CN101029386A - Triple cationic phosphorizing fluid containing calcium, zinc and manganese for steel plate and zinc-coated plate treatment - Google Patents
Triple cationic phosphorizing fluid containing calcium, zinc and manganese for steel plate and zinc-coated plate treatment Download PDFInfo
- Publication number
- CN101029386A CN101029386A CN 200710034699 CN200710034699A CN101029386A CN 101029386 A CN101029386 A CN 101029386A CN 200710034699 CN200710034699 CN 200710034699 CN 200710034699 A CN200710034699 A CN 200710034699A CN 101029386 A CN101029386 A CN 101029386A
- Authority
- CN
- China
- Prior art keywords
- zinc
- manganese
- phosphating
- calcium
- nitrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000011282 treatment Methods 0.000 title claims abstract description 23
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 21
- 239000010959 steel Substances 0.000 title claims abstract description 21
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 16
- 239000011701 zinc Substances 0.000 title description 31
- 239000011572 manganese Substances 0.000 title description 21
- 239000011575 calcium Substances 0.000 title description 15
- 229910052725 zinc Inorganic materials 0.000 title description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title 1
- 229910052791 calcium Inorganic materials 0.000 title 1
- 239000012530 fluid Substances 0.000 title 1
- 229910052748 manganese Inorganic materials 0.000 title 1
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 8
- 239000010452 phosphate Substances 0.000 claims abstract description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 8
- 150000003751 zinc Chemical class 0.000 claims abstract description 7
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 6
- 150000002696 manganese Chemical class 0.000 claims abstract description 6
- QCMLJYVKYRRZQH-UHFFFAOYSA-N [Mn].[Ca].[Zn] Chemical compound [Mn].[Ca].[Zn] QCMLJYVKYRRZQH-UHFFFAOYSA-N 0.000 claims abstract description 5
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 16
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 claims description 6
- 229940062672 calcium dihydrogen phosphate Drugs 0.000 claims description 6
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 6
- 235000019691 monocalcium phosphate Nutrition 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- NAAXGLXYRDSIRS-UHFFFAOYSA-L dihydrogen phosphate;manganese(2+) Chemical compound [Mn+2].OP(O)([O-])=O.OP(O)([O-])=O NAAXGLXYRDSIRS-UHFFFAOYSA-L 0.000 claims description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 4
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- 239000004317 sodium nitrate Substances 0.000 claims description 4
- 235000010344 sodium nitrate Nutrition 0.000 claims description 4
- MFXMOUUKFMDYLM-UHFFFAOYSA-L zinc;dihydrogen phosphate Chemical compound [Zn+2].OP(O)([O-])=O.OP(O)([O-])=O MFXMOUUKFMDYLM-UHFFFAOYSA-L 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 2
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 229960001841 potassium permanganate Drugs 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- LJRGBERXYNQPJI-UHFFFAOYSA-M sodium;3-nitrobenzenesulfonate Chemical compound [Na+].[O-][N+](=O)C1=CC=CC(S([O-])(=O)=O)=C1 LJRGBERXYNQPJI-UHFFFAOYSA-M 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 20
- 239000011248 coating agent Substances 0.000 abstract description 18
- 238000000034 method Methods 0.000 abstract description 17
- 239000003513 alkali Substances 0.000 abstract description 10
- 239000013078 crystal Substances 0.000 abstract description 4
- 238000001962 electrophoresis Methods 0.000 abstract description 4
- 238000002161 passivation Methods 0.000 abstract description 4
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 description 19
- 238000005260 corrosion Methods 0.000 description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 229910001335 Galvanized steel Inorganic materials 0.000 description 12
- 239000008397 galvanized steel Substances 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000004381 surface treatment Methods 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000010422 painting Methods 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- ANFIEGWCRSNVFS-UHFFFAOYSA-N [Na].OCl(=O)=O Chemical compound [Na].OCl(=O)=O ANFIEGWCRSNVFS-UHFFFAOYSA-N 0.000 description 1
- JBMRMLLHFBHFDV-UHFFFAOYSA-N [Ni].[Mn].[Zn] Chemical compound [Ni].[Mn].[Zn] JBMRMLLHFBHFDV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000003666 anti-fingerprint Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 108010025899 gelatin film Proteins 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Landscapes
- Chemical Treatment Of Metals (AREA)
Abstract
本发明为用于钢板及镀锌板处理的含钙锌锰三元阳离子磷化液，它由在水中加入以下组分组成，且所述各组分的用量为每升磷化液中的加入量：钙盐5g～60g、锰盐0.5g～10g、锌盐2g～35g、磷酸盐5g～20g、硝酸盐5g－30g、促进剂0.5g～10g；该磷化液及经其处理的钢板以及镀锌板的磷化膜具有：磷化液及磷化膜中不含有对环境有污染的Cr6+及重金属离子Ni2+；膜层耐碱性好，适合与阴极电泳配合使用；膜层晶粒细致均匀，与涂膜有良好的结合力；工艺简单，无需表调及后续钝化处理，成本低，利于流水线操作。
The present invention is a calcium-zinc-manganese ternary cationic phosphating solution used for the treatment of steel plates and galvanized sheets. Quantity: calcium salt 5g~60g, manganese salt 0.5g~10g, zinc salt 2g~35g, phosphate 5g~20g, nitrate 5g~30g, accelerator 0.5g~10g; the phosphating solution and the steel plate treated by it And the phosphating film of galvanized sheet has: the phosphating solution and the phosphating film do not contain Cr 6+ and heavy metal ions Ni 2+ that pollute the environment; the film layer has good alkali resistance and is suitable for use in conjunction with cathodic electrophoresis; The crystal grains of the layer are fine and uniform, and have good bonding force with the coating film; the process is simple, no surface adjustment and subsequent passivation treatment are required, the cost is low, and it is convenient for assembly line operation.
Description
技术领域technical field
本发明属于化工领域，涉及一种用于镀锌板处理的含Ca2+、Zn2+、Mn2+三元阳离子磷化液。The invention belongs to the field of chemical industry and relates to a phosphating solution containing Ca 2+ , Zn 2+ , and Mn 2+ ternary cations for galvanized sheet treatment.
背景技术Background technique
汽车工业发展迅速，对环境友好的钢板及镀锌板表面处理技术的需求及要求提高。锌电位比铁电位负，工业上常采用电镀及热浸的方式将锌沉积在钢铁表面，通过锌的牺牲阳极保护基材。由于镀锌钢板的冲压加工性、可焊性、对漆膜附着性及变形前、后的耐腐蚀性，大大延长了钢材的使用寿命，镀锌钢板已广泛应用于汽车，家电，化工，航空等领域，特别是电镀锌钢板在汽车工业中得到了广泛的应用。With the rapid development of the automobile industry, the demand and requirements for the surface treatment technology of environmentally friendly steel sheets and galvanized sheets have increased. The potential of zinc is negative than that of iron. In industry, electroplating and hot dipping are often used to deposit zinc on the surface of steel, and the substrate is protected by a sacrificial anode of zinc. Due to the stamping processability, weldability, adhesion to paint film and corrosion resistance before and after deformation of galvanized steel sheet, the service life of steel is greatly extended. Galvanized steel sheet has been widely used in automobiles, home appliances, chemical industry, aviation And other fields, especially electro-galvanized steel sheet has been widely used in the automotive industry.
但镀锌层在温热环境下易发生腐蚀，在表面形成白色的腐蚀产物，影响镀锌的外观及耐蚀性。以前常采用高浓度或中等浓度的铬酸在镀锌板表面进行钝化处理。由于Cr(VI)有自我修复功能，形成的铬/基体金属混合膜层耐蚀性好，且铬酸盐钝化成本较低，工艺简单，在工业上得到广泛应用。但六价铬的毒性对环境和人体都有严重危害，铬酸盐的使用已受到严格的限制。因此迫切需要开发镀锌板上环境友好的无铬表面处理。目前镀锌板的无铬处理方法较多，如日本研究的含钴，铈等离子的转化膜(JP2004263252-A)；郭铁波等提出的含钼酸盐的硅凝胶膜及锆酸膜(环保型无铬含锆电镀锌耐指纹钢板的表面处理方法(CN1763257A)。However, the galvanized layer is prone to corrosion in a warm environment, and white corrosion products are formed on the surface, which affects the appearance and corrosion resistance of galvanized. In the past, high-concentration or medium-concentration chromic acid was often used for passivation treatment on the surface of galvanized sheets. Due to the self-healing function of Cr(VI), the chromium/matrix metal mixed film formed has good corrosion resistance, and the cost of chromate passivation is low, and the process is simple, so it is widely used in industry. However, the toxicity of hexavalent chromium has serious harm to the environment and human body, and the use of chromate has been strictly restricted. Therefore, there is an urgent need to develop environmentally friendly chrome-free surface treatments for galvanized panels. At present, there are many chromium-free treatment methods for galvanized sheets, such as the conversion film containing cobalt and cerium plasma studied in Japan (JP2004263252-A); the silicon gel film containing molybdate and zirconate film (environmental protection type) Surface treatment method of chrome-free zirconium-containing electro-galvanized anti-fingerprint steel plate (CN1763257A).
钢板及镀锌钢板涂装前多采用磷化工艺以提高涂层对基底的附着力及涂膜耐腐蚀性能，在汽车及摩托车涂装线上电泳涂装前广泛采用的处理方法是含锌镍锰离子(Zn2+、Ni2+、Mn2+的)的三元阳离子磷化工艺，有时还加上钝化处理，如KIMHI发明了含50～120ppm的Ni2+的磷化膜(专利号KR2005049905-A)。由于Ni2+属于重金属离子，在环境保护法规日益严格要求的今天，Cr6+及Ni2+的排放已经受到限制，因此研发新的无铬无镍的金属表面处理剂如新的磷化液及其制备是非常重要的。The phosphating process is often used before coating steel sheets and galvanized steel sheets to improve the adhesion of the coating to the substrate and the corrosion resistance of the coating film. The treatment method widely used before electrophoretic coating on automobile and motorcycle coating lines is to contain zinc Nickel-manganese ions (Zn 2+ , Ni 2+ , Mn 2+ ) ternary cationic phosphating process, sometimes with passivation treatment, such as KIMHI invented a phosphating film containing 50-120ppm Ni 2+ ( Patent No. KR2005049905-A). Since Ni 2+ is a heavy metal ion, the discharge of Cr 6+ and Ni 2+ has been restricted in today's increasingly stringent environmental protection regulations. Therefore, a new chromium-free and nickel-free metal surface treatment agent such as a new phosphating solution has been developed. And its preparation is very important.
发明内容Contents of the invention
本发明的目的在于，针对现有技术存在的不足，提出一种既可用于钢板又可用于镀锌板处理的含钙锌锰三元阳离子磷化液，以取代现有的含镍的三元磷化体系，满足越来越严格的环境保护要求，同时满足汽车涂装前处理对磷化膜耐碱性高和结晶细致的性能要求；本发明磷化液用于所述转化膜处理工艺中，具有工艺简单、磷化膜形成快速，结晶细致且无需表调的特点，膜层耐碱性高、与电泳涂层配套性好；既可用于普通钢铁前处理，又可用于镀锌板处理，特别适合汽车涂装流水线上电镀锌板的磷化处理。The purpose of the present invention is to propose a calcium-zinc-manganese ternary cationic phosphating solution that can be used for both steel plate and galvanized sheet treatment to replace the existing nickel-containing ternary phosphating solution. The phosphating system meets increasingly stringent environmental protection requirements, and at the same time satisfies the performance requirements of high alkali resistance and fine crystallization of the phosphating film in the pre-treatment of automobile painting; the phosphating solution of the present invention is used in the conversion film treatment process , has the characteristics of simple process, fast formation of phosphating film, fine crystallization and no need for surface adjustment, high alkali resistance of the film layer, and good compatibility with electrophoretic coating; it can be used for pretreatment of ordinary steel and galvanized sheet treatment , especially suitable for phosphating treatment of electro-galvanized sheets on automobile painting lines.
本发明的技术方案是，所述用于电镀锌板处理的含钙锌锰三元阳离子磷化液由在水中加入以下组分组成，且所述各组分的用量为每升磷化液中的加入量：The technical scheme of the present invention is that the calcium-zinc-manganese-containing ternary cationic phosphating solution used for the treatment of electro-galvanized sheets is composed of adding the following components in water, and the consumption of each component is Amount added:
钙盐 5g～60g；Calcium salt 5g~60g;
锰盐 0.5g～10g；Manganese salt 0.5g～10g;
锌盐 2g～35g；Zinc salt 2g～35g;
磷酸或磷酸盐 5g～20g；Phosphoric acid or phosphate 5g~20g;
硝酸盐 5g～30g；Nitrate 5g～30g;
促进剂 0.5g～10g；Accelerator 0.5g～10g;
其中：in:
所述钙盐为氧化钙或硝酸钙、磷酸二氢钙中的一种或一种以上；The calcium salt is one or more of calcium oxide, calcium nitrate, and calcium dihydrogen phosphate;
所述锰盐为醋酸锰或高锰酸钾、硫酸锰、磷酸二氢锰(马日夫盐)、二氧化锰中的一种或一种以上；The manganese salt is one or more of manganese acetate or potassium permanganate, manganese sulfate, manganese dihydrogen phosphate (Mariv salt), manganese dioxide;
所述锌盐为磷酸二氢锌或氧化锌、硝酸锌中的一种或一种以上；The zinc salt is one or more of zinc dihydrogen phosphate, zinc oxide, and zinc nitrate;
所述磷酸盐为磷酸二氢锌或磷酸二氢钙、磷酸二氢锰中的一种或一种以上；The phosphate is one or more of zinc dihydrogen phosphate, calcium dihydrogen phosphate, and manganese dihydrogen phosphate;
所述硝酸盐为硝酸锌或硝酸钙、硝酸锰中的一种或一种以上；The nitrate is one or more of zinc nitrate, calcium nitrate, and manganese nitrate;
所述促进剂为硝酸钠或硝酸钙、氯酸钠、间硝基苯磺酸钠、柠檬酸、磷酸二氢铵、六次甲级四胺、十二烷基苯磺酸钠中的一种或一种以上。The accelerator is one of sodium nitrate or calcium nitrate, sodium chlorate, sodium m-nitrobenzene sulfonate, citric acid, ammonium dihydrogen phosphate, hexamethylenetetramine, sodium dodecylbenzene sulfonate or more than one.
本发明所述磷化液的制备方法是：在已知体积的容器中，首先将磷酸盐(或磷酸)在水中溶解，依次加入硝酸盐、钙盐、锰盐、锌盐，搅拌均匀；然后加入事先用水溶解了的添加剂，最后加水到指定刻度，即成。The preparation method of phosphating solution of the present invention is: in the container of known volume, at first phosphate (or phosphoric acid) is dissolved in water, add nitrate, calcium salt, manganese salt, zinc salt successively, stir; Then Add the additives dissolved in water in advance, and finally add water to the specified scale, and it is ready.
应用本发明所述磷化液对钢板或镀锌钢板表面处理的工艺流程如下：Apply the phosphating solution of the present invention to the technological process of steel plate or galvanized steel plate surface treatment as follows:
(1)将钢板或镀锌板用低碱度清洗液浸渍或喷射处理，除去表面污物；(1) Dip or spray the steel plate or galvanized sheet with a low-alkalinity cleaning solution to remove surface dirt;
(2)自来水清洗；(2) washing with tap water;
(3)采用上述磷化液对镀锌板进行浸渍或喷射处理，时间为1～10min，控制温度为15～80℃，pH在2～4的范围内；(3) Use the above phosphating solution to dip or spray the galvanized sheet for 1 to 10 minutes, control the temperature to 15 to 80°C, and pH within the range of 2 to 4;
(4)自来水清洗；(4) washing with tap water;
(5)去离子水清洗；(5) cleaning with deionized water;
(6)吹干或直接进入电泳处理。(6) Blow dry or directly enter electrophoresis treatment.
用本发明含Ca2+、Zn2+、Mn2+的三元阳离子的磷化液进行磷化处理时，Ca2+、Mn2+会取代部分Zn2+成膜，可能发生的反应如下：When using the phosphating solution of the present invention containing ternary cations of Ca 2+ , Zn 2+ , and Mn 2+ for phosphating treatment, Ca 2+ , Mn 2+ will replace part of Zn 2+ to form a film, and the possible reactions are as follows :
3Zn2++2PO4 3-+4H2O→Zn3(PO4)2·4H2O3Zn 2+ +2PO 4 3- +4H 2 O→Zn 3 (PO 4 ) 2 4H 2 O
2Zn2++Ca2++2PO4 3-+2H2O→Zn2Ca(PO4)2·2H2O2Zn 2+ +Ca 2+ +2PO 4 3- +2H 2 O→Zn 2 Ca(PO 4 ) 2 2H 2 O
2Zn2++Mn2++2PO4 3-+4H2O→Zn2Mn(PO4)2·4H2O2Zn 2+ +Mn 2+ +2PO 4 3- +4H 2 O→Zn 2 Mn(PO 4 ) 2 4H 2 O
所形成的含Zn2Ca(PO4)2·2H2O和Zn2Mn(PO4)2·4H2O结构的磷化膜较Zn3(PO4)2结构的磷化膜具有更好的耐碱性，可以阻止在电泳过程中由于在钢板或镀锌板界面较高的pH值而导致的磷化膜溶解，有效地提高了磷化膜的耐腐蚀性及和涂层配套性。The phosphating film formed with Zn 2 Ca(PO 4 ) 2 ·2H 2 O and Zn 2 Mn(PO 4 ) 2 ·4H 2 O has better properties than that of Zn 3 (PO 4 ) 2 Excellent alkali resistance, which can prevent the dissolution of the phosphating film caused by the high pH value at the interface of the steel plate or galvanized sheet during the electrophoresis process, effectively improving the corrosion resistance of the phosphating film and the compatibility with the coating.
应用本发明磷化液制得镀锌板表面磷酸盐转化膜性能表征如下：Apply the phosphating solution of the present invention to make the performance characterization of the phosphate conversion film on the surface of the galvanized sheet as follows:
(1)磷化膜结构由日本PHILIPS公司的XL-30扫描电子显微镜(SEM)电子显微镜观察。(1) Phosphate film structure was observed by XL-30 scanning electron microscope (SEM) electron microscope of Japan PHILIPS Company.
(2)磷化膜耐碱性由减重法测定。将2×5×7cm的电镀锌板放入60℃的三元磷化液中磷化10min，取出，水冼后用电吹风吹干，用电子天平称量质量W1，然后放入25℃的0.1mol/L的NaOH溶液中，浸入一定时间后，水冼后吹干，再称量质量W2，W1-W2是失重。作为比较的磷化液为a，普通锌系磷化液b，汽车用含Zn2+、Ni2+、Mn2+三元阳离子磷化液，及本发明的含Ca2+、Zn2+、Mn2+的三元阳离子磷化液c。(2) The alkali resistance of the phosphating film is determined by the weight loss method. Put a 2×5×7cm electro-galvanized sheet into the ternary phosphating solution at 60°C for 10 minutes, take it out, wash it with water and dry it with a hair dryer, weigh the mass W 1 with an electronic balance, and then place it at 25°C After immersing in 0.1mol/L NaOH solution for a certain period of time, wash with water and blow dry, then weigh the mass W 2 , W 1 -W 2 are weight loss. Phosphating solutions for comparison are a, ordinary zinc-based phosphating solutions b, phosphating solutions containing Zn 2+ , Ni 2+ , and Mn 2+ ternary cations for automobiles, and the phosphating solutions containing Ca 2+ , Zn 2+ of the present invention. , Mn 2+ ternary cationic phosphating solution c.
(3)电镀锌板磷化膜与电泳涂料配套后涂膜耐腐蚀性能测试：按照GM9511P方法测试，对比本发明的Ca2+、Zn2+、Mn2+的三元阳离子磷化膜(a)和比Ni2+、Zn2+、Mn2+(b)的耐腐蚀性能及与电泳涂料的配套性。在涂膜表面用刀片划线，划到基底，观察11循环腐蚀试验后划线处腐蚀蔓延的宽度。(3) Corrosion resistance test of the coating film after the phosphating film of the electro-galvanized sheet is matched with the electrophoretic coating: test according to the GM9511P method, and compare the ternary cationic phosphating film (a ) and Ni 2+ , Zn 2+ , Mn 2+ (b) corrosion resistance and compatibility with electrophoretic coatings. Use a blade to draw a line on the surface of the coating film, draw it to the substrate, and observe the width of the corrosion spread at the line after the 11-cycle corrosion test.
结果为：The result is:
(1)本发明的磷化膜结构及普通三元阳离子磷化膜结构比较：如图1和图2所示，本发明的磷化液所形成的磷化膜晶粒呈球粒状，细小而匀均，粒径约为2～3um，与普通三元磷化膜的结晶大小类似，而普通三元磷化膜结晶呈叶片状。(1) phosphating film structure of the present invention and common ternary cationic phosphating film structure comparison: as shown in Fig. 1 and Fig. 2, the phosphating film crystal grain that the phosphating solution of the present invention forms is spherical shape, small and large Uniform, the particle size is about 2 ~ 3um, which is similar to the crystal size of ordinary ternary phosphating film, and the crystallization of ordinary ternary phosphating film is leaf-shaped.
(2)本发明的磷化膜与普通锌系磷化膜及普通三元磷化膜耐碱性测试结果：如图3所示，本发明的磷化膜具有更高的耐碱性，这与其磷化膜结构中Zn2Ca(PO4)2·2H2O和Zn2Mn(PO4)2·4H2O结晶存在有关。(2) phosphating film of the present invention and common zinc series phosphating film and common ternary phosphating film alkali resistance test result: as shown in Figure 3, phosphating film of the present invention has higher alkali resistance, this It is related to the presence of Zn 2 Ca(PO 4 ) 2 ·2H 2 O and Zn 2 Mn(PO 4 ) 2 ·4H 2 O crystals in the phosphating film structure.
(3)本发明磷化膜与电泳涂料配套后涂膜耐腐蚀性能及与普通三元磷化膜与电泳涂料配套后耐腐蚀性能的比较：从图4可以看出，两种不同磷化膜阴极电泳后，在5％NaCl溶液中经过11循环腐蚀实验，可明显而看出镀锌板上Ca2+、Zn2+、Mn2+的三元阳离子磷化膜(a)较Ni2+、Zn2+、Mn2+三元磷化膜(b)腐蚀蔓延小，表明本发明的Ca2+、Zn2+、Mn2+的三元阳离子磷化膜具有良好的附着力、耐蚀性及与电泳涂料的配套性。(3) comparison of the corrosion resistance of the coating film after the phosphating film of the present invention is matched with the electrophoretic coating and the corrosion resistance after matching with the common ternary phosphating film and the electrophoretic coating: as can be seen from Fig. 4, two kinds of different phosphating films After cathodic electrophoresis, after 11 cycles of corrosion experiments in 5% NaCl solution, it can be clearly seen that the ternary cationic phosphating film (a) of Ca 2+ , Zn 2+ , and Mn 2+ on the galvanized plate is better than that of Ni 2+ , Zn 2+ , Mn 2+ ternary phosphating film (b) corrosion spread is small, indicating that the ternary cationic phosphating film of Ca 2+ , Zn 2+ , Mn 2+ of the present invention has good adhesion, corrosion resistance Sex and compatibility with electrophoretic coatings.
由以上可知，本发明为一种用于钢板及镀锌钢板处理的含钙锌锰三元阳离子磷化液，可在钢板和镀锌钢板表面实现无铬、无镍磷化处理工艺，可取代现有的含镍的三元磷化体系，满足越来越严格的环境保护要求，同时满足汽车涂装前处理对磷化膜耐碱性高和结晶细致的性能要求；本发明磷化液用于所述转化膜处理工艺中，具有工艺简单、磷化膜形成快速，结晶细致、无需表调的特点，膜层耐碱性高、与电泳涂层配套性好，既可用于普通钢板处理，又可用于镀锌钢板，特别适合汽车涂装流水线上电镀锌板的磷化处理。From the above, it can be seen that the present invention is a calcium-zinc-manganese ternary cationic phosphating solution for the treatment of steel sheets and galvanized steel sheets, which can realize chromium-free and nickel-free phosphating treatment processes on the surface of steel sheets and galvanized steel sheets. The existing nickel-containing ternary phosphating system meets more and more stringent environmental protection requirements, and at the same time satisfies the performance requirements of high alkali resistance and fine crystallization of the phosphating film in the pre-treatment of automobile painting; the phosphating solution of the present invention is used In the conversion coating treatment process, it has the characteristics of simple process, fast formation of phosphating film, fine crystallization, and no need for surface adjustment. The film layer has high alkali resistance and good compatibility with electrophoretic coating. It can be used for ordinary steel plate treatment, It can also be used for galvanized steel sheets, especially suitable for phosphating treatment of electro-galvanized sheets on automobile painting lines.
附图说明Description of drawings
图1是钢板在本发明的Ca2+、Zn2+、Mn2+的三元阳离子磷化液处理后的磷化膜的SEM图(2000倍)；Fig. 1 is the SEM picture (2000 times) of the phosphating film of steel plate after the ternary cationic phosphating solution of the present invention handles Ca 2+ , Zn 2+ , Mn 2+ ;
图2是电镀锌钢板在本发明的Ca2+、Zn2+、Mn2+的三元阳离子磷化液处理后的磷化膜的SEM图(2000倍)；Fig. 2 is the SEM figure (2000 times) of the phosphating film of electrogalvanized steel plate after the ternary cationic phosphating solution of the present invention handles Ca 2+ , Zn 2+ , Mn 2+ ;
图3是：磷化膜耐碱性失重试验结果。(a)普通锌系磷化液，(b)汽车用含、Zn2+、Ni2+、Mn2+三元阳离子磷化液，及(c)本发明含Ca2+、Zn2+、Mn2+的三元阳离子磷化液，在25℃的0.1mol/L的NaOH溶液中浸泡2hr后膜层失重比较；Figure 3 is: the results of the alkali resistance weight loss test of the phosphating film. (a) ordinary zinc-based phosphating solution, (b) phosphating solution containing Zn 2+ , Ni 2+ , Mn 2+ ternary cations for automobiles, and (c) the present invention containing Ca 2+ , Zn 2+ , Mn 2+ ternary cationic phosphating solution, after soaking in 0.1mol/L NaOH solution at 25°C for 2 hours, the weight loss of the film layer is compared;
图4是按GM9511P标准，电镀锌板上磷化膜与电泳涂料配套后经过11循环腐蚀试验后涂膜划线处腐蚀蔓延宽度。其中：(a)Ca2+、Zn2+、Mn2+的三元阳离子磷化膜，(b)Ni2+、Zn2+、Mn2+三元磷化膜；采用本发明磷化液处理的镀锌钢板涂膜具有较小的腐蚀蔓延宽度。Figure 4 shows the width of corrosion spread at the scribe line of the coating film after 11 cycles of corrosion tests after the phosphating film on the electro-galvanized plate is matched with the electrophoretic coating according to the GM9511P standard. Among them: (a) ternary cationic phosphating film of Ca 2+ , Zn 2+ , Mn 2+ , (b) ternary phosphating film of Ni 2+ , Zn 2+ , Mn 2+ ; using the phosphating solution of the present invention The treated galvanized steel coating has a smaller corrosion propagation width.
具体实施方式Detailed ways
实施例1：磷化液组成为，水为溶剂，每升磷化液中加入硝酸钙5g，醋酸锰10g，硝酸锌2g，磷酸或磷酸二氢钙20g，硝酸钠5g，促进剂柠檬酸10g；用于电镀锌钢板表面处理时，pH值为2～4，温度40～60℃，处理时间为2～10分钟，即可在镀锌钢板上形成均匀细致的磷化膜。Embodiment 1: the phosphating solution is composed of, water is the solvent, 5 g of calcium nitrate, 10 g of manganese acetate, 2 g of zinc nitrate, 20 g of phosphoric acid or calcium dihydrogen phosphate, 5 g of sodium nitrate, and 10 g of accelerator citric acid are added in every liter of the phosphating solution ; When used for the surface treatment of electro-galvanized steel sheets, the pH value is 2-4, the temperature is 40-60°C, and the treatment time is 2-10 minutes, and a uniform and fine phosphating film can be formed on the galvanized steel sheets.
实施例2：磷化液组成为，水为溶剂，每升磷化液中加入硝酸钙60g，醋酸锰0.5g，硝酸锌35g，磷酸或磷酸二氢钙5g，硝酸钠30g，促进剂氯酸钠0.5g；用于电镀锌钢板表面处理时，pH值为2～4，温度40～60℃，样品为钢板，处理时间为3～10分钟，即可在钢板表面形成匀均的磷化膜。Embodiment 2: the phosphating solution is composed of, water is a solvent, calcium nitrate 60g is added in every liter of phosphating solution, manganese acetate 0.5g, zinc nitrate 35g, phosphoric acid or calcium dihydrogen phosphate 5g, sodium nitrate 30g, accelerator chloric acid Sodium 0.5g; when used for the surface treatment of electro-galvanized steel sheets, the pH value is 2-4, the temperature is 40-60°C, the sample is a steel plate, and the treatment time is 3-10 minutes, and a uniform phosphating film can be formed on the surface of the steel plate .
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100346993A CN100471995C (en) | 2007-04-09 | 2007-04-09 | Calcium-zinc-manganese ternary cationic phosphating solution for steel plate and galvanized plate treatment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100346993A CN100471995C (en) | 2007-04-09 | 2007-04-09 | Calcium-zinc-manganese ternary cationic phosphating solution for steel plate and galvanized plate treatment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101029386A true CN101029386A (en) | 2007-09-05 |
| CN100471995C CN100471995C (en) | 2009-03-25 |
Family
ID=38714935
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100346993A Expired - Fee Related CN100471995C (en) | 2007-04-09 | 2007-04-09 | Calcium-zinc-manganese ternary cationic phosphating solution for steel plate and galvanized plate treatment |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100471995C (en) |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831647A (en) * | 2009-03-10 | 2010-09-15 | 刘新智 | Environment-friendly medium-temperature phosphating solution for oilfield pipeline coupling |
| CN101838804A (en) * | 2010-05-10 | 2010-09-22 | 长沙祁胜新材料科技有限公司 | Laminated phosphating liquid and preparation method thereof |
| CN101476119B (en) * | 2009-01-23 | 2012-12-26 | 上海化学试剂研究所 | Surface passivation treatment fluid for martensitic stainless steel parts, preparation and use |
| CN103451638A (en) * | 2013-09-02 | 2013-12-18 | 东南大学 | Pressure phosphating method for enhancing surface oxidation resistance of steel and iron materials |
| CN103866305A (en) * | 2014-03-06 | 2014-06-18 | 山东腾工轴承有限公司 | Manganese-series phosphating liquid and phosphating process |
| CN104451629A (en) * | 2014-12-11 | 2015-03-25 | 国家电网公司 | Process of converting chemically before applying organic coating to steel power transmission and transformation equipment |
| CN104561968A (en) * | 2015-01-12 | 2015-04-29 | 国家电网公司 | A chemical treatment reagent for iron towers of high-voltage transmission lines |
| CN104651820A (en) * | 2015-02-16 | 2015-05-27 | 天津大学 | Ultrasonic phosphating solution for carbon steel, preparation method thereof and method for phosphating carbon steel by adopting phosphating solution |
| CN104962894A (en) * | 2015-06-30 | 2015-10-07 | 大连碧城环保科技股份有限公司 | Special phosphating solution for car and preparing method of phosphating solution |
| CN104962896A (en) * | 2015-06-30 | 2015-10-07 | 大连碧城环保科技股份有限公司 | Zinc-system phosphating solution additive and use method thereof |
| CN104962895A (en) * | 2015-07-14 | 2015-10-07 | 山东省科学院新材料研究所 | Magnetic material phosphating solution |
| CN104962893A (en) * | 2015-06-30 | 2015-10-07 | 大连碧城环保科技股份有限公司 | Environmental phosphating solution |
| CN105256297A (en) * | 2014-07-17 | 2016-01-20 | 烟台盛业钢格板有限公司 | High-corrosion-resistance phosphating solution and preparing method thereof |
| CN106048574A (en) * | 2016-07-15 | 2016-10-26 | 贵州钢绳股份有限公司 | Steel wire rope composite coating agent and coating method |
| CN106756926A (en) * | 2017-01-23 | 2017-05-31 | 江苏理工学院 | A kind of environment-friendly phosphating solution and its application for steel |
| CN107142470A (en) * | 2017-03-28 | 2017-09-08 | 哈尔滨工程大学 | Be conducive to improving the zinc cathode conversion film of corrosion stability of magnesium alloy and the preparation method of epoxy coating |
| CN107406957A (en) * | 2015-03-31 | 2017-11-28 | 安赛乐米塔尔公司 | The panel for vehicle of coated steel plate including local strengthening |
| CN107460466A (en) * | 2016-06-06 | 2017-12-12 | 湖北荣太炊具有限公司 | A kind of wear-resisting complex oxide film of iron-based |
| CN108149234A (en) * | 2017-11-24 | 2018-06-12 | 安徽江南泵阀有限公司 | A kind of pump housing fastener surface parkerizing method |
| CN109023328A (en) * | 2018-10-08 | 2018-12-18 | 于萍 | A kind of combination agent and preparation method thereof for steel surface phosphatization |
| CN109518176A (en) * | 2018-12-14 | 2019-03-26 | 上海大学 | Alkaline phosphating liquid, preparation method and phosphorization treatment process |
| CN111286728A (en) * | 2020-03-30 | 2020-06-16 | 沈阳理工大学 | A kind of phosphating solution, phosphate coating and preparation method and application thereof |
| CN113789507A (en) * | 2021-09-14 | 2021-12-14 | 西安热工研究院有限公司 | Zinc-calcium-manganese phosphating solution and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102899650B (en) * | 2012-10-23 | 2014-06-04 | 自贡勃生表面技术推广有限公司 | Steel normal-temperature blackening solution composite film-forming accelerator, steel normal-temperature blackening solution and preparation method of steel normal-temperature blackening solution |
-
2007
- 2007-04-09 CN CNB2007100346993A patent/CN100471995C/en not_active Expired - Fee Related
Cited By (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101476119B (en) * | 2009-01-23 | 2012-12-26 | 上海化学试剂研究所 | Surface passivation treatment fluid for martensitic stainless steel parts, preparation and use |
| CN101831647A (en) * | 2009-03-10 | 2010-09-15 | 刘新智 | Environment-friendly medium-temperature phosphating solution for oilfield pipeline coupling |
| CN101831647B (en) * | 2009-03-10 | 2013-07-17 | 刘新智 | Environment-friendly medium-temperature phosphating solution for oilfield pipeline coupling |
| CN101838804A (en) * | 2010-05-10 | 2010-09-22 | 长沙祁胜新材料科技有限公司 | Laminated phosphating liquid and preparation method thereof |
| CN101838804B (en) * | 2010-05-10 | 2013-06-19 | 长沙祁胜新材料科技有限公司 | Laminated phosphating liquid and preparation method thereof |
| CN103451638A (en) * | 2013-09-02 | 2013-12-18 | 东南大学 | Pressure phosphating method for enhancing surface oxidation resistance of steel and iron materials |
| CN103451638B (en) * | 2013-09-02 | 2015-10-28 | 东南大学 | A kind of pressure parco-lubrizing strengthening steel material surface resistance of oxidation |
| CN103866305A (en) * | 2014-03-06 | 2014-06-18 | 山东腾工轴承有限公司 | Manganese-series phosphating liquid and phosphating process |
| CN103866305B (en) * | 2014-03-06 | 2015-07-08 | 山东腾工轴承有限公司 | Manganese-series phosphating liquid and phosphating process |
| CN105256297A (en) * | 2014-07-17 | 2016-01-20 | 烟台盛业钢格板有限公司 | High-corrosion-resistance phosphating solution and preparing method thereof |
| CN104451629A (en) * | 2014-12-11 | 2015-03-25 | 国家电网公司 | Process of converting chemically before applying organic coating to steel power transmission and transformation equipment |
| CN104561968A (en) * | 2015-01-12 | 2015-04-29 | 国家电网公司 | A chemical treatment reagent for iron towers of high-voltage transmission lines |
| CN104651820A (en) * | 2015-02-16 | 2015-05-27 | 天津大学 | Ultrasonic phosphating solution for carbon steel, preparation method thereof and method for phosphating carbon steel by adopting phosphating solution |
| CN107406957A (en) * | 2015-03-31 | 2017-11-28 | 安赛乐米塔尔公司 | The panel for vehicle of coated steel plate including local strengthening |
| US11312212B2 (en) | 2015-03-31 | 2022-04-26 | Arcelormittal | Panel for vehicle comprising a coated steel sheet locally reinforced |
| CN104962896A (en) * | 2015-06-30 | 2015-10-07 | 大连碧城环保科技股份有限公司 | Zinc-system phosphating solution additive and use method thereof |
| CN104962893A (en) * | 2015-06-30 | 2015-10-07 | 大连碧城环保科技股份有限公司 | Environmental phosphating solution |
| CN104962894B (en) * | 2015-06-30 | 2017-09-22 | 大连碧城环保科技股份有限公司 | Special phosphating solution of vehicle and preparation method thereof |
| CN104962894A (en) * | 2015-06-30 | 2015-10-07 | 大连碧城环保科技股份有限公司 | Special phosphating solution for car and preparing method of phosphating solution |
| CN104962896B (en) * | 2015-06-30 | 2017-12-05 | 大连碧城环保科技股份有限公司 | A kind of Zinc phosphating solution additive and its application method |
| CN104962895B (en) * | 2015-07-14 | 2018-04-06 | 山东省科学院新材料研究所 | A kind of magnetic material phosphating solution |
| CN104962895A (en) * | 2015-07-14 | 2015-10-07 | 山东省科学院新材料研究所 | Magnetic material phosphating solution |
| CN107460466A (en) * | 2016-06-06 | 2017-12-12 | 湖北荣太炊具有限公司 | A kind of wear-resisting complex oxide film of iron-based |
| CN106048574A (en) * | 2016-07-15 | 2016-10-26 | 贵州钢绳股份有限公司 | Steel wire rope composite coating agent and coating method |
| CN106756926A (en) * | 2017-01-23 | 2017-05-31 | 江苏理工学院 | A kind of environment-friendly phosphating solution and its application for steel |
| CN107142470A (en) * | 2017-03-28 | 2017-09-08 | 哈尔滨工程大学 | Be conducive to improving the zinc cathode conversion film of corrosion stability of magnesium alloy and the preparation method of epoxy coating |
| CN108149234A (en) * | 2017-11-24 | 2018-06-12 | 安徽江南泵阀有限公司 | A kind of pump housing fastener surface parkerizing method |
| CN109023328A (en) * | 2018-10-08 | 2018-12-18 | 于萍 | A kind of combination agent and preparation method thereof for steel surface phosphatization |
| CN109518176A (en) * | 2018-12-14 | 2019-03-26 | 上海大学 | Alkaline phosphating liquid, preparation method and phosphorization treatment process |
| CN111286728A (en) * | 2020-03-30 | 2020-06-16 | 沈阳理工大学 | A kind of phosphating solution, phosphate coating and preparation method and application thereof |
| CN113789507A (en) * | 2021-09-14 | 2021-12-14 | 西安热工研究院有限公司 | Zinc-calcium-manganese phosphating solution and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100471995C (en) | 2009-03-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100471995C (en) | Calcium-zinc-manganese ternary cationic phosphating solution for steel plate and galvanized plate treatment | |
| CA2454042C (en) | Pretreatment method for coating | |
| KR101315417B1 (en) | Composition for metal surface treatment, metal surface treatment method, and metal material | |
| CN103184446B (en) | Forming solution for environment-friendly non-phosphate ceramic film and preparation method and application thereof | |
| CN103797157B (en) | Surface treatment liquid for galvanized steel sheet, galvanized steel sheet, and manufacturing method thereof | |
| US20040163735A1 (en) | Chemical conversion coating agent and surface-treated metal | |
| CN108300988A (en) | A kind of compound chrome-free tanning agent and preparation method of fast filming | |
| JP2004218070A (en) | Pretreatment method for coating | |
| CN102084031A (en) | Chemical conversion liquid for metal structure and surface treating method | |
| AU2012254470B2 (en) | Chemical conversion treatment agent for surface treatment of metal substrate, and surface treatment method of metal substrate using same | |
| CN1890402A (en) | Liquid trivalent chromate for aluminum or aluminum alloy and method for forming corrosion-resistant film over surface of aluminum or aluminum alloy by using same | |
| CA2613639C (en) | Method and agent for chemical conversion treatment and chemically conversion-treated members | |
| Castano et al. | A comparative study on the corrosion resistance of cerium-based conversion coatings on AZ91D and AZ31B magnesium alloys | |
| CN105386025B (en) | A kind of hot galvanized layer chrome-free tanning agent and its preparation method | |
| CN100585002C (en) | A nickel-ion-free phosphating agent for steel plate treatment | |
| CN111074255A (en) | Metal surface pretreatment agent and preparation method and application thereof | |
| JP2014047353A (en) | Chromium-free conversion coating | |
| JP2018095969A (en) | Chromium-free conversion coating | |
| CN115261837A (en) | Pre-painting treatment process for steel-aluminum mixed base material | |
| CN1865503A (en) | Phosphatizing liquid for use in automobile, preparing method and phosphatizing treatment process thereof | |
| CN113512722B (en) | Non-phosphorus and non-nitrogen environment-friendly metal surface film treating agent and application thereof | |
| WO2019131766A1 (en) | Metal surface treatment agent, metal material having surface treatment film, and method for manufacturing same | |
| CN110869535A (en) | Treatment method using zinc dephosphorylating treatment agent comprising cationic polyurethane resin and treated automobile part | |
| CN110869534A (en) | Chemical conversion treatment agent, pretreatment method for coating, and metal member | |
| CN110129784A (en) | Preparation method of neutral surface treatment agent before painting |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Architecture &Decoration Co., Ltd. of China Construction Fifth Engineering Bureau Assignor: Hunan University Contract record no.: 2010430000134 Denomination of invention: Triple cationic phosphorizing fluid containing calcium, zinc and manganese for steel plate and zinc-coated plate treatment Granted publication date: 20090325 License type: Exclusive License Open date: 20070905 Record date: 20101025 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090325 Termination date: 20170409 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |