CN107513701A - A kind of environment-friendly type fluoride-free chromium-free promotees paint film attachment phosphating solution and its application - Google Patents
A kind of environment-friendly type fluoride-free chromium-free promotees paint film attachment phosphating solution and its application Download PDFInfo
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- CN107513701A CN107513701A CN201710710913.6A CN201710710913A CN107513701A CN 107513701 A CN107513701 A CN 107513701A CN 201710710913 A CN201710710913 A CN 201710710913A CN 107513701 A CN107513701 A CN 107513701A
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- 239000003973 paint Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 12
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 239000001509 sodium citrate Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- 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 7
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 6
- 239000010959 steel Substances 0.000 claims description 6
- 229940120146 EDTMP Drugs 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 229910000838 Al alloy Inorganic materials 0.000 claims description 2
- 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 2
- 229940062672 calcium dihydrogen phosphate Drugs 0.000 claims description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 2
- 235000019691 monocalcium phosphate Nutrition 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims 5
- 235000021317 phosphate Nutrition 0.000 claims 5
- -1 phospho acids Chemical class 0.000 claims 5
- 239000002253 acid Substances 0.000 claims 4
- 239000010452 phosphate Substances 0.000 claims 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 3
- 235000011083 sodium citrates Nutrition 0.000 claims 3
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical class [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- 235000002908 manganese Nutrition 0.000 claims 2
- QMPFJHZFXOPGIK-UHFFFAOYSA-N P.P.OC=C Chemical compound P.P.OC=C QMPFJHZFXOPGIK-UHFFFAOYSA-N 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 239000007769 metal material Substances 0.000 abstract description 5
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 abstract description 5
- 230000001737 promoting effect Effects 0.000 abstract description 4
- VPTUPAVOBUEXMZ-UHFFFAOYSA-N (1-hydroxy-2-phosphonoethyl)phosphonic acid Chemical compound OP(=O)(O)C(O)CP(O)(O)=O VPTUPAVOBUEXMZ-UHFFFAOYSA-N 0.000 abstract description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052804 chromium Inorganic materials 0.000 abstract description 3
- 239000011651 chromium Substances 0.000 abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 abstract description 3
- 239000011737 fluorine Substances 0.000 abstract description 3
- 239000013049 sediment Substances 0.000 abstract description 3
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 abstract description 2
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004381 surface treatment Methods 0.000 abstract description 2
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 abstract 1
- 238000005507 spraying Methods 0.000 abstract 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 12
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 6
- 239000004312 hexamethylene tetramine Substances 0.000 description 6
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- NAAXGLXYRDSIRS-UHFFFAOYSA-L dihydrogen phosphate;manganese(2+) Chemical compound [Mn+2].OP(O)([O-])=O.OP(O)([O-])=O NAAXGLXYRDSIRS-UHFFFAOYSA-L 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 210000003298 dental enamel Anatomy 0.000 description 3
- 239000007888 film coating Substances 0.000 description 3
- 238000009501 film coating Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- MFXMOUUKFMDYLM-UHFFFAOYSA-L zinc;dihydrogen phosphate Chemical compound [Zn+2].OP(O)([O-])=O.OP(O)([O-])=O MFXMOUUKFMDYLM-UHFFFAOYSA-L 0.000 description 3
- 229910001094 6061 aluminium alloy Inorganic materials 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- MATBMWGLNMBFBE-UHFFFAOYSA-N [F].[Cr] Chemical compound [F].[Cr] MATBMWGLNMBFBE-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006424 Flood reaction Methods 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 239000002320 enamel (paints) Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- CMYCPTASPDMVFC-UHFFFAOYSA-N n,n,n',n'-tetraaminoethane-1,2-diamine Chemical compound NN(N)CCN(N)N CMYCPTASPDMVFC-UHFFFAOYSA-N 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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
- C23C22/06—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
- C23C22/07—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 phosphates
- C23C22/08—Orthophosphates
- C23C22/18—Orthophosphates containing manganese cations
- C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
-
- 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
- C23C22/07—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 phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
- C23C22/17—Orthophosphates containing zinc cations containing also organic acids
Landscapes
- 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
本发明提出一种环保型无氟无铬促漆膜附着磷化溶液及其应用。磷化溶液不含氟和铬，且包含0～50g/L有机膦酸，其中不包括0，有机膦酸可以是羟基亚乙基二膦酸、氨基三亚甲基膦酸、乙二胺四亚甲基膦酸、二乙烯三胺五甲叉膦酸中的一种或几种。该磷化溶液的应用可以在溶液温度为30～95℃、处理时间为10～40min、处理方式为将工件浸泡入溶液中或者将溶液喷淋在工件表面上予以进行。本发明磷化溶液的优点在于通过加入有机膦酸，可以在金属表面形成有机膦酸盐膜层，极大地促进后续漆膜在膦酸盐膜层上的附着力；并且可以有效减缓磷化溶液的沉渣量，延长磷化溶液的使用寿命；磷化溶液使用温度区间范围广，环保易回收，综合成本低，可以应用在金属材料表面处理领域。
The invention provides an environment-friendly fluorine-free, chrome-free and phosphating solution for promoting paint film adhesion and its application. The phosphating solution does not contain fluorine and chromium, and contains 0~50g/L organic phosphonic acid, excluding 0. The organic phosphonic acid can be hydroxyethylene diphosphonic acid, aminotrimethylene phosphonic acid, ethylenediaminetetramethylene One or more of methylphosphonic acid and diethylenetriaminepentamethylenephosphonic acid. The application of the phosphating solution can be carried out when the solution temperature is 30-95° C., the treatment time is 10-40 minutes, and the treatment method is immersing the workpiece in the solution or spraying the solution on the surface of the workpiece. The advantage of the phosphating solution of the present invention is that by adding organic phosphonic acid, an organic phosphonate film layer can be formed on the metal surface, which greatly promotes the adhesion of the subsequent paint film on the phosphonate film layer; The amount of sediment is low, prolonging the service life of the phosphating solution; the phosphating solution has a wide temperature range, is environmentally friendly and easy to recycle, and has low overall cost. It can be applied in the field of surface treatment of metal materials.
Description
技术领域technical field
本发明涉及一种环保型无氟无铬促漆膜附着磷化溶液及其应用，属于材料表面处理领域。The invention relates to an environment-friendly fluorine-free and chrome-free phosphating solution for promoting paint film adhesion and application thereof, belonging to the field of material surface treatment.
背景技术Background technique
长期以来，人们在使用金属的过程中，就一直伴随着金属材料的腐蚀问题。特别是近年来，城市基础建设、汽车及轨道交通、机械化工行业等呈现跨越式发展，消耗掉大量钢铁、铝、镁等金属材料，如何控制材料的腐蚀问题直接影响了各类工程设施的使用寿命。根据相关统计，腐蚀给人类造成的危害和损失甚至超过了风灾、水灾、火灾和地震等所有自然灾害的总和，我国每年为腐蚀所付出的代价相当于每年经济生产总值的4％～5％。For a long time, people have been accompanied by the corrosion of metal materials in the process of using metal. Especially in recent years, urban infrastructure, automobiles and rail transit, machinery and chemical industries have shown great-leap-forward development, consuming a large amount of metal materials such as steel, aluminum, magnesium, etc. How to control the corrosion of materials directly affects the use of various engineering facilities life. According to relevant statistics, the harm and loss caused by corrosion to humans even exceeds the sum of all natural disasters such as wind disasters, floods, fires and earthquakes. The annual cost of corrosion in my country is equivalent to 4% to 5% of the annual gross economic product. .
防护涂层可以有效提高金属材料的耐蚀性，目前已开发出多种金属材料防护涂层制备技术。其中，以磷化处理打底外加电泳等漆膜涂装技术制备的复合涂层具有较好的防护效果，广泛应用于钢铁、铝、镁等金属的防护。Protective coatings can effectively improve the corrosion resistance of metal materials. At present, a variety of protective coating preparation technologies for metal materials have been developed. Among them, the composite coating prepared by phosphating treatment plus electrophoresis and other paint film coating technologies has a good protective effect and is widely used in the protection of steel, aluminum, magnesium and other metals.
然而，现有磷化处理外加漆膜涂装技术存在有诸多弊端。其一，现有磷化处理溶液为了提高处理效果通常含有氟和铬元素。一方面，含氟铬磷化废液的回收处理需要浪费大量的人力和财力；另一方面，含氟铬磷化废液的排放容易造成水体和土壤污染，对人类和动植物造成严重危害。其二，现有磷化处理溶液在磷化处理过程中容易产生磷化沉渣，造成磷化溶液使用寿命短，磷化成本提高。其三，现有磷化处理溶液主体组分通常为无机盐，所形成的磷化膜为无机磷酸盐，与后续漆膜的结合更多地是依靠物理吸附作用，漆膜附着力不高，工件在后期使用过程中容易发生漆膜鼓泡甚至脱落，从而降低膜层的防护作用。However, the existing phosphating treatment plus paint film coating technology has many disadvantages. First, the existing phosphating treatment solutions usually contain fluorine and chromium elements in order to improve the treatment effect. On the one hand, the recycling and treatment of chromium-fluorine-containing phosphating waste liquid requires a lot of waste of manpower and financial resources; on the other hand, the discharge of chromium-fluorine-containing phosphating waste liquid is likely to cause water and soil pollution, causing serious harm to humans, animals and plants. Second, the existing phosphating treatment solution is prone to produce phosphating sediment during the phosphating treatment process, resulting in short service life of the phosphating solution and increased phosphating cost. Third, the main component of the existing phosphating treatment solution is usually inorganic salt, and the formed phosphating film is inorganic phosphate, and the combination with the subsequent paint film is more dependent on physical adsorption, and the paint film adhesion is not high. The workpiece is prone to bubbling or even peeling off of the paint film in the later use process, thereby reducing the protective effect of the film layer.
发明内容Contents of the invention
本发明针对现有金属磷化处理外加漆膜涂装技术所存在的不足，提供一种环保型无氟无铬促漆膜附着磷化溶液及其应用，可同时解决环保、成本和漆膜附着力问题。Aiming at the deficiencies in the existing metal phosphating treatment plus paint film coating technology, the present invention provides an environmentally friendly fluorine-free, chromium-free paint film adhesion promoting phosphating solution and its application, which can simultaneously solve environmental protection, cost and paint film adhesion. focus on the problem.
为此，本发明的目的在于提出一种环保型无氟无铬促漆膜附着磷化溶液及其应用。For this reason, the object of the present invention is to propose an environment-friendly fluorine-free and chrome-free phosphating solution for promoting paint film adhesion and application thereof.
所述磷化溶液包含以下成分：0～50g/L有机膦酸，其中不包括0。The phosphating solution contains the following components: 0-50 g/L organic phosphonic acid, excluding 0.
优选地，所述磷化溶液组成为：20～60g/L磷酸二氢盐，0～20g/L硝酸盐，0～3g/L柠檬酸钠，0～2g/L六亚甲基四胺，0.01～50g/L有机膦酸，溶剂为去离子水。Preferably, the composition of the phosphating solution is: 20-60g/L dihydrogen phosphate, 0-20g/L nitrate, 0-3g/L sodium citrate, 0-2g/L hexamethylenetetramine, 0.01～50g/L organic phosphonic acid, the solvent is deionized water.
优选地，所述有机膦酸为羟基亚乙基二膦酸、氨基三亚甲基膦酸、乙二胺四亚甲基膦酸、二乙烯三胺五甲叉膦酸中的一种或几种。Preferably, the organic phosphonic acid is one or more of hydroxyethylenediphosphonic acid, aminotrimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid .
优选地，所述磷酸二氢盐为磷酸二氢锰、磷酸二氢锌、磷酸二氢钙中的一种或几种，所述硝酸盐为硝酸锰、硝酸锌、硝酸钙中的一种或几种。Preferably, the dihydrogen phosphate is one or more of manganese dihydrogen phosphate, zinc dihydrogen phosphate, and calcium dihydrogen phosphate, and the nitrate is one or more of manganese nitrate, zinc nitrate, and calcium nitrate. Several kinds.
优选地，所述磷化溶液组成为：30～50g/L磷酸二氢锰，5～15g/L硝酸锰，0.5～2g/L柠檬酸钠，0.1～1g/L六亚甲基四胺，5～30g/L乙二胺四亚甲基膦酸，溶剂为去离子水。Preferably, the composition of the phosphating solution is: 30-50 g/L manganese dihydrogen phosphate, 5-15 g/L manganese nitrate, 0.5-2 g/L sodium citrate, 0.1-1 g/L hexamethylenetetramine, 5-30g/L ethylenediamine tetramethylene phosphonic acid, the solvent is deionized water.
优选地，所述磷化溶液组成为：40g/L磷酸二氢锰，10g/L硝酸锰，1g/L柠檬酸钠，0.3g/L六亚甲基四胺，10g/L乙二胺四亚甲基膦酸，溶剂为去离子水。Preferably, the composition of the phosphating solution is: 40g/L manganese dihydrogen phosphate, 10g/L manganese nitrate, 1g/L sodium citrate, 0.3g/L hexamethylenetetramine, 10g/L ethylenediaminetetramine Methylene phosphonic acid, the solvent is deionized water.
所述环保型无氟无铬促漆膜附着磷化溶液对工件进行磷化处理的应用包括以下步骤：步骤一、配制所述磷化溶液，调整溶液pH值为2.0～5.0；步骤二、将经过预处理的工件用步骤一中所配制磷化溶液进行磷化处理，其中磷化溶液温度为30～95℃、磷化处理时间为10～40min、磷化处理方式为将工件浸泡入磷化溶液中或者将磷化溶液喷淋在工件表面上；步骤三、将步骤二中经磷化处理的工件取出，用自来水或去离子水清洗3～10min，然后晾干。The application of the environment-friendly fluorine-free and chromium-free paint-promoting film-adhering phosphating solution to the workpiece for phosphating treatment includes the following steps: Step 1, preparing the phosphating solution, adjusting the pH value of the solution to 2.0-5.0; Step 2, adding The pretreated workpiece is phosphating with the phosphating solution prepared in step 1. The temperature of the phosphating solution is 30-95°C, the phosphating treatment time is 10-40min, and the phosphating treatment method is to soak the workpiece in the phosphating solution. solution or spray the phosphating solution on the surface of the workpiece; step 3, take out the workpiece that has been phosphated in step 2, wash it with tap water or deionized water for 3-10 minutes, and then dry it.
优选地，所述工件的材质为镁合金、铝合金、钢中的一种或几种的连接件。Preferably, the workpiece is made of one or more of magnesium alloy, aluminum alloy, and steel.
本发明的优点及有益效果在于：Advantage of the present invention and beneficial effect are:
(1)本发明所述磷化溶液不含氟和铬，属于环保型磷化溶液。(1) The phosphating solution of the present invention does not contain fluorine and chromium, and belongs to the environment-friendly phosphating solution.
(2)本发明所述磷化溶液通过加入有机膦酸，可以在金属表面形成有机膦酸盐膜层，使膦酸盐膜层与后续漆膜间发生化学作用和范德华作用，极大地促进后续漆膜在膦酸盐膜层上的附着力。(2) The phosphating solution of the present invention can form an organic phosphonate film layer on the metal surface by adding organic phosphonic acid, so that chemical action and Van der Waals action take place between the phosphonate film layer and the subsequent paint film, which greatly promotes the follow-up process. Adhesion of paint films to phosphonate film layers.
(3)本发明所述的磷化溶液通过加入有机膦酸，可以有效减缓磷化溶液的沉渣量，延长磷化溶液的使用寿命。(3) The phosphating solution of the present invention can effectively slow down the amount of sediment in the phosphating solution and prolong the service life of the phosphating solution by adding organic phosphonic acid.
附图说明Description of drawings
构成本申请的一部分的说明书附图用来提供对本申请的进一步理解，本申请的示意性实施例及其说明用于解释本申请，并不构成对本申请的不当限定。The accompanying drawings constituting a part of the present application are used to provide further understanding of the present application, and the schematic embodiments and descriptions of the present application are used to explain the present application, and do not constitute improper limitations to the present application.
图1为ZK60镁合金磷化膜的显微形貌图。Figure 1 is the microscopic topography of ZK60 magnesium alloy phosphating film.
图2为经磷化处理的ZK60镁合金工件喷涂白色氨基烘干磁漆后的漆膜宏观形貌图。Fig. 2 is a macroscopic morphological diagram of the paint film after the phosphating-treated ZK60 magnesium alloy workpiece is sprayed with white amino drying enamel.
具体实施方式detailed description
下面对本发明的实施例进行详细说明，本实施例是在以本发明技术方案为前提下进行实施，给出了详细的实施方式和具体的操作过程，但本发明的保护范围不限于下述的实施例。The embodiments of the present invention are described in detail below. This embodiment is implemented under the premise of the technical solution of the present invention, and detailed implementation methods and specific operating procedures are provided, but the protection scope of the present invention is not limited to the following Example.
实施例1Example 1
磷化溶液组成为：40g/L磷酸二氢锰，10g/L硝酸锰，1g/L柠檬酸钠，0.3g/L六亚甲基四胺，10g/L乙二胺四亚甲基膦酸，溶剂为去离子水。该磷化溶液的应用包括以下步骤：步骤一、配制上述磷化溶液，调整溶液pH值为2.5；步骤二、将经过预处理的ZK60镁合金工件用上述磷化溶液进行磷化处理，其中磷化溶液温度为85摄氏度、磷化处理时间为20分钟、磷化处理方式为将工件浸泡入磷化溶液中；步骤三、将步骤二中经磷化处理的工件取出，用去离子水清洗6分钟，然后晾干。制备出的磷化膜的显微形貌如图1所示，磷化膜致密均匀、无污点残渣。对上述经磷化处理的ZK60镁合金工件喷涂白色氨基烘干磁漆，漆膜宏观形貌如图2所示，漆膜光亮平滑，根据GB/T 9286-1998标准通过划格法附着力测试表明漆膜对磷化膜的附着力为1级。Phosphating solution consists of: 40g/L manganese dihydrogen phosphate, 10g/L manganese nitrate, 1g/L sodium citrate, 0.3g/L hexamethylenetetramine, 10g/L ethylenediaminetetramethylenephosphonic acid , the solvent is deionized water. The application of this phosphating solution comprises the following steps: step one, prepare the above-mentioned phosphating solution, and adjust the pH value of the solution to 2.5; step two, carry out phosphating treatment with the above-mentioned phosphating solution on the pretreated ZK60 magnesium alloy workpiece, wherein the phosphorus The temperature of the phosphating solution is 85 degrees Celsius, the phosphating treatment time is 20 minutes, and the phosphating treatment method is to soak the workpiece in the phosphating solution; step 3, take out the phosphating treated workpiece in step 2, and clean it with deionized water for 6 minutes, then dry. The microscopic appearance of the prepared phosphating film is shown in Fig. 1 , the phosphating film is dense and uniform without stain residue. The above phosphating-treated ZK60 magnesium alloy workpiece was sprayed with white amino drying enamel. The macroscopic appearance of the paint film is shown in Figure 2. The paint film is bright and smooth. According to the GB/T 9286-1998 standard, the cross-cut adhesion test shows that The adhesion of the paint film to the phosphating film is grade 1.
实施例2Example 2
磷化溶液组成为：40g/L磷酸二氢锌，10g/L硝酸锌，1g/L柠檬酸钠，0.3g/L六亚甲基四胺，20g/L羟基亚乙基二膦酸，溶剂为去离子水。该磷化溶液的应用包括以下步骤：步骤一、配制上述磷化溶液，调整溶液pH值为2.5；步骤二、将经过预处理的6061铝合金工件用上述磷化溶液进行磷化处理，其中磷化溶液温度为70摄氏度、磷化处理时间为20分钟、磷化处理方式为将工件浸泡入磷化溶液中；步骤三、将步骤二中经磷化处理的工件取出，用去离子水清洗6分钟，然后晾干。制备出的磷化膜致密均匀、无污点残渣。对上述经磷化处理的6061铝合金工件喷涂白色氨基烘干磁漆，漆膜光亮平滑，根据GB/T 9286-1998标准通过划格法附着力测试表明漆膜对磷化膜的附着力为1级。Phosphating solution consists of: 40g/L zinc dihydrogen phosphate, 10g/L zinc nitrate, 1g/L sodium citrate, 0.3g/L hexamethylenetetramine, 20g/L hydroxyethylene diphosphonic acid, solvent for deionized water. The application of this phosphating solution comprises the following steps: Step 1, preparing the above phosphating solution, and adjusting the pH value of the solution to 2.5; Step 2, carrying out phosphating treatment with the above-mentioned phosphating solution on the pretreated 6061 aluminum alloy workpiece, wherein the phosphorus The temperature of the phosphating solution is 70 degrees Celsius, the phosphating treatment time is 20 minutes, and the phosphating treatment method is to soak the workpiece in the phosphating solution; step 3, take out the phosphating treated workpiece in step 2, and clean it with deionized water for 6 minutes, then dry. The prepared phosphating film is dense and uniform without stain residue. The phosphating-treated 6061 aluminum alloy workpiece was sprayed with white amino drying enamel, and the paint film was bright and smooth. According to the GB/T 9286-1998 standard, the cross-hatch adhesion test showed that the adhesion of the paint film to the phosphating film was 1 class.
实施例3Example 3
磷化溶液组成为：50g/L磷酸二氢锌，5g/L硝酸锌，0.5g/L柠檬酸钠，0.2g/L六亚甲基四胺，10g/L氨基三亚甲基膦酸，溶剂为去离子水。该磷化溶液的应用包括以下步骤：步骤一、配制上述磷化溶液，调整溶液pH值为3.0；步骤二、将经过预处理的45号钢工件用上述磷化溶液进行磷化处理，其中磷化溶液温度为40摄氏度、磷化处理时间为15分钟、磷化处理方式为将工件浸泡入磷化溶液中；步骤三、将步骤二中经磷化处理的工件取出，用去离子水清洗6分钟，然后晾干。制备出的磷化膜致密均匀、无污点残渣。对上述经磷化处理的45号钢工件喷涂白色氨基烘干磁漆，漆膜光亮平滑，根据GB/T 9286-1998标准通过划格法附着力测试表明漆膜对磷化膜的附着力为1级。Phosphating solution consists of: 50g/L zinc dihydrogen phosphate, 5g/L zinc nitrate, 0.5g/L sodium citrate, 0.2g/L hexamethylenetetramine, 10g/L aminotrimethylene phosphonic acid, solvent for deionized water. The application of this phosphating solution comprises the following steps: step one, preparing the above-mentioned phosphating solution, and adjusting the pH value of the solution to 3.0; step two, carrying out phosphating treatment with the above-mentioned phosphating solution on the pretreated No. 45 steel workpiece, wherein the phosphorus The temperature of the phosphating solution is 40 degrees Celsius, the phosphating treatment time is 15 minutes, and the phosphating treatment method is to soak the workpiece in the phosphating solution; step 3, take out the phosphating-treated workpiece in step 2, and clean it with deionized water for 6 minutes, then dry. The prepared phosphating film is dense and uniform without stain residue. Spray white amino drying enamel paint on the 45th steel workpiece after phosphating treatment, the paint film is bright and smooth, according to the GB/T 9286-1998 standard, the cross-hatch adhesion test shows that the adhesion of the paint film to the phosphating film is 1 class.
尽管已经示出和描述了本发明的实施例，对于本领域的普通技术人员而言，可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型，本发明的范围由所附权利要求及其等同限定。Although the embodiments of the present invention have been shown and described, those skilled in the art can understand that various changes, modifications and substitutions can be made to these embodiments without departing from the principle and spirit of the present invention. and modifications, the scope of the invention is defined by the appended claims and their equivalents.
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