CN102560484B - 镁合金表面防腐处理方法及其镁制品 - Google Patents
镁合金表面防腐处理方法及其镁制品 Download PDFInfo
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- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 89
- 239000011777 magnesium Substances 0.000 title claims abstract description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 15
- 238000005260 corrosion Methods 0.000 title abstract description 11
- 238000003672 processing method Methods 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 239000000758 substrate Substances 0.000 claims abstract description 56
- 238000005524 ceramic coating Methods 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 238000001771 vacuum deposition Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 58
- 239000000243 solution Substances 0.000 claims description 27
- 230000009466 transformation Effects 0.000 claims description 18
- 238000000844 transformation Methods 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 12
- 239000008158 vegetable oil Substances 0.000 claims description 12
- 239000004411 aluminium Substances 0.000 claims description 8
- 229940071182 stannate Drugs 0.000 claims description 8
- 125000005402 stannate group Chemical group 0.000 claims description 8
- 239000003921 oil Substances 0.000 claims description 7
- 235000019198 oils Nutrition 0.000 claims description 7
- 150000002736 metal compounds Chemical class 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000003870 refractory metal Substances 0.000 claims description 6
- 150000000703 Cerium Chemical class 0.000 claims description 5
- 235000013311 vegetables Nutrition 0.000 claims description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005642 Oleic acid Substances 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- -1 ketone compounds Chemical class 0.000 claims description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 4
- 150000002978 peroxides Chemical class 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 238000001994 activation Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 150000004767 nitrides Chemical class 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 238000007739 conversion coating Methods 0.000 abstract description 5
- 238000005238 degreasing Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 229910052684 Cerium Inorganic materials 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000007654 immersion Methods 0.000 description 6
- 238000001755 magnetron sputter deposition Methods 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- 230000009977 dual effect Effects 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 241000218218 Ficus <angiosperm> Species 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000002421 anti-septic effect Effects 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 230000003245 working effect Effects 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
- C23C22/73—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 characterised by the process
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0664—Carbonitrides
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0676—Oxynitrides
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
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- 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
- C23C22/10—Orthophosphates containing oxidants
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- 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
- C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/57—Treatment of magnesium or alloys based thereon
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- 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
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
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- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
Abstract
本发明提供一种镁合金表面防腐处理方法，包括以下步骤：提供镁合金基体；对镁合金基体进行化学除油；对镁合金基体进行无机化学转化处理，以于该镁合金基体上形成一层无机化学转化膜；对该镁合金基体进行有机化学转化处理，以于该无机化学转化膜上形成一层有机化学转化膜；通过真空镀膜方法在该有机化学转化膜上形成由难熔化合物组成的陶瓷涂层。本发明提供一种上述防腐处理方法制得的镁制品。
Description
技术领域
本发明涉及一种镁合金表面防腐处理方法及其镁制品。
背景技术
镁合金具有质量轻、散热性能好等优点，在通讯、电子、交通运输、建筑及航天航空等领域应用广泛。然而，由于镁合金的化学活性较高，在空气中很容易氧化，生成疏松、保护能力差的氧化膜，导致镁合金在潮湿的大气、土壤和海水中容易发生严重腐蚀，导致采用镁合金制作的产品的使用寿命缩短，阻碍了镁合金的广泛应用。
为了提高镁合金的耐腐蚀性能，通常需要对镁合金表面进行表面成膜处理，常见的处理手段有阳极氧化处理、烤漆等，但这些工艺都存在较大的环境污染问题。而真空镀膜(PVD)技术虽是一种非常环保的镀膜工艺，且可镀制的膜层种类丰富、耐磨性能优异，但当承镀基体表面具有微观凹陷或空隙时，PVD工艺沉积的膜层通常具有基体表面的仿形结构，且沉积于这些凹陷或空隙内的膜层往往其它区域的要薄，所以在使用过程中，所述凹陷或空隙区域往往更容易发生点蚀，使膜层无法有效地防止镁合金基体被防腐。
发明内容
有鉴于此，有必要提供一种可效提高镁合金防腐性能的防腐处理方法。
另外，还有必要提供一种由上述方法制得的镁制品。
一种镁合金表面防腐处理方法，包括以下步骤：
提供镁合金基体；
对镁合金基体进行化学除油；
对镁合金基体进行无机化学转化处理，以于该镁合金基体上形成一层无机化学转化膜；
对该镁合金基体进行有机化学转化处理，以于该无机化学转化膜上形成一层有机化学转化膜，该有机化学转化处理采用植物油酸为成膜剂的溶液，该有机化学转化处理是将该经无机化学转化处理的镁合金基体浸泡于30-50℃、含10-30ml/L植物油油酸及酮类化合物的水溶液中2-4分钟，该植物油酸溶液的pH值为2-5；
通过真空镀膜方法在该有机化学转化膜上形成由难熔化合物组成的陶瓷涂层。
由上述镁合金表面防腐处理方法所获得的镁制品，包括镁合金基体、形成于该镁合金基体表面的无机化学转化膜、形成于该无机化学转化膜上的有机化学转化膜及形成于该有机化学转化膜上的由难熔化合物组成的陶瓷涂层。
本发明的镁合金表面防腐处理方法先通过化学转化处理于镁合金基体上制备无机-有机双重化学转化膜，然后于该无机-有机双重化学转化膜上镀覆耐磨陶瓷涂层。其中该无机-有机双重化学转化膜一方面将镁合金基体表面平整化，另一方面该无机-有机双重化学转化膜自身结构致密，阻挡性好，化学稳定性高，与镁合金基体结合力强，具有良好的防腐功能。而外层耐磨的陶瓷涂层，可保护无机-有机双重转化膜不易受到机械损伤。因此，经该方法处理的镁制品具有良好的抗腐蚀性能。
附图说明
图1为由本发明较佳实施例的镁合金表面防腐处理方法所制得的镁制品的剖视示意图。
图2为本发明较佳实施例的镁合金表面防腐处理方法中所用镀膜设备示意图。
主要元件符号说明
镁制品 10
镁合金基体 20
无机-有机复合转化膜 30
无机化学转化膜 31
有机化学转化膜 32
陶瓷涂层 40
氧化铝层 42
氮氧化铝层 43
磁控溅射设备 1
真空室 2
真空泵 3
转架 4
铝靶 5
气源通道 7
具体实施方式
本发明较佳实施例镁合金表面防腐处理方法主要包括如下步骤：
请参阅图1，提供镁合金基体20。
对镁合金基体20进行化学除油。化学除油是将镁合金基体20浸渍于60-80℃的除油溶液中30-60s，所用除油溶液为含25-30g/L碳酸钠、20-25g/L磷酸三钠(Na3PO4·12H2O)及1-3g/L乳化剂的水溶液，其中所述乳化剂可用OP-10乳化剂，其主要组分为烷基酚与环氧乙烷的缩合物。
对镁合金基体20进行活化处理。该活化处理步骤是将镁合金基体20浸渍于含质量百分比浓度为1％-3％的HF水溶液中3-5s，以去除镁合金基体20因暴露于空气中的时间过长而在表面形成的氧化膜，使镁合金基体20表面被活化。
对镁合金基体20进行无机-有机复合化学转化处理，以于镁合金基体20上制备无机-有机复合转化膜30。该无机-有机复合化学转化处理包括先对镁合金基体20进行无机化学转化处理，以于该镁合金基体20上形成一层无机化学转化膜31，再对该镁合金基体20进行有机化学转化处理，以于该无机化学转化膜31上形成一层有机化学转化膜32。
该无机化学转化处理可采用锡酸盐为主要成膜剂或铈盐为主要成膜剂的溶液。
其中，选用锡酸盐处理的溶液配方可为含150-250g/LNa2SnO3·3H2O及80-150g/L KH2PO4的水溶液。较佳地，该锡酸盐溶液可为含200g/L Na2SnO3·3H2O及100g/L KH2PO4的水溶液。处理方法可将镁合金基体20浸泡于60-80℃的该锡酸盐溶液中1-2小时，浸泡过程中可搅拌溶液。较佳地，浸泡过程中锡酸盐溶液的温度保持为70℃，浸泡时间为2小时。经该锡酸盐处理的镁合金基体上可形成以MgSnO3·H2O为主要成分的转化膜。
选用铈盐处理的溶液配方可为含10-30g/L Ce(NO3)3、20-30ml/L质量浓度为50％的过氧水及1-2g/L H3BO3的水溶液。较佳地，该铈盐溶液可为含15g/L Ce(NO3)3、25ml/L质量浓度为50％的过氧水及2g/L H3BO3的水溶液。处理方法可将镁合金基体20浸泡于30-60℃的该铈盐溶液中0.2-2小时，浸泡过程中可搅拌溶液。较佳地，浸泡过程中铈盐溶液的温度保持为40℃，浸泡时间为0.5小时。经该铈盐处理的镁合金基体上可形成以铈的氢氧化物为主要成分的转化膜。
该有机化学转化处理可采用植物油酸(也称顺-9-十八碳烯酸)为成膜剂的溶液。用植物油酸处理的溶液配方可为含10-30ml/L质量浓度为99.8％的植物油油酸及酮类化合物的水溶液，其中该酮类化合物用于促进植物油酸的溶解，该植物油酸溶液的pH值为2-5。较佳地，该植物油酸溶液为含15ml/L及丙酮的水溶液，其pH值为2.8。处理方法可将经上述无机化学转化处理的镁合金基体20浸泡于30-50℃的该植物油酸溶液中2-4分钟，浸泡过程中可搅拌溶液。较佳地，浸泡过程中该植物油酸溶液的温度保持为35℃，浸泡时间为2.5分钟。
然后，对形成有所述无机-有机复合转化膜30的镁合金基体20进行真空镀膜处理，以在无机-有机复合转化膜30上形成由难熔化合物组成的陶瓷涂层40。该陶瓷涂层40包括一层或多层金属难熔化合物层，该金属难熔化合物可选自钛、铝、铬、锆及钴的氮化物、氧化物、氮碳化物及氮氧化物中的一种或几种的组合。本实施例中，该陶瓷涂层40包括一层氧化铝(Al2O3)层42及一层氮氧化铝(AlON)层43，该氧化铝层42直接形成于该无机-有机复合转化膜30上，该氮氧化铝层43形成于该氧化铝层42上。
该真空镀膜处理可采用磁控溅射或电弧离子镀，下面以磁控溅射制备该陶瓷涂层40为例对该真空镀膜处理进行说明。
请参阅图2，提供一磁控溅射设备1，磁控溅射设备1包括一真空室2、用以对真空室2抽真空的真空泵3以及与真空室2相通的气源通道7。该真空室2内设有转架4及相对设置的二铝靶5。转架4带动镁合金基体20做圆周运行，且镁合金基体20在随转架4运行的同时也进行自转。镀膜时，溅射气体与反应气体经由气源通道7进入真空室2。
在该无机-有机复合转化膜30上溅射该氧化铝层42。将形成有该无机-有机复合转化膜30的镁合金基体20放置于磁控溅射设备1的转架4上，对真空室2抽真空至6.0×10-3～8.0×10-3Pa后通入溅射气体氩气，氩气流量为150～300sccm(标准状态毫升/分钟)，同时通入反应气体氧气，氧气流量为50～90sccm，镁合金基体20施加偏压至-100～-300V，开启铝靶5，铝靶5的功率为8～10kw，调节真空室2内温度为100～150℃，转架4的转速为0.5～1.0rpm(revolution perminute，转/分钟)，对镁合金基体20溅射0.5～1小时，以于该无机-有机复合转化膜30表面形成该氧化铝层42。
在氧化铝层42上溅射该氮氧化铝层43。通入反应气体氮气，氮气流量为15～40sccm，调节氧气流量为30～60sccm，其它参数保持不变，溅射0.5～2小时，以在该氧化铝层42上沉积一层氮氧化铝层43。
镀膜结束后，关闭负偏压及铝靶5电源，停止通入氩气、氧气和氮气，待所述氮氧化铝层43冷却后，向真空室2内通入空气，打开真空室门，取出镀覆好的镁制品10。
请参阅图1，由上述镁合金表面防腐处理方法所获得的镁制品10，包括镁合金基体20、形成于镁合金基体20表面的无机-有机复合转化膜30及形成于该无机-有机复合转化膜30上的由难熔化合物组成的陶瓷涂层40。
该无机-有机复合转化膜30包括一层无机化学转化膜31及一层形成于该无机化学转化膜31上的有机化学转化膜32。该无机化学转化膜31可为锡酸盐转化膜或铈盐转化膜。该有机化学转化膜32为植物油酸转化膜。该陶瓷涂层40包括一层或多层金属难熔化合物层，该金属难熔化合物可选自钛、铝、铬、锆及钴的氮化物、氧化物、氮碳化物及氮氧化物中的一种或几种的组合。本实施例中，该陶瓷涂层40包括一层氧化铝(Al2O3)层42及一层氮氧化铝(AlON)层43，该氧化铝层42直接形成于该无机-有机复合转化膜30上，该氮氧化铝层43形成于该氧化铝层42上。
该陶瓷涂层40的总体厚度大约为2-5微米。
对由本发明的防腐处理方法所制备的镁制品10试样进行35℃中性盐雾(NaCl浓度为5％)测试。结果发现，镁制品10试样在72小时后才出现有腐蚀现象，具有良好的防腐性能。
本发明的镁合金表面防腐处理方法先通过化学转化处理于镁合金基体20上制备一层无机-有机复合转化膜30，然后于该无机-有机复合转化膜30上镀覆耐磨陶瓷涂层40。其中该无机-有机复合转化膜30一方面将镁合金基体20表面平整化，另一方面无机-有机复合转化膜30自身结构致密，阻挡性好，化学稳定性高，与镁合金基体20结合力强，具有良好的防腐功能。而外层耐磨的陶瓷涂层40，可保护无机-有机复合转化膜30不易受到机械损伤。因此，经该方法处理的镁制品10具有良好的抗腐蚀性能。
Claims (11)
1.一种镁合金表面防腐处理方法，包括以下步骤：
提供镁合金基体；
对镁合金基体进行化学除油；
对镁合金基体进行无机化学转化处理，以于该镁合金基体上形成无机化学转化膜；
对该镁合金基体进行有机化学转化处理，以于该无机化学转化膜上形成有机化学转化膜，该有机化学转化处理采用植物油酸为成膜剂的溶液，该有机化学转化处理是将该经无机化学转化处理的镁合金基体浸泡于30-50℃、含10-30ml/L植物油油酸及酮类化合物的水溶液中2-4分钟，该植物油酸溶液的pH值为2-5；
通过真空镀膜方法在该有机化学转化膜上形成由难熔化合物组成的陶瓷涂层。
2.如权利要求1所述的镁合金表面防腐处理方法，其特征在于：所述无机化学转化处理采用锡酸盐为主要成膜剂的溶液。
3.如权利要求2所述的镁合金表面防腐处理方法，其特征在于：所述无机化学转化处理是将该镁合金基体浸泡于60-80℃、含150-250g/L Na2SnO3·3H2O及80-150g/L KH2PO4的水溶液中1-2小时。
4.如权利要求3所述的镁合金表面防腐处理方法，其特征在于：所述无机化学转化处理是将该镁合金基体浸泡于70℃、含200g/LNa2SnO3·3H2O及100g/L KH2PO4的水溶液中2小时。
5.如权利要求1所述的镁合金表面防腐处理方法，其特征在于：所述无机化学转化处理采用铈盐为主要成膜剂的溶液。
6.如权利要求5所述的镁合金表面防腐处理方法，其特征在于：所述无机化学转化处理是将该镁合金基体浸泡于30-60℃、含10-30g/L Ce(NO3)3、20-30ml/L质量浓度为50％的过氧水及1-2g/LH3BO3的水溶液中0.2-2小时。
7.如权利要求6所述的镁合金表面防腐处理方法，其特征在于：所述无机化学转化处理是将该镁合金基体浸泡于40℃、含15g/LCe(NO3)3、25ml/L质量浓度为50％的过氧水及2g/L H3BO3的水溶液中0.5小时。
8.如权利要求1所述的镁合金表面防腐处理方法，其特征在于：该有机化学转化处理是将该经无机化学转化处理的镁合金基体浸泡于35℃、含15ml/L植物油油酸及丙酮的水溶液中2.5分钟，该植物油酸溶液的pH值为2.8。
9.如权利要求1所述的镁合金表面防腐处理方法，其特征在于：该陶瓷涂层包括一层或多层金属难熔化合物层，该金属难熔化合物选自钛、铝、铬、锆及钴的氮化物、氧化物、氮碳化物及氮氧化物中的一种或几种的组合。
10.如权利要求1所述的镁合金表面防腐处理方法，其特征在于：该镁合金表面防腐处理方法还包括在所述无机化学转化处理前将镁合金基体浸渍于含质量百分比浓度为1％-3％HF的水溶液中3-5s的活化处理步骤。
11.一种由权利要求1-10的任意一项所述的镁及镁合金表面防腐处理方法所制备的镁制品。
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