CN107740085A - 一种环保型复合彩色钝化液及其制备方法 - Google Patents
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 24
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims abstract description 24
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 20
- HTJDQJBWANPRPF-UHFFFAOYSA-N Cyclopropylamine Chemical group NC1CC1 HTJDQJBWANPRPF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 13
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims abstract description 13
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- 235000019795 sodium metasilicate Nutrition 0.000 claims abstract description 13
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 13
- 239000011975 tartaric acid Substances 0.000 claims abstract description 13
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 13
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011698 potassium fluoride Substances 0.000 claims abstract description 12
- 235000003270 potassium fluoride Nutrition 0.000 claims abstract description 12
- 239000000176 sodium gluconate Substances 0.000 claims abstract description 12
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- 229940005574 sodium gluconate Drugs 0.000 claims abstract description 12
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 12
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- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004317 sodium nitrate Substances 0.000 claims abstract description 10
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- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- 239000011775 sodium fluoride Substances 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 description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims 1
- 229910052750 molybdenum Inorganic materials 0.000 claims 1
- 239000011733 molybdenum Substances 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 26
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- 238000005516 engineering process Methods 0.000 abstract description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000011701 zinc Substances 0.000 abstract description 7
- 229910052725 zinc Inorganic materials 0.000 abstract description 7
- 239000002932 luster Substances 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- 239000011651 chromium Substances 0.000 abstract description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052804 chromium Inorganic materials 0.000 abstract description 3
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- 150000003839 salts Chemical class 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 3
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 3
- 239000004902 Softening Agent Substances 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- GTTYPHLDORACJW-UHFFFAOYSA-N nitric acid;sodium Chemical compound [Na].O[N+]([O-])=O GTTYPHLDORACJW-UHFFFAOYSA-N 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
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- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 1
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- 238000005246 galvanizing Methods 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
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- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-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
Abstract
本发明公开一种环保型复合彩色钝化液及其制备方法,属金属材料表面处理技术领域。本发明钝化液的组成为:硅酸钠17~22g/L、钼酸钠4~8g/L、硝酸钠6~10g/L、双氧水3~7 mL/L、氟化钾1~3 g/L、氨基三亚甲基叉膦酸2~6 mL/L、葡萄糖酸钠2~4 g/L、酒石酸2~4 mL/L、其余为水,pH值为2.0~2.5;该钝化液的制备方法为将硅酸钠、钼酸钠、硝酸钠、氟化钾、氨基三亚甲基叉膦酸、葡萄糖酸钠、酒石酸、双氧水依次加入到去离子水中混合均匀,加水定容到所需体积,采用硫酸调节pH值为2.0~2.5即得环保型复合彩色钝化液。该钝化液处理后的锌镀层钝化膜为彩色,色彩鲜艳,成膜均匀,耐蚀性能优良,并且钝化液中不含三价铬、六价铬及其它有害物质,环保无污染,钝化工艺简单,钝化效率高,膜层耐蚀性好。
Description
技术领域
本发明涉及一种环保型复合彩色钝化液及其制备方法,属金属材料表面处理技术领域。
背景技术
电镀锌属于表面覆盖层保护法中的重要方法之一,该方法用耐蚀性良好的锌覆盖在耐蚀性较差的被保护材料表面,将被保护材料与腐蚀性介质隔开,以达到控制腐蚀的目的。它不仅能大大提高被保护材料的耐蚀性能,而且电镀技术具有设备简单,操作容易,成本低廉等优点。使该方法成为应用最普通、最重要的防腐方法。锌电镀后如果不进行很好的后处理,镀层很快就会变暗,并相继出现白色腐蚀产物。为了提高钢铁制品的抗腐蚀性能和外观装饰性能,一般都要在镀锌后对其进行钝化处理,使锌层表面上形成一层转化膜层。
常见的无铬钝化工艺中有机物钝化耐蚀性好,但附着力和耐热性能较差,单一无机物钝化耐蚀性略差于有机物钝化。无机与有机物复合钝化是无机分子或离子和有机分子之间的协同缓蚀和性能互补作用,进一步提高了钝化膜的耐蚀性能应该指出,单独使用这些无铬钝化技术还存在不少缺陷,或耐蚀性差,或外观不佳,或电接地性能差,或价格较高,很难达到应用要求。
目前无铬彩色钝化体系中硅酸盐钝化具有很好的应用前景,但稳定性和耐蚀性有待提高;钼酸盐体系具有良好的延缓腐蚀作用,低毒,但对膜层厚度要求太高,成本高;稀土金属盐体系,低毒,稳定性好,具有较好的缓蚀作用,但成本高;钛盐体系抗蚀性较高,但成本高,成分多;有机物体系抗蚀性高,但成膜剂种类较多,钝化工艺较复杂,钝化成本偏高。
发明内容
本发明为了克服现有的硅酸盐、钼酸盐钝化液技术的不足,提供一种环保型复合彩色钝化液,该钝化液的组分为:硅酸钠 17~22g/L、钼酸钠 4~8g/L、硝酸钠 6~10g/L、双氧水 3~7 mL/L、氟化钾或氟化钠1~3 g/L、氨基三亚甲基叉膦酸 2~6 mL/L、葡萄糖酸钠 2~4g/L、酒石酸2~4 mL/L、其余为水,pH值为2.0~2.5。
本发明环保型复合彩色钝化液的配制方法为:将硅酸钠、钼酸钠、硝酸钠、氟化钾、氨基三亚甲基叉膦酸、葡萄糖酸钠、酒石酸、双氧水依次加入到去离子水中混合均匀,加水定容到所需体积,采用硫酸调节pH值为2.0~2.5即得环保型复合彩色钝化液。
所述环保型复合彩色钝化液可以用于钢铁件镀锌后处理工艺,使用本钝化液进行处理后的锌镀层钝化膜为彩色,色彩鲜艳,成膜均匀,耐蚀性能优良,钝化效率高,膜层耐蚀性好。
本发明所述硅酸钠、钼酸钠、硝酸钠、氟化钾、氨基三亚甲基叉膦酸、葡萄糖酸钠、酒石酸、双氧水均为市售分析纯化学试剂。
使用本发明的环保型复合彩色钝化液对电镀锌材料进行钝化处理的方法为:将经过电镀锌的材料(常规方法得到)用水清洗干净,按常规方法进行出光处理后,取出材料水洗,再将材料浸入所述环保型复合彩色钝化液中,室温下浸泡 30~50 秒后,取出并用水清洗后,干燥即可。
所述出光处理(常规方法)为:将镀锌后的材料放入由HNO3和H2O组成的出光液中,于室温下浸泡3~5秒后,取出即可,其中出光液为:质量浓度为3%的 HNO3溶液。
所述经镀锌、出光和钝化后的材料的清洗方法为:自来水冲洗,或者在装有清洁水的槽中或池中漂洗,直至将镀件表面清洗干净为宜。
所述经钝化后的镀锌材料的干燥方法为:自然晾干,或者用吹风机吹干,或者用恒温箱60℃恒温烘干。
本发明所涉及各个工艺过程中所使用的水为自来水,或者是蒸馏水。
本发明的有益效果为:
(1)本发明的环保型复合彩色钝化液可以用于钢铁件镀锌后处理工艺,使用本钝化液进行处理后的锌镀层钝化膜为彩色,色彩鲜艳,成膜均匀,耐蚀性能优良,钝化效率高,膜层耐蚀性好;
(2)本发明钝化液中不含铬等有毒物质,克服了铬酸盐钝化技术毒性大、不环保等缺点,可实现镀锌产品的清洁生产;
(3)本发明钝化液的钝化处理工艺简单,钝化时间短,钝化效率高,膜层附着力强,膜层厚度均匀;
(4)经本发明钝化液处理得到的钝化膜,耐蚀性优良,经中性盐雾试验出现白锈时间超过96小时。
具体实施方式
下面结合具体实施方式对本发明作进一步详细说明,但本发明的保护范围并不限于所述内容。
实施例1:本实施例环保型复合彩色钝化液的组分为:硅酸钠 17g/L、钼酸钠 4g/L、硝酸钠 6g/L、双氧水 3 mL/L、氟化钾 1 g/L、氨基三亚甲基叉膦酸 4 mL/L、葡萄糖酸钠3 g/L、酒石酸2 mL/L、其余为水,pH值为2.0;
本实施例环保型复合彩色钝化液的配制方法为:按照上述组分将硅酸钠、钼酸钠、硝酸钠、氟化钾、氨基三亚甲基叉膦酸、葡萄糖酸钠、酒石酸、双氧水依次加入到去离子水中混合均匀,加水定容到所需体积,采用硫酸调节pH值为2.0即得环保型复合彩色钝化液;
本实施例制备得到的钝化液用于钝化电镀锌钢板:
(1)所述电镀锌钢板经下列方法得到:将 40mm*50mm*1.0mm的低碳钢板在进行电镀之前按常规进行除锈、除油、活化等前处理后,放入常规电镀液中进行电镀处理,镀锌处理工艺的镀液组成及操作条件为:ZnCl2 70 g/L、KCl 175 g/L、硼酸 30 g/L、光亮剂 0.5ml/L、柔软剂 17 ml/L、镀液的pH值为5.4,电流密度为 1.5 A/ dm2,温度为室温,电镀时间为20min,得电镀锌钢板,备用;
(2)配制出光液:将化学纯的HNO3与水配制成浓度为3%的出光液,备用;
(3)将步骤(1)得到的电镀锌钢板用自来水清洗干净后浸入步骤(2)中得到的出光液中,室温下停留5秒,取出后用自来水清洗干净,再浸入钝化液中,室温下浸泡40秒后,取出,经自来水清洗干净后用吹风机吹干;
经钝化液处理后的钢板为金黄色,色彩鲜艳,颜色均匀、成膜均匀,钝化效率高,膜层耐蚀性好,经中性盐雾试验出现白锈时间超过96小时。
实施例2:本实施例环保型复合彩色钝化液的组分为:硅酸钠 18g/L、钼酸钠 6g/L、硝酸钠 8g/L、双氧水 5 mL/L、氟化钾 2 g/L、氨基三亚甲基叉膦酸 2 mL/L、葡萄糖酸钠4 g/L、酒石酸3 mL/L、其余为水,pH值为2.2;
本实施例环保型复合彩色钝化液的配制方法为:按照上述组分将硅酸钠、钼酸钠、硝酸钠、氟化钾、氨基三亚甲基叉膦酸、葡萄糖酸钠、酒石酸、双氧水依次加入到去离子水中混合均匀,加水定容到所需体积,采用硫酸调节pH值为2.0即得环保型复合彩色钝化液;
本实施例制备得到的钝化液用于钝化电镀锌钢板:
(1)所述电镀锌钢板经下列方法得到:将 40mm*50mm*1.0mm的低碳钢板在进行电镀之前按常规进行除锈、除油、活化等前处理后,放入常规电镀液中进行电镀处理,镀锌处理工艺的镀液组成及操作条件为:ZnCl2 70 g/L、KCl 175 g/L、硼酸 30 g/L、光亮剂 0.5ml/L、柔软剂 17 ml/L、镀液的pH值为5.6,电流密度为 1.5 A/ dm2,温度为室温,电镀时间为20分钟,得电镀锌钢板,备用;
(2)配制出光液:将化学纯的HNO3与水配制成质量浓度为3%的出光液,备用;
(3)将步骤(1)得到的电镀锌钢板用自来水清洗干净后浸入步骤(2)中得到的出光液中,室温下停留3秒,取出后用自来水清洗干净,再浸入钝化液中,室温下浸泡30秒后,取出,经自来水清洗干净后用吹风机吹干;
经钝化液处理后的钢板为金黄色,色彩鲜艳,颜色均匀、成膜均匀,钝化效率高,膜层耐蚀性好,经中性盐雾试验出现白锈时间超过120小时。
实施例3:本实施例环保型复合彩色钝化液的组分为:硅酸钠 20g/L、钼酸钠 8g/L、硝酸钠 10g/L、双氧水 7 mL/L、氟化钠 3 g/L、氨基三亚甲基叉膦酸 6 mL/L、葡萄糖酸钠 2 g/L、酒石酸4 mL/L、其余为水,pH值为2.5;
本实施例环保型复合彩色钝化液的配制方法为:按照上述组分将硅酸钠、钼酸钠、硝酸钠、氟化钾、氨基三亚甲基叉膦酸、葡萄糖酸钠、酒石酸、双氧水依次加入到去离子水中混合均匀,加水定容到所需体积,采用硫酸调节pH值为2.0即得环保型复合彩色钝化液;
本实施例制备得到的钝化液用于钝化电镀锌钢板:
(1)所述电镀锌钢板经下列方法得到:将 40mm*50mm*1.0mm的低碳钢板在进行电镀之前按常规进行除锈、除油、活化等前处理后,放入常规电镀液中进行电镀处理,镀锌处理工艺的镀液组成及操作条件为:ZnCl2 70 g/L、KCl 175 g/L、硼酸 30 g/L、光亮剂 0.5ml/L、柔软剂 17 ml/L、镀液的pH值为5.8,电流密度为 1.5 A/ dm2,温度为室温,电镀时间为20分钟,得电镀锌钢板,备用;
(2)配制出光液:将化学纯的HNO3与水配制成质量浓度为3%的出光液,备用;
(3)将步骤(1)得到的电镀锌钢板用自来水清洗干净后浸入步骤(2)中得到的出光液中,室温下停留4秒,取出后用自来水清洗干净,再浸入钝化液中,室温下浸泡50秒后,取出,经自来水清洗干净后用吹风机吹干;
经钝化液处理后的钢板为金黄色,色彩鲜艳,颜色均匀、成膜均匀,钝化效率高,膜层耐蚀性好,经中性盐雾试验出现白锈时间超过100小时。
以上对本发明的具体实施方式作了详细说明,但是本发明并不限于上述实施方式,在本领域普通技术人员所具备的知识范围内,还可以在不脱离本发明宗旨的前提下做出各种变化。
Claims (2)
1.一种环保型复合彩色钝化液,其特征在于:该钝化液的组分为硅酸钠 17~22g/L、钼酸钠 4~8g/L、硝酸钠 6~10g/L、双氧水 3~7 mL/L、氟化钾或氟化钠 1~3 g/L、氨基三亚甲基叉膦酸 2~6 mL/L、葡萄糖酸钠 2~4 g/L、酒石酸2~4 mL/L、其余为水,pH值为2.0~2.5。
2.权利要求1所述环保型复合彩色钝化液的制备方法,其特征在于,具体步骤如下:将硅酸钠、钼酸钠、硝酸钠、氟化钾、氨基三亚甲基叉膦酸、葡萄糖酸钠、酒石酸、双氧水依次加入到去离子水中混合均匀,加水定容到所需体积,采用硫酸调节pH值为2.0~2.5即得环保型复合彩色钝化液。
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