CN107130235B - 一种钢板用无铬化学转化膜处理液 - Google Patents
一种钢板用无铬化学转化膜处理液 Download PDFInfo
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 31
- 239000010959 steel Substances 0.000 title claims abstract description 31
- 239000012530 fluid Substances 0.000 title claims abstract description 25
- 238000007739 conversion coating Methods 0.000 title claims abstract description 18
- 239000000126 substance Substances 0.000 title claims abstract description 18
- 239000004227 calcium gluconate Substances 0.000 claims abstract description 21
- 229960004494 calcium gluconate Drugs 0.000 claims abstract description 21
- 235000013927 calcium gluconate Nutrition 0.000 claims abstract description 21
- NEEHYRZPVYRGPP-UHFFFAOYSA-L calcium;2,3,4,5,6-pentahydroxyhexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(O)C([O-])=O.OCC(O)C(O)C(O)C(O)C([O-])=O NEEHYRZPVYRGPP-UHFFFAOYSA-L 0.000 claims abstract description 21
- 235000019832 sodium triphosphate Nutrition 0.000 claims abstract description 21
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 19
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims abstract description 19
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical class OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 7
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 14
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 12
- BEGBSFPALGFMJI-UHFFFAOYSA-N ethene;sodium Chemical group [Na].C=C BEGBSFPALGFMJI-UHFFFAOYSA-N 0.000 claims description 8
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- 239000000203 mixture Substances 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 4
- HKHVZIHSDZVIFJ-UHFFFAOYSA-N [K].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCN Chemical group [K].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCN HKHVZIHSDZVIFJ-UHFFFAOYSA-N 0.000 claims description 4
- UZKLEUIGRDLZRP-UHFFFAOYSA-N acetic acid azane ethane-1,2-diamine Chemical compound N.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCN UZKLEUIGRDLZRP-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- -1 fluoride Compound Chemical class 0.000 claims description 2
- 229960004418 trolamine Drugs 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims 1
- 229960005069 calcium Drugs 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 239000008103 glucose Substances 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 13
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052804 chromium Inorganic materials 0.000 abstract description 2
- 239000011651 chromium Substances 0.000 abstract description 2
- 230000007935 neutral effect Effects 0.000 abstract description 2
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- 239000007788 liquid Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
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- 229910000162 sodium phosphate Inorganic materials 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 3
- 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 description 2
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- 239000011734 sodium Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
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- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
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- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- QLBHNVFOQLIYTH-UHFFFAOYSA-L dipotassium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [K+].[K+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O QLBHNVFOQLIYTH-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
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- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
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- 235000019830 sodium polyphosphate Nutrition 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- C23C22/68—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 solutions with pH between 6 and 8
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
本发明公开一种钢板用无铬化学转化膜处理液，其化学组成的含量如下：三聚磷酸盐0.06～0.1mol/L，三乙醇胺0.12～0.2mol/L，乙二胺四乙酸盐0.03～0.05mol/L，葡萄糖酸钙0.03～0.05mol/L，可溶性氟化物0.02～0.04mol/L，且三聚磷酸盐和葡萄糖酸钙的摩尔浓度比为2:1。本发明处理液成分简单，易于控制，不含有机易挥发物质，工艺稳定。本发明处理时间短，常温成膜，原料易得，成本低，适于工业化生产。本发明制得的转化膜膜层均匀，耐蚀性好，中性盐雾试验2小时无腐蚀。本发明处理液不含任何形式的铬元素，所以环境负担小，满足绿色化学和WEES&ROHS指令要求。
Description
技术领域
本发明属于钢板表面处理技术领域，特别涉及一种钢板用无铬化学转化膜处理液。
背景技术
目前为了防止钢板在长期储存和运输过程中发生锈蚀问题，均涂布防锈油并包装防锈纸。然而由于生产过程中涂油工艺可能出现缺陷，或者储藏运输中出现的挤压、叠放等，将造成钢板表面防锈油不均匀分布，从而导致腐蚀。在钢板加工过程中，祛除防锈油产生的含油废水引起环境问题也日益受到重视，随着环境保护意识的提高和绿色化学技术的不断发展，此种防锈技术终将被替代。专利CN1875123B公开了一种化学转化成膜性能优良的热轧钢板及其制造方法，此专利采用浸渍处理液的方法制备钢板表面钝化膜，但需要一定的浸渍时间以保证成膜。
发明内容
本发明提供一种钢板用无铬化学转化膜处理液及其制备方法，提供处理速度快、常温即可固化的具有优良耐蚀性的、对环境影响小的无铬处理液。
为解决上述技术问题，本发明采用如下技术方案：
一种钢板用无铬化学转化膜处理液的化学组成包括：三聚磷酸盐、三乙醇胺、乙二胺四乙酸盐、葡萄糖酸钙和可溶性氟化物，其中各化学组成的含量如下：三聚磷酸盐0.06～0.1mol/L，三乙醇胺0.12～0.2mol/L，乙二胺四乙酸盐0.03～0.05mol/L，葡萄糖酸钙0.03～0.05mol/L，可溶性氟化物0.02～0.04mol/L，且三聚磷酸盐和葡萄糖酸钙的摩尔浓度比为2:1。
优选的，所述的钢板用无铬化学转化膜处理液中的三聚磷酸盐为三聚磷酸钾、三聚磷酸钠或三聚磷酸铵。
优选的，所述的钢板用无铬化学转化膜处理液中的乙二胺四乙酸盐为乙二胺四乙酸钾、乙二胺四乙酸钠或乙二胺四乙酸铵。
优选的，所述的钢板用无铬化学转化膜处理液中的可溶性氟化物为氟化钾、氟化钠或氟化铵。
与现有技术相比较，本发明至少具有如下有益效果：
本发明处理液成分简单，原料易得，易于控制，成本低不含有机易挥发物质。本发明属于吸附成膜机制，处理时间短，吸附过程焓值小于零，无需加热常温即可成膜，适于工业化生产。铁属于第一过渡元素，其次外层d轨道处于未充满的空轨道态易于接受孤对电子形成配位键。三乙醇胺是一种常见的四齿螯合剂，其氮原子上存在孤对电子可以与铁原子的空轨道形成稳定配位键，以化学吸附的形式吸附在钢板表面，通过阳极缓蚀作用提高钢板耐蚀性。葡萄糖酸钙通过阴极极化作用可以有效抑制阴极电化学过程抑制腐蚀，在氟化物的存在条件下抑制作用进一步增强。三聚磷酸盐和乙二胺四乙酸盐的存在增强了处理液的稳定性，并提高膜层的均匀性和附着性。
本发明制得的转化膜膜层均匀，耐蚀性好，中性盐雾试验2小时无腐蚀。本发明处理液不含任何形式的铬元素，所以环境负担小，满足绿色化学和WEES&ROHS指令要求。
具体实施方式
本发明实施例中采用的三聚磷酸盐、乙二胺四乙酸盐、三乙醇胺、葡萄糖酸钙和可溶性氟化物均为工业级产品。
本发明实施例中采用的钢板为工业常规生产的酸洗板。
本发明实施例中的盐雾试验为GB/T10125-2012人造气氛腐蚀试验盐雾试验方法。
本发明实施例中的盐雾试验后的钢板样品采用GBT 6461-2002金属基体上金属和其他无机覆盖层经腐蚀试验后的试样和试件的评级方法评价。
本发明实施例中的附着力试验为GB/T 13448-2006彩色涂层钢板及钢带试验方法中划格实验。
实施例1
向700ml水中加入三聚磷酸钠并搅拌均匀，然后加入三乙醇胺并搅拌均匀，再加入乙二胺四乙酸钠并搅拌均匀，然后在搅拌条件下加入葡萄糖酸钙，然后加入氟化铵搅拌均匀，并定容至1000ml制备成钢板用无铬化学转化膜处理液，其成分按物质的量浓度为三聚磷酸钠0.1mol/L，三乙醇胺0.2mol/L，乙二胺四乙酸钠0.05mol/L，葡萄糖酸钙0.05mol/L，氟化铵0.04mol/L。
实施例2
向700ml水中加入三聚磷酸钾并搅拌均匀，然后加入三乙醇胺并搅拌均匀，再加入乙二胺四乙酸钾并搅拌均匀，然后在搅拌条件下加入葡萄糖酸钙，然后加入氟化钾搅拌均匀，并定容至1000ml制备成钢板用无铬化学转化膜处理液，其成分按物质的量浓度为三聚磷酸钾0.06mol/L，三乙醇胺0.12mol/L，乙二胺四乙酸钾0.03mol/L，葡萄糖酸钙0.03mol/L，氟化钾0.02mol/L。
实施例3
向700ml水中加入三聚磷酸铵并搅拌均匀，然后加入三乙醇胺并搅拌均匀，再加入乙二胺四乙酸钠并搅拌均匀，然后在搅拌条件下加入葡萄糖酸钙，然后加入氟化钠搅拌均匀，并定容至1000ml制备成钢板用无铬化学转化膜处理液，其成分按物质的量浓度为三聚磷酸铵0.08mol/L，三乙醇胺0.16mol/L，乙二胺四乙酸钠0.04mol/L，葡萄糖酸钙0.04mol/L，氟化钠0.03mol/L。
实施例4
向700ml水中加入三聚磷酸钠并搅拌均匀，然后加入三乙醇胺并搅拌均匀，再加入乙二胺四乙酸铵并搅拌均匀，然后在搅拌条件下加入葡萄糖酸钙，然后加入氟化钾搅拌均匀，并定容至1000ml制备成钢板用无铬化学转化膜处理液，其成分按物质的量浓度为三聚磷酸钠0.07mol/L，三乙醇胺0.2mol/L，乙二胺四乙酸铵0.05mol/L，葡萄糖酸钙0.035mol/L，氟化钾0.04mol/L。
实施例5
向700ml水中加入三聚磷酸钠并搅拌均匀，然后加入三乙醇胺并搅拌均匀，再加入乙二胺四乙酸钾并搅拌均匀，然后在搅拌条件下加入葡萄糖酸钙，然后加入氟化钠搅拌均匀，并定容至1000ml制备成钢板用无铬化学转化膜处理液，其成分按物质的量浓度为三聚磷酸钠0.06mol/L，三乙醇胺0.2mol/L，乙二胺四乙酸二钾0.05mol/L，葡萄糖酸钙0.03mol/L，氟化钠0.02mol/L。
实施例6
向700ml水中加入三聚磷酸钾并搅拌均匀，然后加入三乙醇胺并搅拌均匀，再加入乙二胺四乙酸钠并搅拌均匀，然后在搅拌条件下加入葡萄糖酸钙，然后加入氟化钠搅拌均匀，并定容至1000ml制备成钢板用无铬化学转化膜处理液，其成分按物质的量浓度为三聚磷酸钾0.1mol/L，三乙醇胺0.2mol/L，乙二胺四乙酸钠0.04mol/L，葡萄糖酸钙0.05mol/L，氟化钠0.03mol/L。
实施例的试验方法
1、将规格为70mm×50mm的酸洗板浸入上述六种实施例的处理液中5s后取出吹干，然后按照GB/T10125-2012金属覆盖层盐雾腐蚀实验方法进行实验，按照GBT 6461-2002金属基体上金属和其他无机覆盖层经腐蚀试验后的试样和试件的评级方法评价，盐雾试验结果列于表1。
表1实施例盐雾试验结果
2、将规格为70mm×50mm的酸洗板浸入上述六种实施例的处理液中5s后取出吹干，然后涂装聚氨酯漆，按照GB/T 1720—1979《漆膜附着力测定法》(划圈法)、GB/T 9286—1998《色漆和清漆漆膜的划格试验》方法进行实验。
表2实施例涂装后试验结果
| 实施例编号 | 划格附着力(级别) | 划圈附着力(T) |
| 实施例1 | 1 | 1 |
| 实施例2 | 1 | 1 |
| 实施例3 | 1 | 1 |
| 实施例4 | 1 | 1 |
| 实施例5 | 1 | 1 |
| 实施例6 | 1 | 1 |
本发明虽然公开部分实施例，但并不是用来限制本发明。本发明还可以有其他多种实施方式，本领域技术人员可根据本发明做成各种相应的改变，但这些相应的改变都应属于本发明所附权力要求的保护范围。
Claims (4)
1.一种钢板用无铬化学转化膜处理液，其特征在于：处理液的化学组成包括：三聚磷酸盐、三乙醇胺、乙二胺四乙酸盐、葡萄糖酸钙和可溶性氟化物，其中各化学组成的含量如下：三聚磷酸盐0.06～0.1mol/L，三乙醇胺0.12～0.2mol/L，乙二胺四乙酸盐0.03～0.05mol/L，葡萄糖酸钙0.03～0.05mol/L，可溶性氟化物0.02～0.04mol/L，且三聚磷酸盐和葡萄糖酸钙的摩尔浓度比为2:1。
2.根据权利要求1所述的钢板用无铬化学转化膜处理液，其特征在于：所述的三聚磷酸盐为三聚磷酸钾、三聚磷酸钠或三聚磷酸铵。
3.根据权利要求1所述的钢板用无铬化学转化膜处理液，其特征在于：所述的乙二胺四乙酸盐为乙二胺四乙酸钾、乙二胺四乙酸钠或乙二胺四乙酸铵。
4.根据权利要求1所述的钢板用无铬化学转化膜处理液，其特征在于所述的可溶性氟化物为氟化钾、氟化钠或氟化铵。
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