术领域
本发明涉及船用铝合金装饰与防护涂层领域，具体为一种船用铝合金环保型抗划伤、耐指纹无铬化学转化液及其在化学转化膜中的应用(即：化学转化膜的制备方法)。
背景技术
5xxx和6xxx铝合金由于其良好的耐蚀性、可焊性及力学性能，近年来被广泛用于舰船结构材料。由于铝合金自发形成的氧化膜较薄，不能满足海洋等苛刻环境下的使用要求。由于海水及湿热海洋大气的侵蚀作用，裸露铝合金表面会被腐蚀而出现腐蚀坑，并在整个表面形成沙砾状的白色粉末状腐蚀产物，从而严重影响未涂装区域(尤其是内舱)铝合金基体外观。因此，通常需要在铝合金基体上进行阳极氧化或化学转化处理来提高铝合金基体的耐蚀性能和涂层附着力。对于大面积铝合金型材的表面处理来说，化学转化无疑具有明显优势，而目前常用的传统铬酸盐钝化及磷化处理工艺由于存在环境污染严重等问题，已受到国内外环保法规的严格限制。可取代传统化学转化处理工艺的新型环保工艺包括钼酸盐处理、钛锆酸盐处理、钴盐处理等，但这些新型工艺均存在诸如耐蚀性不理想、成本较高、大面积施工困难等诸多问题。因此，亟待寻求高防护性能、低成本、施工方便的新型环保化学转化技术。
船用铝合金工件由于长期工作于海水及海洋大气等苛刻腐蚀环境下，其表面通常需要进行化学转化处理来提高铝合金基体的抗划伤、耐指纹无铬性能。然而，传统的处理方式(如铬酸盐处理及磷化处理)由于存在环境污染问题，目前已被限制使用。因此，开发同时具有良好抗划伤、耐指纹无铬性能的环保型无铬化学转化技术成为当务之急。
发明内容
本发明的目的在于提供一种船用铝合金环保型抗划伤、耐指纹无铬化学转化液及其在化学转化膜中的应用，解决现有环保型化学转化处理工艺难以满足抗划伤、耐指纹性能等问题，其施工简单、维护方便。
本发明的技术方案是：
一种船用铝合金抗划伤、耐指纹无铬化学转化液，包含钛盐、锆盐、硅化合物、加速剂、表面活性剂等，溶剂为水。其中，
钛盐可从四氯化钛、硫酸钛、硫酸氧钛、草酸钛钾、硝酸钛、六氟钛酸、氟钛酸铵、氟钛酸钾等中之一种或一种以上选择。钛盐在无铬化学转化液中的浓度范围为0.02～10g/L，优选0.5～5g/L，最优选1～3g/L。
锆盐可从氧氯化锆、硫酸锆、硫酸氧锆、硝酸锆、硝酸氧锆、碳酸锆、碳酸锆铵、乙酸锆、六氟锆酸、氟锆酸铵、氟锆酸钾等中之一种或一种以上选择。锆盐在无铬化学转化液中的浓度范围为0.1～10g/L，优选1～8g/L，最优选3～6g/L。
硅化合物可从正硅酸钠、偏硅酸钠、正硅酸钾、偏硅酸钾、正硅酸锂、偏硅酸锂、六氟硅酸、氟硅酸钠、氟硅酸铵、硅溶胶等中之一种或一种以上选择。硅化合物在无铬化学转化液中的浓度范围为2～25g/L，优选5～20g/L，最优选8～15g/L。
加速剂为氟化物、羧酸、磺酸、过硫酸盐、过氧化氢等之一种或一种以上。氟化物可从氟化钠、氟化钾、氟化铵、氟化氢铵、氟化氢等中之一种或一种以上选择。羧酸可从甲酸、乙酸、丙酸、丁酸、戊酸、苯甲酸、硝基苯甲酸、丙二酸、丁二酸、柠檬酸、酒石酸、苹果酸、水杨酸、肉桂酸、马来酸、富马酸、葡萄糖酸、葡庚糖酸等中之一种或一种以上选择。磺酸可从氨基磺酸、苯基磺酸、硝基苯磺酸等中之一种或一种以上选择。过硫酸盐可从过硫酸钾、过硫酸钠、过硫酸铵中之一种或一种以上选择。加速剂在无铬化学转化液中的浓度范围为0.5～12g/L，优选1～8g/L，最优选3～5g/L。
pH调整剂为矿物酸、碱金属氢氧化物、氨水、碳酸盐等之一种或一种以上。矿物酸为盐酸、硝酸、硫酸、氢氟酸之一种或一种以上，碱金属氢氧化物为氢氧化物、氢氧化钾、氢氧化锂等之一种或一种以上。碳酸盐可从碳酸钠、碳酸氢钠、碳酸钾、碳酸氢钾、碳酸铵、碳酸氢铵等中之一种或一种以上选择。使用pH调整剂将无铬化学转化液pH值调整为1.0～5.0，优选2.0～4.5，最优选2.5～3.5。
表面活性剂由阳离子表面活性剂和非离子表面活性剂组成，阳离子表面活性剂可以使用十二烷基三甲基氯化铵、十二烷基二甲基苄基氯化铵、十四烷基三甲基氯化铵、十六烷基三甲基氯化铵、十六烷基三甲基溴化铵、十八烷基三甲基溴化铵等之一种或一种以上。非离子表面活性剂为烷基酚聚氧乙烯醚、脂肪醇聚氧乙烯醚、脂肪酸聚氧乙烯酯、失水山梨醇脂肪酸酯及氟碳表面活性剂、聚氧乙烯脂肪酸酯LAE-9、山梨醇酐单月桂酸酯SPAN-20、OP-10乳化剂、聚乙二醇辛基苯基醚TX-100、壬基酚聚氧乙烯醚NP-10等之一种或一种以上。表面活性剂在化学转化液中的浓度范围为0.1～10g/L，优选0.5～5g/L，最优选1～2g/L。
船用铝合金抗划伤、耐指纹无铬化学转化液由钛盐、锆盐、硅化合物、加速剂、表面活性剂和水等均匀混合而成。使用pH调整剂将无铬化学转化液pH值调整为1.0～5.0，优选2.0～4.5，最优选2.5～3.5。
利用上述船用铝合金抗划伤、耐指纹无铬化学转化液，无铬无磷纳米级化学转化膜的成膜工艺步骤包括：脱脂→水洗→酸蚀→水洗→化学转化→水洗→干燥。其中，
化学转化可使用下述工艺：
施工方法包括浸渍、刷涂、辊涂或喷淋，处理温度为10～50℃，优选20～40℃，最优选25～35℃；处理时间为0.5～5min，优选1～4min，最优选2～3min。无铬化学转化液在5xxx或6xxx铝合金表面形成化学转化膜，化学转化膜外观随成膜时间延长逐渐呈现白→微蓝→五彩色。
脱脂步骤可使用下述工艺：
碳酸钠 30g/L 磷酸钠 20g/L
硅酸钠 8g/L 十二烷基苯磺酸钠 1g/L
其余为水。
温度 50～60℃ 处理时间 1～5min。
酸蚀步骤可使用下述工艺：
浓硝酸300mL/L，其余为水，温度25℃，处理时间0.5～2min。
本发明的有益效果是：
1、本发明抗划伤、耐指纹无铬化学转化液可由有机硅、钛酸酯、锆酸酯、缓蚀组份、pH调整剂、溶剂、助剂等组成，所形成的化学转化膜主要由氧化硅、氧化钛、氧化锆等复合氧化物组成，无铬化学转化膜具有良好的耐腐蚀性、抗划伤性及耐指纹性，可用作船用铝合金表面装饰与防护涂层。
2、本发明适于船用铝合金包括5xxx或6xxx系列铝合金。
具体实施方式
以下就本发明具体实施方法进行详细说明，但不受限制：
本发明船用铝合金抗划伤、耐指纹无铬化学转化液，包含钛盐、锆盐、硅化合物、加速剂、表面活性剂等，溶剂为水。船用铝合金抗划伤、耐指纹无铬化学转化液由钛盐、锆盐、硅化合物、加速剂、pH调整剂、表面活性剂和水等均匀混合而成。使用pH调整剂将无铬化学转化液pH值调整为1.0～5.0，优选2.0～4.5，最优选2.5～3.5。
利用上述船用铝合金抗划伤、耐指纹无铬化学转化液，无铬无磷纳米级化学转化膜的成膜工艺步骤包括：脱脂→水洗→酸蚀→水洗→化学转化→水洗→干燥。其中，
化学转化可使用下述工艺：
施工方法包括浸渍、刷涂、辊涂或喷淋，处理温度为10～50℃，优选20～40℃，最优选25～35℃；处理时间为0.5～5min，优选1～4min，最优选2～3min。无铬化学转化液在5xxx或6xxx铝合金表面形成化学转化膜，化学转化膜外观随成膜时间延长逐渐呈现白→微蓝→五彩色。
脱脂步骤可使用下述工艺：
碳酸钠 30g/L 磷酸钠 20g/L
硅酸钠 8g/L 十二烷基苯磺酸钠 1g/L
其余为水。
温度 50～60℃ 处理时间 1～5min。
酸蚀步骤可使用下述工艺：
浓硝酸300mL/L，其余为水，温度25℃，处理时间0.5～2min。
所形成的化学转化膜主要由氧化硅、氧化钛、氧化锆等复合氧化物组成，转化膜的厚度为0.5～1μm。
表1(g/L)
本发明无铬无磷纳米级化学转化膜具有良好的耐腐蚀性和涂层附着力，中性盐雾试验可达168小时以上不变色，可用于船用铝合金取代传统含铬化学转化和磷化处理。
Claims (5)
1.一种船用铝合金抗划伤、耐指纹无铬化学转化液，其特征在于，该化学转化液用于船用铝合金表面装饰及防护涂层，船用铝合金为5xxx系列或6xxx系列铝合金，包含钛盐、锆盐、硅化合物、加速剂、表面活性剂和水；其中：
钛盐在无铬化学转化液中的浓度范围为1～3 g/L，锆盐在无铬化学转化液中的浓度范围为3～6 g/L，硅化合物在无铬化学转化液中的浓度范围为8～15 g/L，加速剂在无铬化学转化液中的浓度范围为3～5 g/L，表面活性剂在化学转化液中的浓度范围为1～2 g/L，其余为水；
钛盐为四氯化钛、硫酸钛、硫酸氧钛、草酸钛钾、硝酸钛、六氟钛酸、氟钛酸铵、氟钛酸钾中之一种以上；
锆盐为氧氯化锆、硫酸锆、硫酸氧锆、硝酸锆、硝酸氧锆、碳酸锆、碳酸锆铵、乙酸锆、六氟锆酸、氟锆酸铵、氟锆酸钾中之一种以上；
硅化合物为正硅酸钠、偏硅酸钠、正硅酸钾、偏硅酸钾、正硅酸锂、偏硅酸锂、六氟硅酸、氟硅酸钠、氟硅酸铵、硅溶胶中之一种以上；
加速剂为氟化物、羧酸、磺酸、过硫酸盐、过氧化氢之一种以上，氟化物为氟化钠、氟化钾、氟化铵、氟化氢铵、氟化氢中之一种以上，羧酸为甲酸、乙酸、丙酸、丁酸、戊酸、苯甲酸、硝基苯甲酸、丙二酸、丁二酸、柠檬酸、酒石酸、苹果酸、水杨酸、肉桂酸、马来酸、富马酸、葡萄糖酸、葡庚糖酸中之一种以上，磺酸为氨基磺酸、苯基磺酸、硝基苯磺酸中之一种以上，过硫酸盐为过硫酸钾、过硫酸钠、过硫酸铵中之一种以上；
表面活性剂由阳离子表面活性剂和非离子表面活性剂组成，阳离子表面活性剂为十二烷基三甲基氯化铵、十二烷基二甲基苄基氯化铵、十四烷基三甲基氯化铵、十六烷基三甲基氯化铵、十六烷基三甲基溴化铵、十八烷基三甲基溴化铵之一种以上，非离子表面活性剂为烷基酚聚氧乙烯醚、脂肪醇聚氧乙烯醚、脂肪酸聚氧乙烯酯、失水山梨醇脂肪酸酯及氟碳表面活性剂之一种以上。
2.一种利用权利要求1所述的船用铝合金抗划伤、耐指纹无铬化学转化液制备化学转化膜的方法，其特征在于，无铬无磷纳米级化学转化膜的成膜工艺步骤包括：脱脂→水洗→酸蚀→水洗→化学转化→水洗→干燥，船用铝合金抗划伤、耐指纹无铬化学转化液由钛盐、锆盐、硅化合物、加速剂、表面活性剂和水均匀混合而成，使用pH调整剂将无铬化学转化液pH值调整为1.0～5.0；化学转化液的施工方法包括浸渍、刷涂、辊涂或喷淋，处理温度为10～50 ℃，处理时间为0.5～5 min，无铬化学转化液在5xxx或6xxx铝合金表面形成化学转化膜，化学转化膜外观随成膜时间延长逐渐呈现白→微蓝→五彩色，获得化学转化膜厚度为0.5-1 μm。
3.按照权利要求2所述的化学转化膜的制备方法，其特征在于，pH调整剂为矿物酸、碱金属氢氧化物、氨水、碳酸盐之一种以上，矿物酸为盐酸、硝酸、硫酸、氢氟酸之一种以上，碱金属氢氧化物为氢氧化物、氢氧化钾、氢氧化锂之一种以上，碳酸盐为碳酸钠、碳酸氢钠、碳酸钾、碳酸氢钾、碳酸铵、碳酸氢铵中之一种以上。
4.按照权利要求2所述的化学转化膜的制备方法，其特征在于，脱脂步骤采用的脱脂液为：碳酸钠30g/L，磷酸钠20 g/L，硅酸钠8 g/L，十二烷基苯磺酸钠1 g/L，其余为水；脱脂步骤使用下述工艺：温度50～60 ℃，处理时间1～5 min。
5.按照权利要求2所述的化学转化膜的制备方法，其特征在于，酸蚀步骤采用酸蚀液为浓硝酸 300 mL/L，其余为水；酸蚀步骤使用下述工艺：温度25 ℃，处理时间0.5～2 min。
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