CN112126920A - Chromium-free conversion agent suitable for roller coating process and preparation method thereof - Google Patents
Chromium-free conversion agent suitable for roller coating process and preparation method thereof Download PDFInfo
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000007761 roller coating Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 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 abstract description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011734 sodium Substances 0.000 claims abstract description 22
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 22
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002562 thickening agent Substances 0.000 claims abstract description 14
- 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 12
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 12
- 239000011975 tartaric acid Substances 0.000 claims abstract description 12
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 claims abstract description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 9
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract 2
- -1 dodecyl alcohol ester Chemical class 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 10
- LQZZUXJYWNFBMV-UHFFFAOYSA-N ethyl butylhexanol Natural products CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 6
- 239000000661 sodium alginate Substances 0.000 claims description 6
- 235000010413 sodium alginate Nutrition 0.000 claims description 6
- 229940005550 sodium alginate Drugs 0.000 claims description 6
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 6
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 5
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 claims description 3
- 229920003064 carboxyethyl cellulose Polymers 0.000 claims description 2
- 238000002161 passivation Methods 0.000 abstract description 15
- 238000007739 conversion coating Methods 0.000 abstract description 12
- 229910000838 Al alloy Inorganic materials 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 6
- 238000010924 continuous production Methods 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000007598 dipping method Methods 0.000 abstract description 3
- 238000005507 spraying Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 16
- 238000000576 coating method Methods 0.000 description 16
- 150000003839 salts Chemical class 0.000 description 12
- 239000007921 spray Substances 0.000 description 11
- 230000007935 neutral effect Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 230000003628 erosive effect Effects 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000004383 yellowing Methods 0.000 description 6
- 238000004381 surface treatment Methods 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 3
- 150000001844 chromium Chemical class 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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
- C23C22/34—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
- C23C22/36—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 containing also phosphates
- C23C22/361—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 containing also phosphates containing titanium, zirconium or hafnium compounds
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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
Description
技术领域technical field
本发明涉及金属表面处理技术领域，主要涉及一种无铬的环保型转换剂，特别适用于铝及其合金、黑色金属等材料在辊筒涂覆等连续生产工艺中获得高质量的转换涂层。The invention relates to the technical field of metal surface treatment, and mainly relates to a chromium-free environment-friendly conversion agent, which is particularly suitable for obtaining high-quality conversion coatings in continuous production processes such as roller coating for materials such as aluminum and its alloys and ferrous metals. .
背景技术Background technique
对金属表面进行处理，形成转换涂层可以延缓金属的腐蚀，延长其使用寿命。目前，应用最广泛的依旧是铬酸盐钝化工艺。该工艺虽然简单、成熟，生成的转换涂层耐蚀性及装饰性较好，但铬酸盐毒性高，具有致癌性，对人体和环境的危害巨大。近年来，世界各国都对铬的排放进行了严格的管制。欧盟颁布了ROHS、WEEE和ELV等法规明令禁止含有六价铬的汽车及电子零部件进入市场。我国也要求废水中铬离子必须零排放。铬酸盐钝化技术已受到严格控制，因此，开发一种无毒、环保、高性能的绿色钝化技术已成成为当前的研究热点。Treating the metal surface to form a conversion coating can delay the corrosion of the metal and prolong its service life. At present, the most widely used is still the chromate passivation process. Although the process is simple and mature, the resulting conversion coating has good corrosion resistance and decorative properties, but the chromate is highly toxic, carcinogenic, and harmful to the human body and the environment. In recent years, countries around the world have strictly controlled the emission of chromium. The EU has promulgated regulations such as ROHS, WEEE and ELV, which explicitly prohibit automobiles and electronic parts containing hexavalent chromium from entering the market. my country also requires zero emission of chromium ions in wastewater. Chromate passivation technology has been strictly controlled, therefore, the development of a non-toxic, environmentally friendly, high-performance green passivation technology has become a current research focus.
近来，科研工作者们开发了各种各样的无铬钝化工艺，取得了较大的进展。但目前的钝化剂普遍只适用于浸渍或喷淋工艺，例如，一种成膜剂及其在铝型材表面处理无铬钝化液中的应用（CN110629214A），需要将铝材完全浸没在钝化液中，再经过三道水洗，沥干，烘烤10-20分钟后，才可得到一层致密的钝化膜。又如，无铬钝化组合物、无铬钝化剂及其制备方法（CN107653449B），需要将铝材浸泡在钝化剂中3-5分钟，再清洗，烘烤，才能制得一层钝化膜。此外，目前的钝化剂大多只针对单一的金属种类，无法同时满足不同种类的金属表面处理需求，例如，一种成膜剂及其在铝型材表面处理无铬钝化液中的应用（CN110629214A）只适用于铝材的表面处理。又如，一种在铝及其合金表面上形成转化膜的环保型工艺（CN1614090A），也只适用于铝及其合金表面的处理。到目前为止，还没有适用于多种不同金属的、可以在辊筒涂覆等连续生产工艺中应用的、能够生成高性能转换涂层的环保型无铬钝化剂。Recently, researchers have developed various chromium-free passivation processes and have made great progress. But the current passivation agent is generally only suitable for dipping or spraying process. For example, a film-forming agent and its application in the chromium-free passivation solution for the surface treatment of aluminum profiles (CN110629214A), the aluminum material needs to be completely immersed in the passivation solution. After three washings, draining, and baking for 10-20 minutes, a dense passivation film can be obtained. In another example, the chromium-free passivation composition, the chromium-free passivation agent and the preparation method thereof (CN107653449B), the aluminum material needs to be soaked in the passivation agent for 3-5 minutes, then cleaned and baked to obtain a layer of passivation chemical film. In addition, most of the current passivation agents are only aimed at a single metal type, and cannot meet the needs of different types of metal surface treatment at the same time. ) is only suitable for surface treatment of aluminum. For another example, an environmentally friendly process (CN1614090A) for forming a conversion film on the surface of aluminum and its alloys is also only suitable for the treatment of the surfaces of aluminum and its alloys. So far, there are no environmentally friendly chromium-free passivators that can produce high-performance conversion coatings for many different metals and can be used in continuous production processes such as roll coating.
发明内容SUMMARY OF THE INVENTION
本发明针对现有技术存在的不足，提供了一种适用于辊筒涂覆工艺的无铬转换剂及其制备方法，具体技术方案如下：In view of the deficiencies existing in the prior art, the present invention provides a chromium-free conversion agent suitable for a roller coating process and a preparation method thereof, and the specific technical scheme is as follows:
一种适用于辊筒涂覆工艺的无铬转换剂及其制备方法，其特征在于，所述转换剂按质量百分比含有：磷酸5.0-20.0%，硝酸1.0-5.0%，氟钛酸钠1.5-6.0%，氟锆酸钠1.5-6.0%，酒石酸2.5-8.0%，碳酸锆1.0-12.0%，成膜助剂1.0-10.0%，增稠剂0.2-3.5%，其余的为去离子水。A chromium-free conversion agent suitable for a roller coating process and a preparation method thereof, characterized in that the conversion agent contains by mass percentage: phosphoric acid 5.0-20.0%, nitric acid 1.0-5.0%, sodium fluorotitanate 1.5- 6.0%, sodium fluorozirconate 1.5-6.0%, tartaric acid 2.5-8.0%, zirconium carbonate 1.0-12.0%, film-forming aid 1.0-10.0%, thickener 0.2-3.5%, and the rest are deionized water.
上述的成膜助剂包括十二碳醇酯、乙二醇丁醚、丙二醇乙醚的一种或几种。The above-mentioned film-forming auxiliary includes one or more of dodecyl alcohol ester, ethylene glycol butyl ether and propylene glycol ethyl ether.
上述的增稠剂为羧乙基纤维素、海藻酸钠、聚丙烯酸钠、聚乙烯醇的一种或几种混合物。The above-mentioned thickener is one or more mixtures of carboxyethyl cellulose, sodium alginate, sodium polyacrylate and polyvinyl alcohol.
上述转换剂所适用的材料为铝及其合金、黑色金属等多种材料。The applicable materials for the conversion agent are aluminum and its alloys, ferrous metals and other materials.
上述转换剂的制备方法包括下述步骤：The preparation method of above-mentioned conversion agent comprises the steps:
（1）按原料的配方组成，磷酸、硝酸、氟钛酸钠、氟锆酸钠、去离子水，充分搅拌制得溶液A；(1) According to the formula of the raw materials, phosphoric acid, nitric acid, sodium fluorotitanate, sodium fluorozirconate, and deionized water are fully stirred to prepare solution A;
（2）按原料的配方组成，酒石酸、碳酸锆、成膜助剂、增稠剂等溶于适量去离子水中，充分搅拌待其溶解制得溶液B；(2) According to the formulation of the raw materials, tartaric acid, zirconium carbonate, film-forming aids, thickeners, etc. are dissolved in an appropriate amount of deionized water, and the solution B is prepared by fully stirring until they are dissolved;
（3）将溶液B缓慢的加入溶液A中，充分搅拌制得无铬转换剂。(3) Slowly add solution B to solution A, and stir well to obtain a chromium-free conversion agent.
本发明的有益效果：Beneficial effects of the present invention:
（1）本发明的转换剂为无铬的绿色环保型产品；(1) The conversion agent of the present invention is a chromium-free green and environment-friendly product;
（2）本发明的转换剂除了适用于传统的浸渍、喷淋等工艺，还特别适用于辊筒涂覆等卷材机组连续生产工艺；(2) The conversion agent of the present invention is not only suitable for traditional dipping, spraying and other processes, but also especially suitable for continuous production processes of coiled material units such as roller coating;
（3）本发明的转换剂可适用于铝及其合金、黑色金属等多种材料的表面处理；(3) The conversion agent of the present invention can be applied to the surface treatment of aluminum and its alloys, ferrous metals and other materials;
（4）本发明的转换剂所生成的转换涂层具有很强的结合力和抗腐蚀能力；(4) The conversion coating produced by the conversion agent of the present invention has strong binding force and anti-corrosion ability;
（5）本发明的转换剂的钝化时间短、成本低、效率高。(5) The conversion agent of the present invention has short passivation time, low cost and high efficiency.
具体实施方式Detailed ways
实施例1Example 1
一种适用于辊筒涂覆工艺的无铬转换剂，所述转换剂中各组分的含量如下：磷酸7.5%，硝酸2.5%，氟钛酸钠3.0%，氟锆酸钠3.0%，酒石酸4.0%，碳酸锆4.5%，成膜助剂2.5%，增稠剂0.35%，其余的为去离子水。A chromium-free conversion agent suitable for a roller coating process, the content of each component in the conversion agent is as follows: phosphoric acid 7.5%, nitric acid 2.5%, sodium fluorotitanate 3.0%, sodium fluorozirconate 3.0%, tartaric acid 4.0%, zirconium carbonate 4.5%, coalescence aid 2.5%, thickener 0.35%, and the rest is deionized water.
上述成膜助剂为：十二碳醇酯2.5%；The above film-forming aids are: dodecyl alcohol ester 2.5%;
上述的增稠剂为：海藻酸钠0.35%。Above-mentioned thickener is: sodium alginate 0.35%.
上述转换剂的制备方法包括下述步骤：The preparation method of above-mentioned conversion agent comprises the steps:
（1）按原料的配方组成，磷酸、硝酸、氟钛酸钠、氟锆酸钠、去离子水，充分搅拌制得溶液A；(1) According to the formula of the raw materials, phosphoric acid, nitric acid, sodium fluorotitanate, sodium fluorozirconate, and deionized water are fully stirred to prepare solution A;
（2）按原料的配方组成，酒石酸、碳酸锆、十二碳醇酯、海藻酸钠等溶于适量去离子水中，充分搅拌待其溶解制得溶液B；(2) According to the formula composition of the raw materials, tartaric acid, zirconium carbonate, dodecyl alcohol ester, sodium alginate, etc. are dissolved in an appropriate amount of deionized water, and fully stirred until they are dissolved to obtain solution B;
（3）将溶液B缓慢的加入溶液A中，充分搅拌制得无铬转换剂。(3) Slowly add solution B to solution A, and stir well to obtain a chromium-free conversion agent.
本实施例制得的转换剂对4032铝合金表面进行辊筒涂覆工艺处理（10 m/min），处理后转换涂层致密、平整、色泽均匀，对其进行防腐耐磨实验（耐中性盐雾实验为4%的氯化钠氛围下，出现白蚀或起泡的现象所需时间；耐溶剂实验为在95%乙醇溶液中浸泡15分钟后，再置于中性盐雾条件下，出现白蚀或起泡的现象所需时间；耐黄变实验为在300°C下，大气环境下，保持15分钟后，再置于中性盐雾条件下，出现白蚀或起泡的现象所需时间）。同时，对转换涂层的附着力进行测试（附着力测试方法为在涂层表面划格，刀齿间距为2毫米，将粘着力大于10N/25mm的胶带粘附在划格上，压紧并排除空气，再以垂直涂层表面的角度快速拉起胶带，目视检测涂层表面。分级表示：0级，切割边缘完全平滑，无一格脱落；1级，在切口交叉处有少许涂层脱落，但交叉切割面积受影响不能明显大于5%；2级，在切口交叉处和/或沿切口边缘有涂层脱落，受影响的交叉切割面积明显大于5%，但不能明显大于15%。），测得数据如下：The conversion agent prepared in this example is subjected to a roller coating process (10 m/min) on the surface of 4032 aluminum alloy. After the treatment, the conversion coating is dense, smooth, and uniform in color. The salt spray test is the time required for white erosion or foaming in a 4% sodium chloride atmosphere; the solvent resistance test is immersed in a 95% ethanol solution for 15 minutes, and then placed in a neutral salt spray condition. The time required for white erosion or blistering; the yellowing resistance test is at 300°C, in the atmospheric environment, after 15 minutes, and then placed under neutral salt spray conditions, white erosion or blistering phenomenon occurs time required). At the same time, the adhesion of the conversion coating was tested (the adhesion test method is to draw a grid on the surface of the coating, the spacing between the teeth is 2 mm, and the adhesive tape with an adhesive force greater than 10N/25mm is attached to the grid, press and Remove the air, and then quickly pull up the tape at an angle perpendicular to the coating surface, and visually inspect the coating surface.Grading representation: Grade 0, the cutting edge is completely smooth, and no strips fall off; Grade 1, there is a little coating at the intersection of the incision Falling off, but the affected cross-cut area cannot be significantly greater than 5%; Grade 2, the coating has fallen off at the intersection of the incision and/or along the edge of the incision, and the affected cross-cut area is significantly greater than 5%, but not significantly greater than 15%. ), the measured data are as follows:
实施例2Example 2
一种适用于辊筒涂覆工艺的无铬转换剂，所述转换剂中各组分的含量如下：磷酸10%，硝酸3.5%，氟钛酸钠3.5%，氟锆酸钠3.5%，酒石酸5.5%，碳酸锆5.5%，成膜助剂3%，增稠剂0.3%，其余的为去离子水。A chromium-free conversion agent suitable for roller coating process, the content of each component in the conversion agent is as follows: phosphoric acid 10%, nitric acid 3.5%, sodium fluorotitanate 3.5%, sodium fluorozirconate 3.5%, tartaric acid 5.5%, 5.5% zirconium carbonate, 3% film-forming aid, 0.3% thickener, and the rest is deionized water.
上述成膜助剂为：十二碳醇酯2.5%，乙二醇丁醚0.5%；The above film-forming aids are: dodecyl alcohol ester 2.5%, butyl glycol ether 0.5%;
上述的增稠剂为：海藻酸钠0.2%，聚丙烯酸钠0.1%。The above-mentioned thickeners are: sodium alginate 0.2%, sodium polyacrylate 0.1%.
上述转换剂的制备方法包括下述步骤：The preparation method of above-mentioned conversion agent comprises the steps:
（1）按原料的配方组成，磷酸、硝酸、氟钛酸钠、氟锆酸钠、去离子水，充分搅拌制得溶液A；(1) According to the formula of the raw materials, phosphoric acid, nitric acid, sodium fluorotitanate, sodium fluorozirconate, and deionized water are fully stirred to prepare solution A;
（2）按原料的配方组成，酒石酸、碳酸锆、十二碳醇酯、乙二醇丁醚、海藻酸钠、聚丙烯酸钠等溶于适量去离子水中，充分搅拌待其溶解制得溶液B；(2) According to the formula of the raw materials, tartaric acid, zirconium carbonate, dodecyl alcohol ester, ethylene glycol butyl ether, sodium alginate, sodium polyacrylate, etc. are dissolved in an appropriate amount of deionized water, and fully stirred until they are dissolved to obtain solution B ;
（3）将溶液B缓慢的加入溶液A中，充分搅拌制得无铬转换剂。(3) Slowly add solution B to solution A, and stir well to obtain a chromium-free conversion agent.
本实施例制得的转换剂对3003铝合金表面进行辊筒涂覆工艺处理（10 m/min），处理后转换涂层致密、平整、色泽均匀，对其进行防腐耐磨实验（耐中性盐雾实验为4%的氯化钠氛围下，出现白蚀或起泡的现象所需时间；耐溶剂实验为在95%乙醇溶液中浸泡15分钟后，再置于中性盐雾条件下，出现白蚀或起泡的现象所需时间；耐黄变实验为在300°C下，大气环境下，保持15分钟后，再置于中性盐雾条件下，出现白蚀或起泡的现象所需时间）。同时，对转换涂层的附着力进行测试（附着力测试方法为在涂层表面划格，刀齿间距为2毫米，将粘着力大于10N/25mm的胶带粘附在划格上，压紧并排除空气，再以垂直涂层表面的角度快速拉起胶带，目视检测涂层表面。分级表示：0级，切割边缘完全平滑，无一格脱落；1级，在切口交叉处有少许涂层脱落，但交叉切割面积受影响不能明显大于5%；2级，在切口交叉处和/或沿切口边缘有涂层脱落，受影响的交叉切割面积明显大于5%，但不能明显大于15%。），测得数据如下：The conversion agent prepared in this example is subjected to a roller coating process (10 m/min) on the surface of 3003 aluminum alloy. After the treatment, the conversion coating is dense, smooth and uniform in color. The salt spray test is the time required for white erosion or foaming in a 4% sodium chloride atmosphere; the solvent resistance test is immersed in a 95% ethanol solution for 15 minutes, and then placed in a neutral salt spray condition. The time required for white erosion or blistering; the yellowing resistance test is at 300°C, in the atmospheric environment, after 15 minutes, and then placed under neutral salt spray conditions, white erosion or blistering phenomenon occurs time required). At the same time, the adhesion of the conversion coating was tested (the adhesion test method is to draw a grid on the surface of the coating, the spacing between the teeth is 2 mm, and the adhesive tape with an adhesive force greater than 10N/25mm is attached to the grid, press and Remove the air, and then quickly pull up the tape at an angle perpendicular to the coating surface, and visually inspect the coating surface.Grading representation: Grade 0, the cutting edge is completely smooth, and no strips fall off; Grade 1, there is a little coating at the intersection of the incision Falling off, but the affected cross-cut area cannot be significantly greater than 5%; Grade 2, the coating has fallen off at the intersection of the incision and/or along the edge of the incision, and the affected cross-cut area is significantly greater than 5%, but not significantly greater than 15%. ), the measured data are as follows:
实施例3Example 3
一种适用于辊筒涂覆工艺的无铬转换剂，所述转换剂中各组分的含量如下：磷酸12%，硝酸4%，氟钛酸钠3%，氟锆酸钠3%，酒石酸6%，碳酸锆6.5%，成膜助剂3.5%，增稠剂0.35%，其余的为去离子水。A chromium-free conversion agent suitable for roller coating process, the content of each component in the conversion agent is as follows: phosphoric acid 12%, nitric acid 4%, sodium fluorotitanate 3%, sodium fluorozirconate 3%, tartaric acid 6%, zirconium carbonate 6.5%, coalescent 3.5%, thickener 0.35%, and the rest is deionized water.
上述成膜助剂为：十二碳醇酯3%，丙二醇乙醚0.5%；The above film-forming aids are: dodecyl alcohol ester 3%, propylene glycol ether 0.5%;
上述的增稠剂为：聚丙烯酸钠0.15%，聚乙烯醇0.15%。The above-mentioned thickeners are: sodium polyacrylate 0.15%, polyvinyl alcohol 0.15%.
上述转换剂的制备方法包括下述步骤：The preparation method of above-mentioned conversion agent comprises the steps:
（1）按原料的配方组成，磷酸、硝酸、氟钛酸钠、氟锆酸钠、去离子水，充分搅拌制得溶液A；(1) According to the formula of the raw materials, phosphoric acid, nitric acid, sodium fluorotitanate, sodium fluorozirconate, and deionized water are fully stirred to prepare solution A;
（2）按原料的配方组成，酒石酸、碳酸锆、十二碳醇酯、丙二醇乙醚、聚丙烯酸钠、聚乙烯醇等溶于适量去离子水中，充分搅拌待其溶解制得溶液B；(2) According to the formulation of the raw materials, tartaric acid, zirconium carbonate, dodecyl alcohol ester, propylene glycol ethyl ether, sodium polyacrylate, polyvinyl alcohol, etc. are dissolved in an appropriate amount of deionized water, and fully stirred until they are dissolved to obtain solution B;
（3）将溶液B缓慢的加入溶液A中，充分搅拌制得无铬转换剂。(3) Slowly add solution B to solution A, and stir well to obtain a chromium-free conversion agent.
本实施例制得的转换剂对HT100钢表面进行辊筒涂覆工艺处理（10 m/min），处理后转换涂层致密、平整、色泽均匀，对其进行防腐耐磨实验（耐中性盐雾实验为4%的氯化钠氛围下，出现白蚀或起泡的现象所需时间；耐溶剂实验为在95%乙醇溶液中浸泡15分钟后，再置于中性盐雾条件下，出现白蚀或起泡的现象所需时间；耐黄变实验为在300°C下，大气环境下，保持15分钟后，再置于中性盐雾条件下，出现白蚀或起泡的现象所需时间）。同时，对转换涂层的附着力进行测试（附着力测试方法为在涂层表面划格，刀齿间距为2毫米，将粘着力大于10N/25mm的胶带粘附在划格上，压紧并排除空气，再以垂直涂层表面的角度快速拉起胶带，目视检测涂层表面。分级表示：0级，切割边缘完全平滑，无一格脱落；1级，在切口交叉处有少许涂层脱落，但交叉切割面积受影响不能明显大于5%；2级，在切口交叉处和/或沿切口边缘有涂层脱落，受影响的交叉切割面积明显大于5%，但不能明显大于15%。），测得数据如下：The conversion agent prepared in this example is subjected to roller coating process treatment (10 m/min) on the surface of HT100 steel. After the treatment, the conversion coating is dense, smooth and uniform in color, and the anti-corrosion and wear-resisting test (neutral salt resistance) is carried out on it. The fog test is the time required for white corrosion or blistering in a 4% sodium chloride atmosphere; the solvent resistance test is immersed in a 95% ethanol solution for 15 minutes, and then placed in a neutral salt spray condition. The time required for the phenomenon of white erosion or blistering; the yellowing resistance test is at 300 ° C, in the atmospheric environment, after 15 minutes, and then placed under neutral salt spray conditions, the phenomenon of white erosion or blistering occurs. takes time). At the same time, the adhesion of the conversion coating was tested (the adhesion test method is to draw a grid on the surface of the coating, the spacing between the teeth is 2 mm, and the adhesive tape with an adhesive force greater than 10N/25mm is attached to the grid, press and Remove the air, and then quickly pull up the tape at an angle perpendicular to the coating surface, and visually inspect the coating surface.Grading representation: Grade 0, the cutting edge is completely smooth, and no strips fall off; Grade 1, there is a little coating at the intersection of the incision Falling off, but the affected cross-cut area cannot be significantly greater than 5%; Grade 2, the coating has fallen off at the intersection of the incision and/or along the edge of the incision, and the affected cross-cut area is significantly greater than 5%, but not significantly greater than 15%. ), the measured data are as follows:
上述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明配方及制备工艺可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The above are only preferred embodiments of the present invention, and are not intended to limit the present invention. For those skilled in the art, various modifications and changes can be made to the formulation and preparation process of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5468734A (en) * | 1977-11-11 | 1979-06-02 | Nippon Packaging Kk | Surface treatment of tin plated steel plate and can |
| EP1612294A1 (en) * | 2004-07-02 | 2006-01-04 | Italtecno S.R.L. | Bath and associated method for the conversion coating of articles made of aluminium and alloys thereof |
| CN101967633A (en) * | 2010-09-16 | 2011-02-09 | 华南理工大学 | Treatment liquid and method or preparing Ti/Zr-containing yellow passive film on surface of aluminum alloy |
| CN103194742A (en) * | 2013-04-28 | 2013-07-10 | 马鞍山金泉工业介质科技有限公司 | Inorganic-resin black coating agent applied to metal surface treatment, as well as preparation method and application of black coating agent |
| CN103498137A (en) * | 2013-09-24 | 2014-01-08 | 华南理工大学 | A treatment liquid and treatment method for preparing zirconium-based colored conversion film on the surface of magnesium alloy |
| CN103668154A (en) * | 2013-12-13 | 2014-03-26 | 三达奥克化学股份有限公司 | Chromium-free vitrified film forming agent for aluminum alloy profiles and plate workpieces before spraying |
| CN104178757A (en) * | 2014-08-08 | 2014-12-03 | 东北大学 | Chromium-free composite passivator for hot-dip galvanized steel sheet and preparation and application methods of composite passivator |
| CN106702362A (en) * | 2016-11-27 | 2017-05-24 | 湖南金裕化工有限公司 | Fingerprint-resistant treating agent, preparing method and application thereof |
| CN107475704A (en) * | 2017-07-11 | 2017-12-15 | 沈阳瑞驰表面技术有限公司 | Metal surface silane treatment agent and preparation method thereof |
| CN107653449A (en) * | 2017-10-12 | 2018-02-02 | 佛山市顺德区美硕金属表面技术有限公司 | Chromium-free deactivation composition, chrome-free tanning agent and preparation method thereof |
| CN108070852A (en) * | 2016-11-18 | 2018-05-25 | 中国科学院金属研究所 | One kind is applied to 2024 aluminum alloy surface titanium zirconium conversion fluids and its application method |
-
2020
- 2020-09-25 CN CN202011023970.5A patent/CN112126920A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5468734A (en) * | 1977-11-11 | 1979-06-02 | Nippon Packaging Kk | Surface treatment of tin plated steel plate and can |
| EP1612294A1 (en) * | 2004-07-02 | 2006-01-04 | Italtecno S.R.L. | Bath and associated method for the conversion coating of articles made of aluminium and alloys thereof |
| CN101967633A (en) * | 2010-09-16 | 2011-02-09 | 华南理工大学 | Treatment liquid and method or preparing Ti/Zr-containing yellow passive film on surface of aluminum alloy |
| CN103194742A (en) * | 2013-04-28 | 2013-07-10 | 马鞍山金泉工业介质科技有限公司 | Inorganic-resin black coating agent applied to metal surface treatment, as well as preparation method and application of black coating agent |
| CN103498137A (en) * | 2013-09-24 | 2014-01-08 | 华南理工大学 | A treatment liquid and treatment method for preparing zirconium-based colored conversion film on the surface of magnesium alloy |
| CN103668154A (en) * | 2013-12-13 | 2014-03-26 | 三达奥克化学股份有限公司 | Chromium-free vitrified film forming agent for aluminum alloy profiles and plate workpieces before spraying |
| CN104178757A (en) * | 2014-08-08 | 2014-12-03 | 东北大学 | Chromium-free composite passivator for hot-dip galvanized steel sheet and preparation and application methods of composite passivator |
| CN108070852A (en) * | 2016-11-18 | 2018-05-25 | 中国科学院金属研究所 | One kind is applied to 2024 aluminum alloy surface titanium zirconium conversion fluids and its application method |
| CN106702362A (en) * | 2016-11-27 | 2017-05-24 | 湖南金裕化工有限公司 | Fingerprint-resistant treating agent, preparing method and application thereof |
| CN107475704A (en) * | 2017-07-11 | 2017-12-15 | 沈阳瑞驰表面技术有限公司 | Metal surface silane treatment agent and preparation method thereof |
| CN107653449A (en) * | 2017-10-12 | 2018-02-02 | 佛山市顺德区美硕金属表面技术有限公司 | Chromium-free deactivation composition, chrome-free tanning agent and preparation method thereof |
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