CN85101297A - 金属磷化工艺 - Google Patents
金属磷化工艺 Download PDFInfo
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- CN85101297A CN85101297A CN198585101297A CN85101297A CN85101297A CN 85101297 A CN85101297 A CN 85101297A CN 198585101297 A CN198585101297 A CN 198585101297A CN 85101297 A CN85101297 A CN 85101297A CN 85101297 A CN85101297 A CN 85101297A
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- phosphatization liquid
- phosphatization
- salt
- zinc
- trichloroacetate
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- 238000000034 method Methods 0.000 title claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 title claims description 9
- 239000002184 metal Substances 0.000 title claims description 9
- 150000002739 metals Chemical class 0.000 title claims description 4
- 239000011701 zinc Substances 0.000 claims abstract description 21
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 14
- 239000012190 activator Substances 0.000 claims abstract description 10
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims abstract description 6
- 229940009662 edetate Drugs 0.000 claims abstract description 6
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical class OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229940066528 trichloroacetate Drugs 0.000 claims abstract description 6
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000010422 painting Methods 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 22
- 229910000831 Steel Inorganic materials 0.000 claims description 17
- 239000010959 steel Substances 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- 239000007921 spray Substances 0.000 claims description 5
- HWTDMFJYBAURQR-UHFFFAOYSA-N 80-82-0 Chemical class OS(=O)(=O)C1=CC=CC=C1[N+]([O-])=O HWTDMFJYBAURQR-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 3
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 239000008397 galvanized steel Substances 0.000 claims description 3
- -1 glycol ester Chemical class 0.000 claims description 3
- 150000004761 hexafluorosilicates Chemical class 0.000 claims description 3
- 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 2
- 239000002253 acid Substances 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229940095064 tartrate Drugs 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 229910001453 nickel ion Inorganic materials 0.000 claims 1
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 claims 1
- 229910019142 PO4 Inorganic materials 0.000 abstract description 18
- 239000010452 phosphate Substances 0.000 abstract description 18
- 239000011248 coating agent Substances 0.000 abstract description 17
- 238000000576 coating method Methods 0.000 abstract description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 17
- 238000005516 engineering process Methods 0.000 abstract description 13
- 238000002425 crystallisation Methods 0.000 description 11
- 230000008025 crystallization Effects 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000001962 electrophoresis Methods 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical class OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 1
- 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 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241000233855 Orchidaceae Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- PYRZPBDTPRQYKG-UHFFFAOYSA-N cyclopentene-1-carboxylic acid Chemical compound OC(=O)C1=CCCC1 PYRZPBDTPRQYKG-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical class [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229940005740 hexametaphosphate Drugs 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 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 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000010729 system oil Substances 0.000 description 1
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 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
- C23C22/07—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
- C23C22/23—Condensed phosphates
-
- 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
-
- 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
- C23C22/362—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 also zinc cations
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- 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)
- Paints Or Removers (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Electrolytic Production Of Metals (AREA)
- Catalysts (AREA)
- Glass Compositions (AREA)
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- Superconductors And Manufacturing Methods Therefor (AREA)
Abstract
在低锌磷化工艺中，覆盖层的质量通过加入甲酸盐，次氮基三乙酸盐，三氯乙酸盐，乙二胺四乙酸盐中一种活化剂而得到改善，生成的磷化层均匀，特别适于电泳涂漆。
Description
本发明涉及金属磷化工艺，特别是钢和镀锌钢的磷化工艺。本发明使用含有加速剂锌、镍（如合适的话）的含水酸性磷化液，采用喷淋法实施，用于电泳涂漆之前。
德国专利申请公开说明书描述了一种含水酸性磷化液。该溶液Zn∶PO4（重量比）为1∶（12～110），用于金属特别是钢铁的表面处理上。由于锌含量低于普通磷化液，因而生成了一层薄而均匀的磷化层。该磷化层附着性强，耐蚀性能好，特别适于做为后续电泳涂漆的底层。
专利合作条约刊物WO 84/00386公开了一种磷化液。该溶液含有0.2～0.6g/l的锌和镍，Zn∶Ni（摩尔比）为1∶（5.2～16）。特别是金属在该溶液中磷化后，其表面生成了难溶于碱的磷化层。
日本专利刊物（按照化学文摘99/216843μ）58114477中描述了一种用于钢的喷淋磷化液。该溶液含有0.1～0.5g/l的锌，15～30g/l的磷酸盐，0.01～0.2g/l的亚硝酸盐，由此产生的磷化层特别适于后续阴极电泳涂漆的予处理。以前的其它刊物包括美国的Serial No.373475，现在的美国专利4419199都公开了适用于某些磷酸锌溶液的活化剂。
采用锌浓度为0.1～0.6g/l的磷化槽液的普通工艺的缺点是：当这种磷化液用来喷淋金属时，经常产生不平整的磷化层，而且部分发灰，部分呈兰绿彩虹色。这种不均匀性在后面进行阴极电泳涂漆时就会变得更为明显，而且后处理的费用可能很高。此外，当面漆承截时，例如在与水接触的弯曲或拉伸中，其附着力往往不能满足形变的要求。
本发明旨在提供一项比普通工艺先进的工艺方法。利用该方法能够生产一层平整、均匀与面漆附着良好的磷化层。
如果按照本发明的内容完成上述工艺，这种目的就可达到。在本发明中，金属表面与含水的酸性磷化液相接触，该溶液含有
Zn++0.2～0.5g/l
Ni++0～1g/l
P2O58～20g/l
NO20.5～0.2g/l和/或硝基苯磺酸盐0.1～1g/l并且该磷化液中至少含有甲酸盐，次氮基三乙酸盐，三氯乙酸盐，乙二胺四乙酸盐中的一种化合物作为活化剂。
按照本发明，本工艺特别适用于铁、钢和镀锌钢的磷化处理，但也适用于锌合金，铝合金的磷化处理。
该磷化处理采用喷淋法，例如与铁、钢和铝的接触时间是90～240秒，锌为5～240秒。
根据本发明，磷化液一般在槽温30～60℃中使用。
一般说来，镍加到磷化液中对磷化速度，难磷化的钢表面层的形成，锌表面的磷化以及抗腐蚀性都起了有利作用。
在磷化过程中，为了建立平衡，按照本发明所使用的磷化液最好含有碱金属离子，例如钠、钾、锂或氨，如果需要，还可含有阴离子，如NO3、C1、或SO4。此外，磷化槽中还可含有磷化技术中常用的其它阳离子，例如，钴、铜、锰、钙、镁和铁。
在本发明的工艺中，用亚硝酸盐和/或硝基苯磺酸盐作为氧化反应的促进剂。此外，还可使用氧化反应促进剂的伴随化合物，例如氯酸盐，这可对氧化反应有利。
本发明的工艺中所使用的活化剂对磷化层的生成起了加速和均匀作用并且控制了磷化层单位面积的重量。例如，它们可以以相应的酸、碱金属盐的形式添加。在磷化液中，单一组份的活化剂的最佳浓度如下：甲酸盐5～15g/l，次氮基三乙酸盐0.3～3g/l，三氯乙酸盐2～15g/l，乙二胺四乙酸盐0.1～3g/l。除上述外，还可加其它添加剂/活化剂：氟化物0.5～3g/l，六氟硅酸盐1～5g/l，四氟硼酸盐3～10g/l，乙二醇脂（盐）0.3～5g/l，柠檬酸盐0.01～0.5g/l，酒石酸盐0.03～0.8g/l，缩合磷酸盐例如：焦磷酸盐，三聚磷酸盐，六偏磷酸盐0.03～0.3g/l。
根据本发明由该工艺产生的金属表面磷化层单位面积重一般在0.8和2.5g/m2之间。为了进一步促进特别细而薄的结晶磷化层的生成，最好使用普通活化剂例如，磷酸钛基的活化剂用在予清洗或最后清理阶段。
按本发明工艺产生的磷化层，原理上适用于磷化层的通用用途。磷化层与面漆的结合大大改善了面漆在腐蚀应力下的耐穿透性。在遭到刮伤，冲击和弯曲应力时，明显的增加了面层与金属底层的附着力，这些优点是显而易见的，特别是在电泳涂漆或阴极电泳涂漆后更为显著。鉴于此，这种工艺最适合作为以这种方法涂漆前的准备工作中。根据本发明，这种工艺已用在实际中，例如：汽车车体磷化。
下面根据本发明的工艺，通过举例的方法，较为详细的说明这种工艺。
实例
通过喷淋的方法，首先将钢板用弱碱、活性清洗剂除油，然后用水冲洗。将该钢板在55℃下喷淋磷化液不到两分钟，再用水冲洗，用稀Cr（Ⅵ）/Cr（Ⅲ）液钝化，用去离子水喷淋洗净，部分钢板干燥后，然后将此部分钢板进行阴极电泳。根据实例1～7，每种磷化液含有：Ni 0.5g/l
P2O514g/l
CLO31.5g/l
NO20.1g/l
锌含量在表中表明。
根据实例8～11，磷化液含有：
Zn 0.4g/l
Ni 0.5g/l
P2O514.0g/l
CLO31.5g/l
NO20.1g/l
另外，表中提到了活化剂的含量。阐述过的每一种磷化液都应用碱进行磷化平衡。
用评价磷化层的形式说明磷化处理的效果，如下：
表1
磷化液 磷化层评价
1 Zn 0.1g/l 兰亮
2 Zn 0.2g/l 约80%兰亮
约20%灰色细结晶
3 Zn 0.3g/l 约60%兰亮
约40%灰色细结晶
4 锌 0.4g/l 约30%兰亮
约70%灰色细结晶
5 锌 0.5g/l 约20%兰亮
约80%灰色细结晶
6 锌 0.6g/l 约5%兰亮
约95%灰色细结晶
7 锌 0.7g/l 灰色细结晶
8 甲酸盐7g/l 灰色细结晶
9 次氮基三乙酸盐1 灰色细结晶
10 三氯乙酸盐10g/l 灰色细结晶
11 乙二胺四乙酸盐0.3g/l 灰色细结晶
根据本发明工艺的优点与根据先有技术的例1～6相比的磷化层评定情况，清楚地表明在例8～11中。由于分批轧制的钢板显示出不同的化学活性，尽管这不会严重影响相对差别，但自测评定的绝对值受到了一定的影响。
如果适当地加一些亚硝酸盐，使用含亚硝酸盐无氯酸盐的磷化液和含有硝基苯磺酸盐的磷化液进行磷化处理，所得磷化层的评价结果类似。
在阴极电泳涂漆后，根据实例1～6磷化得到的钢板表面漆膜不平，而根据实例7～11磷化的钢板漆膜平整。
使用自动涂漆方法所得到的某些阴极电泳钢板的漆膜厚度可达100μA，并用多种方法对其检测。通过盐雾对VVV路面碎石冲击试验，在湿热大气中暴露后的交叉影线试验及在园锥轴芯上的弯曲试验，表明根据本发明处理的钢板实验结果很好，比按先有技术中实例4和实例7所得到的钢板实验结果好的多。
补正 85101297
文件名称 页 行 补正前 补正后
说明书 1 4 说明书描述 说明书2232067描述
1 9 刊物 公告
2 倒数4 还可使用氧化反 “还可伴随使用氧化反应
应促进剂的伴随 促进剂”
化合物
3 5 乙二醇脂 甘醇酸酯
5 8 自测 目测
权利要求书 1 11、12 乙二醇酯 甘醇酸酯
1 19 所述 所述的方法
Claims (6)
1、金属磷化工艺，特别是钢和镀锌钢磷化工艺，通过喷淋的方法，使用含锌促进剂的水溶液酸性磷化液，其中金属表面与磷化液相接触。该溶液含有：
zn++0.2～0.5g/l
P2O58～20g/l
NO2 -0.05～0.2g/l
硝基苯磺酸盐 0.1～1g/l
且至少从含有甲酸盐，次氮基三乙酸盐，三氯乙酸盐，乙二胺四乙酸盐中选取一种化合物做为促进剂。
2、根据权项1所述的方法，其中金属表面与磷化液相接触，该溶液至少含有下列一种添加剂：氟化物，六氟硅酸盐，四氟硼酸盐，乙二醇酯，柠檬酸盐，酒石酸和浓缩磷酸盐。
3、根据权项1所述的方法，其中金属表面与磷化液相接触，在该磷化液中活化剂的含量为
甲酸盐 5～15g/l
次氮基三乙酸盐 0.3～3g/l
三氯乙酸盐 2～15g/l
乙二胺四乙酸盐 0.1～3g/l
4、根据权项2或3所述，含有的其它添加剂如下：
氟化物 0.5～3g/l
六氟硅酸盐 1～5g/l
四氟硼酸盐 3～10g/l
乙二醇酸盐 0.3～5g/l
柠檬酸盐 0.01～0.5g/l
5、根据权项1或2所述的方法，其中磷化后的表面要经过电泳涂漆。
6、根据权项1或2所述的方法，其中磷化液还含有0～1g/l的镍离子。
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19843408577 DE3408577A1 (de) | 1984-03-09 | 1984-03-09 | Verfahren zur phosphatierung von metallen |
Publications (1)
| Publication Number | Publication Date |
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| CN85101297A true CN85101297A (zh) | 1987-01-24 |
Family
ID=6229954
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| Application Number | Title | Priority Date | Filing Date |
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| CN198585101297A Pending CN85101297A (zh) | 1984-03-09 | 1985-04-01 | 金属磷化工艺 |
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| Country | Link |
|---|---|
| US (1) | US4637838A (zh) |
| EP (1) | EP0154367B1 (zh) |
| CN (1) | CN85101297A (zh) |
| AT (1) | ATE37203T1 (zh) |
| AU (1) | AU575380B2 (zh) |
| CA (1) | CA1224121A (zh) |
| DE (2) | DE3408577A1 (zh) |
| ES (1) | ES541015A0 (zh) |
| GB (1) | GB2155960A (zh) |
| ZA (1) | ZA851761B (zh) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103668149A (zh) * | 2013-12-19 | 2014-03-26 | 湖南金裕化工有限公司 | 常温快速磷化液及其制备方法 |
| CN103695881A (zh) * | 2013-12-19 | 2014-04-02 | 湖南金裕化工有限公司 | 常温无渣快速磷化液及其制备方法 |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8527833D0 (en) * | 1985-11-12 | 1985-12-18 | Pyrene Chemicals Services Ltd | Phosphate coating of metals |
| DE3630246A1 (de) * | 1986-09-05 | 1988-03-10 | Metallgesellschaft Ag | Verfahren zur erzeugung von phosphatueberzuegen sowie dessen anwendung |
| DE3871031D1 (de) * | 1987-08-19 | 1992-06-17 | Metallgesellschaft Ag | Verfahren zur phosphatierung von metallen. |
| JPH01100281A (ja) * | 1987-10-13 | 1989-04-18 | Nippon Parkerizing Co Ltd | 金属表面の皮膜化成処理液 |
| JPH0730455B2 (ja) * | 1988-09-27 | 1995-04-05 | 日本パーカライジング株式会社 | リン酸塩化成処理液 |
| JP2781844B2 (ja) * | 1988-10-20 | 1998-07-30 | 日本ペイント株式会社 | 塗装用下地処理剤 |
| JP2636919B2 (ja) * | 1989-01-26 | 1997-08-06 | 日本パーカライジング株式会社 | 鉄鋼の冷間塑性加工用潤滑処理方法 |
| DE3916498A1 (de) * | 1989-05-20 | 1990-11-22 | Kolbenschmidt Ag | Verfahren zum aufbringen einer phosphat-laufschicht auf eine lagermetallschicht |
| DE4409306A1 (de) * | 1994-03-18 | 1995-09-21 | Basf Ag | Verfahren zur Modifizierung von Metalloberflächen |
| DE4417965A1 (de) * | 1994-05-21 | 1995-11-23 | Henkel Kgaa | Eisenphosphatierung unter Verwendung von substituierten Monocarbonsäuren |
| US6716192B1 (en) * | 1997-09-30 | 2004-04-06 | Charles F. Schroeder | Medical needle having a visibly marked tip |
| US6551417B1 (en) | 2000-09-20 | 2003-04-22 | Ge Betz, Inc. | Tri-cation zinc phosphate conversion coating and process of making the same |
| DE102005047424A1 (de) * | 2005-09-30 | 2007-04-05 | Henkel Kgaa | Phosphatierlösung mit Wasserstoffperoxid und chelatbildenden Carbonsäuren |
| CN102839374A (zh) * | 2012-09-05 | 2012-12-26 | 业纮企业股份有限公司 | 球阀用碳钢球体表面处理方法 |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL91161C (zh) * | 1952-08-28 | |||
| US2884351A (en) * | 1956-01-25 | 1959-04-28 | Parker Rust Proof Co | Method of cold rolling ferrous strip stock |
| GB865497A (en) * | 1958-10-03 | 1961-04-19 | Pyrene Co Ltd | Improvements relating to the cleaning and phosphate coating of metallic surfaces |
| GB1414484A (en) * | 1972-05-03 | 1975-11-19 | Pyrene Chemical Services Ltd | Treatment of zinc surfaces |
| SU800240A1 (ru) * | 1977-03-05 | 1981-01-30 | Научно-Исследовательский Институтхимии Саратовского Государственногоордена Трудового Красного Знамениуниверситета Им.H.Г.Чернышевского | Раствор дл фосфатировани кадми |
| GB1591039A (en) * | 1977-05-03 | 1981-06-10 | Pyrene Chemical Services Ltd | Processes and compositions for coating metal surfaces |
| JPS5811513B2 (ja) * | 1979-02-13 | 1983-03-03 | 日本ペイント株式会社 | 金属表面の保護方法 |
| DE2907094A1 (de) * | 1979-02-23 | 1980-09-04 | Metallgesellschaft Ag | Phosphatierungsloesungen |
| GB2072225B (en) * | 1980-03-21 | 1983-11-02 | Pyrene Chemical Services Ltd | Process and composition for coating metal surfaces |
| DE3016576A1 (de) * | 1980-04-30 | 1981-11-05 | Metallgesellschaft Ag, 6000 Frankfurt | Verfahren zur phosphatierung von metalloberflaechen sowie dessen anwendung |
| DE3118375A1 (de) * | 1981-05-09 | 1982-11-25 | Metallgesellschaft Ag, 6000 Frankfurt | Verfahren zur phosphatierung von metallen sowie dessen anwendung zur vorbehandlung fuer die elektrotauchlackierung |
| US4498935A (en) * | 1981-07-13 | 1985-02-12 | Parker Chemical Company | Zinc phosphate conversion coating composition |
| US4486241A (en) * | 1981-09-17 | 1984-12-04 | Amchem Products, Inc. | Composition and process for treating steel |
| JPS58144477A (ja) * | 1982-02-20 | 1983-08-27 | Nippon Paint Co Ltd | 金属表面のリン酸塩処理法 |
| DE3311738A1 (de) * | 1983-03-31 | 1984-10-04 | Metallgesellschaft Ag, 6000 Frankfurt | Verfahren zur phosphatierung von metalloberflaechen |
-
1984
- 1984-03-09 DE DE19843408577 patent/DE3408577A1/de not_active Withdrawn
-
1985
- 1985-02-15 AT AT85200192T patent/ATE37203T1/de not_active IP Right Cessation
- 1985-02-15 DE DE8585200192T patent/DE3564967D1/de not_active Expired
- 1985-02-15 EP EP85200192A patent/EP0154367B1/de not_active Expired
- 1985-03-05 US US06/708,463 patent/US4637838A/en not_active Expired - Fee Related
- 1985-03-06 AU AU39574/85A patent/AU575380B2/en not_active Ceased
- 1985-03-07 ES ES541015A patent/ES541015A0/es active Granted
- 1985-03-07 CA CA000475958A patent/CA1224121A/en not_active Expired
- 1985-03-08 ZA ZA851761A patent/ZA851761B/xx unknown
- 1985-03-08 GB GB08506049A patent/GB2155960A/en not_active Withdrawn
- 1985-04-01 CN CN198585101297A patent/CN85101297A/zh active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103668149A (zh) * | 2013-12-19 | 2014-03-26 | 湖南金裕化工有限公司 | 常温快速磷化液及其制备方法 |
| CN103695881A (zh) * | 2013-12-19 | 2014-04-02 | 湖南金裕化工有限公司 | 常温无渣快速磷化液及其制备方法 |
| CN103695881B (zh) * | 2013-12-19 | 2016-08-24 | 湖南金裕化工有限公司 | 常温无渣快速磷化液及其制备方法 |
| CN103668149B (zh) * | 2013-12-19 | 2016-08-24 | 湖南金裕化工有限公司 | 常温快速磷化液及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0154367A2 (de) | 1985-09-11 |
| EP0154367A3 (en) | 1986-08-20 |
| CA1224121A (en) | 1987-07-14 |
| ATE37203T1 (de) | 1988-09-15 |
| ES8602152A1 (es) | 1985-12-01 |
| AU575380B2 (en) | 1988-07-28 |
| EP0154367B1 (de) | 1988-09-14 |
| AU3957485A (en) | 1985-09-12 |
| GB8506049D0 (en) | 1985-04-11 |
| ES541015A0 (es) | 1985-12-01 |
| GB2155960A (en) | 1985-10-02 |
| DE3408577A1 (de) | 1985-09-12 |
| ZA851761B (en) | 1985-11-27 |
| US4637838A (en) | 1987-01-20 |
| DE3564967D1 (en) | 1988-10-20 |
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