CN103820792B - A kind of surface treatment method of kirsite - Google Patents
A kind of surface treatment method of kirsite Download PDFInfo
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- CN103820792B CN103820792B CN201410107140.9A CN201410107140A CN103820792B CN 103820792 B CN103820792 B CN 103820792B CN 201410107140 A CN201410107140 A CN 201410107140A CN 103820792 B CN103820792 B CN 103820792B
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- acid
- surface treatment
- treatment method
- kirsite
- organic acid
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- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000004381 surface treatment Methods 0.000 title claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 35
- 238000007747 plating Methods 0.000 claims abstract description 24
- 238000005240 physical vapour deposition Methods 0.000 claims abstract description 20
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims abstract description 13
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 8
- 238000000151 deposition Methods 0.000 claims abstract description 8
- 150000007524 organic acids Chemical class 0.000 claims description 34
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 24
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 21
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 19
- 229910052804 chromium Inorganic materials 0.000 claims description 19
- 239000011651 chromium Substances 0.000 claims description 19
- 229910052802 copper Inorganic materials 0.000 claims description 17
- 239000010949 copper Substances 0.000 claims description 17
- 238000005238 degreasing Methods 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 13
- 150000002500 ions Chemical class 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 230000004913 activation Effects 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 11
- KRQUFUKTQHISJB-YYADALCUSA-N 2-[(E)-N-[2-(4-chlorophenoxy)propoxy]-C-propylcarbonimidoyl]-3-hydroxy-5-(thian-3-yl)cyclohex-2-en-1-one Chemical compound CCC\C(=N/OCC(C)OC1=CC=C(Cl)C=C1)C1=C(O)CC(CC1=O)C1CCCSC1 KRQUFUKTQHISJB-YYADALCUSA-N 0.000 claims description 10
- 101150095401 AURKA gene Proteins 0.000 claims description 10
- 229910002651 NO3 Inorganic materials 0.000 claims description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 10
- -1 inorganic acid salt Chemical class 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 9
- 238000004512 die casting Methods 0.000 claims description 9
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 9
- 239000011975 tartaric acid Substances 0.000 claims description 9
- 235000002906 tartaric acid Nutrition 0.000 claims description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 8
- 235000006408 oxalic acid Nutrition 0.000 claims description 8
- 238000002161 passivation Methods 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052681 coesite Inorganic materials 0.000 claims description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052682 stishovite Inorganic materials 0.000 claims description 7
- 229910052905 tridymite Inorganic materials 0.000 claims description 7
- 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 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 6
- 235000015165 citric acid Nutrition 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 239000012188 paraffin wax Substances 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 230000036760 body temperature Effects 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 235000011194 food seasoning agent Nutrition 0.000 claims description 5
- 238000001771 vacuum deposition Methods 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- VCZQFJFZMMALHB-UHFFFAOYSA-N tetraethylsilane Chemical compound CC[Si](CC)(CC)CC VCZQFJFZMMALHB-UHFFFAOYSA-N 0.000 claims description 4
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 238000004544 sputter deposition Methods 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000756 V alloy Inorganic materials 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- HBVFXTAPOLSOPB-UHFFFAOYSA-N nickel vanadium Chemical compound [V].[Ni] HBVFXTAPOLSOPB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 229910001297 Zn alloy Inorganic materials 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 6
- 230000008021 deposition Effects 0.000 abstract description 5
- 238000009713 electroplating Methods 0.000 abstract description 5
- 239000002351 wastewater Substances 0.000 abstract description 3
- 231100000004 severe toxicity Toxicity 0.000 abstract description 2
- GTLDTDOJJJZVBW-UHFFFAOYSA-N zinc cyanide Chemical compound [Zn+2].N#[C-].N#[C-] GTLDTDOJJJZVBW-UHFFFAOYSA-N 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000000843 powder Substances 0.000 description 10
- 239000001993 wax Substances 0.000 description 10
- 239000008139 complexing agent Substances 0.000 description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 239000000080 wetting agent Substances 0.000 description 4
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241001272567 Hominoidea Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium
Abstract
The invention discloses a kind of surface treatment method of kirsite, first using plasma strengthens the fine and close anticorrosive coat of chemical vapour deposition (CVD), again using the mode depositing metal layers of physical vapour deposition (PVD) as prime coat, for follow-up plating provides the surface treatment method of the pre-plating layer with good combination power. The present invention replaces the cyanide Zinc alloy electroplating pre-treating technology of high pollution, severe toxicity by PECVD and PVD mode deposition zinc alloy prime coat, reduce discharge of wastewater and the pollution to environment, can be applicable to the plating accessory of bathroom, electronics, household electrical appliances, automobile and other industries.
Description
Technical field
The invention belongs to field of metal surface treatment, be specifically related to a kind of surface treatment method of kirsite.
Background technology
Kirsite is the alloy that adds other element compositions taking zinc as base. The alloying element often adding has aluminium, copper, magnesium, cadmium, tin, lead, titanium etc. Zinc alloy diecasting has that material is inexpensive, fusing point is low, power consumption less, mobility and good moldability, filling be abundant, the advantages such as the cast(ing) surface polishing pressing out, therefore, its surface ratio is applicable to the processing such as polishing, plating and spraying. At present, zinc alloy diecasting is applied to the fields such as automobile, electronics, household electrical appliances, bathroom more and more.
Owing to containing lead impurity element, cadmium, tin etc. in kirsite composition, cause foundry goods aging and deform, after long-term use, show as volume and swell, mechanical performance particularly plasticity significantly declines. Due to the poor chemical stability of kirsite, in air, easily corroded, in strong acid, highly basic, all can be subject to strong etch, therefore reach at present the object of anticorrosion or decoration by plating electrodeposited coating.
Conventional zinc alloy piece electroplating technology is: plating pre-treatment, the pre-copper facing of cyanide, pyrophosphoric acid copper facing, acid copper-plating, bright nickel plating, chromium plating; Other zinc alloy diecasting pre-plating process also has electroless copper, HEDP (HEDP) copper facing, signal bronze plating etc., but fails to obtain practical application because of different problems such as adhesion, cost, wastewater treatments in industry.
Because existing Electroplating on Zinc Die Castings technique almost all adopts cyanide electroplating to carry out bottoming and adopts pyrophosphoric acid copper facing to add thickness coating, cyanide has hypertoxicity and phosphorus-containing wastewater discharges the pollution to water quality; The superseded institute that is gesture containing backwardness production technologies such as cyanogen, phosphorous plating becomes. For implementing country's " heavy metal pollution integrated control " 12 " planning ", solve plating industry old skill upgrading and upgrade difficult problem, realize electroplate technology environmental protection, energy-conservation, reduction of discharging. Kirsite environment-friendly type new surface treatment process technological development application is imperative.
Plasma enhanced chemical vapor deposition method (PlasmaEn-hancedChemicalVaporDeposition) is utilized glow discharge, under high-frequency electric field, make low density gas ionization produce plasma, these ions are accelerated and obtain energy in electric field, can realize at a lower temperature SiO2The deposit of film. The feature of this method is that deposition temperature reduces greatly, and generally can be from LPCVD 700 DEG C drop to minimum 100 DEG C, and deposition rate is fast, can accurately control deposition rate (about 60nm/min), the membrane structure densification of generation.
Summary of the invention
The object of the present invention is to provide a kind of surface treatment method of kirsite, the present invention replaces the cyanide Zinc alloy electroplating pre-treating technology of high pollution, severe toxicity by PECVD and PVD mode deposition zinc alloy prime coat, reduce discharge of wastewater and the pollution to environment, can be applicable to the plating accessory of bathroom, electronics, household electrical appliances, automobile and other industries.
For achieving the above object, the present invention adopts following technical scheme:
A kind of surface treatment method of kirsite, it is characterized in that: first using plasma strengthens the fine and close anticorrosive coat of chemical vapour deposition (CVD), again using the mode depositing metal layers of physical vapour deposition (PVD) as prime coat, for follow-up plating provides the surface treatment method of the pre-plating layer with good combination power.
Concrete steps are as follows:
1) kirsite good die casting is carried out to ultrasonic paraffin removal processing; Wax removal water 10-30mL/L, temperature 60-70 DEG C, time 10min;
2) ultrasonic hot oil removing; Degreasing powder 20-40g/L, temperature 40-60 DEG C, time 4-6min;
3) electrolytic degreasing: Na2CO310-20g/L，Na2SiO310-20g/L, surfactant (one or more in alkylol APEO, APES, straight chain alcohol sodium sulphate) 5-10mL/L, temperature 40-60 DEG C, time 3-5min;
4) acid activation; Inorganic acid salt 30-50g/L, organic acid 10-30mL/L, temperature 30-40 DEG C, time 0.5-1min;
5) trivalent chromium passivation; Chromic salt 3g/L, nitrate 5-50g/L, organic acid 10-30mL/L, pH value 2-3, time 0.5-1min;
6) hot-air seasoning;
7) be transferred in vacuum coating equipment, be evacuated to 1 × 10-2Pa；
8) plasma aura activation; Ion gun power 5-10kW, dutycycle 75%, argon gas flow velocity 100-300SCCM, body of heater internal pressure 1.0-2.0Pa, temperature 80-100 DEG C, aura time 5-10min;
9) plasma enhanced chemical vapor deposition (PECVD) SiO2Fine and close anticorrosive coat; Furnace body temperature 80-150 DEG C, reactive material is tetramethylsilane or tetraethyl silane, O250-200SCCM, Ar50-200SCCM, vacuum pressure 5-20Pa in body of heater, radio-frequency power is 100-300W, time 5-15min;
10) physical vapor deposition (PVD) metal conducting layer; Multi-arc ion coating method or sputter coating method; Metal conducting layer comprises metal back layer and metal surface: metal back layer is one or both in titanium, zirconium, silver, chromium, nickel, stainless steel, nickel-vanadium alloy; Metal surface is the one in nickel, copper;
11) turn plating, organic acid for activating; Organic acid: 20-50mL/L;
12) electroplate without cyanogen, without phosphorus alkali copper; Taking cathode copper as anode, be 0.4-0.8A/dm in current density2, temperature is that 35-40 DEG C, surface tension are less than under the condition of 85dyne/cm and carry out; Electrolyte chief component is: complexing agent 40-60g/L, copper sulphate 12-20g/L and wetting agent 0.1-0.5g/L;
13) follow-up electro-coppering, nickel, chromium etc.
The described inorganic acid salt of step (4) is the one in sodium sulphate, niter cake, sodium chloride, and organic acid is the one in pyrovinic acid, citric acid, tartaric acid, oxalic acid.
The described chromic salt of step (5) is the one in chromium chloride, chromium sulfate, chromium sulfate basic; Nitrate is the one in potassium nitrate, sodium nitrate, ammonium nitrate, zinc nitrate; Organic acid is the one in oxalic acid, citric acid, tartaric acid.
The described organic acid of step (11) is the one in oxalic acid, citric acid, tartaric acid.
Remarkable advantage of the present invention is:
(1) adopt without phosphorus paraffin removal, oil removing process;
(2) trivalent chromium passivation process;
(3) carry out kirsite base material surface passivation layer by plasma glow discharge mode and carry out modification;
(4) using plasma strengthens chemical vapour deposition (CVD) (PECVD) SiO2Fine and close masking film;
(5) adopt physical vapor deposition (PVD) metal conducting layer.
Brief description of the drawings
Fig. 1 is film layer structure schematic diagram of the present invention.
Detailed description of the invention
Embodiment 1 kirsite panel
A kind of concrete steps of surface treatment method of kirsite are as follows:
1) kirsite good die casting is carried out to ultrasonic paraffin removal processing; Wax removal water 10mL/L, temperature 60 C, time 10min;
2) ultrasonic hot oil removing; Degreasing powder 20g/L, 40 DEG C of temperature, time 4min;
3) electrolytic degreasing: Na2CO310g/L，Na2SiO310g/L, surfactant 5mL/L, 40 DEG C of temperature, time 3min;
4) acid activation: inorganic acid salt 30g/L, organic acid 10mL/L, 30 DEG C of temperature, time 0.5min;
5) trivalent chromium passivation; Chromic salt 3g/L, nitrate 5g/L, organic acid 10mL/L, pH value 2, time 0.5min;
6) hot-air seasoning;
7) be transferred in vacuum coating equipment, be evacuated to 1 × 10-2Pa；
8) plasma aura activation; Ion gun power 5kW, dutycycle 75%, argon gas flow velocity 100SCCM, body of heater internal pressure 1.0Pa, 80 DEG C of temperature, aura time 5min;
9) plasma enhanced chemical vapor deposition (PECVD) SiO2Fine and close anticorrosive coat; 120 DEG C of furnace body temperatures, reactive material is tetramethylsilane, O250SCCM, Ar50SCCM, vacuum pressure 5Pa in body of heater, radio-frequency power is 100W, time 5min;
10) physical vapor deposition (PVD) metal conducting layer; Metal conducting layer comprises metal back layer and metal surface: metal back layer adopts sputter plating stainless steel, stainless steel target power output 7kW, argon gas flow velocity 200sccm, furnace pressure 0.4Pa, plated film time 8min; Metal surface adopts multi-arc ion coating nickel, nickel target current 80A, argon gas flow velocity 80sccm, furnace pressure 0.3Pa, plated film time 10min.
11) turn plating, organic acid for activating; Organic acid: 20mL/L;
12) electroplate without cyanogen, without phosphorus alkali copper; Taking cathode copper as anode, be 0.4A/dm in current density2, temperature is that 35 DEG C, surface tension are less than under the condition of 85dyne/cm and carry out; Electrolyte chief component is: complexing agent 40g/L, copper sulphate 12g/L and wetting agent 0.1g/L;
13) follow-up electro-coppering, nickel, chromium etc.
The described inorganic acid salt of step (4) is sodium sulphate, and organic acid is pyrovinic acid.
The described chromic salt of step (5) is chromium chloride; Nitrate is potassium nitrate; Organic acid is oxalic acid.
The described organic acid of step (11) is oxalic acid.
Described Wax removal water adopts Atotech company that UniCleanSoakBCR Wax removal water is provided.
Described degreasing powder adopts Atotech company that UniClean151 degreasing powder is provided.
Embodiment 2 kirsite handles
A kind of concrete steps of surface treatment method of kirsite are as follows:
1) kirsite good die casting is carried out to ultrasonic paraffin removal processing; Wax removal water 30mL/L, temperature 70 C, time 10min;
2) ultrasonic hot oil removing; Degreasing powder 40g/L, temperature 60 C, time 6min;
3) electrolytic degreasing: Na2CO320g/L，Na2SiO320g/L, surfactant 10mL/L, temperature 60 C, time 5min;
4) acid activation: inorganic acid salt 50g/L, organic acid 30mL/L, 40 DEG C of temperature, time 1min;
5) trivalent chromium passivation; Chromic salt 3g/L, nitrate 50g/L, organic acid 30mL/L, pH value 3, time 1min;
6) hot-air seasoning;
7) be transferred in vacuum coating equipment, be evacuated to 1 × 10-2Pa；
8) plasma aura activation; Ion gun power 10kW, dutycycle 75%, argon gas flow velocity 300SCCM, body of heater internal pressure 2.0Pa, 100 DEG C of temperature, aura time 10min;
9) plasma enhanced chemical vapor deposition (PECVD) SiO2Fine and close anticorrosive coat; 100 DEG C of furnace body temperatures, reactive material is tetraethyl silane, O2200SCCM, Ar200SCCM, vacuum pressure 20Pa in body of heater, radio-frequency power is 300W, time 15min;
10) physical vapor deposition (PVD) metal conducting layer; Metal conducting layer comprises metal back layer and metal surface: metal back layer adopts multi-arc ion coating chromium, chromium target current 70A, argon gas flow velocity 50sccm, furnace pressure 0.2Pa, plated film time 5min; Metal surface adopts sputter copper facing, copper target power output 8kW, argon gas flow velocity 200sccm, furnace pressure 0.4Pa, plated film time 10min.
11) turn plating, organic acid for activating; Organic acid: 50mL/L;
12) electroplate without cyanogen, without phosphorus alkali copper; Taking cathode copper as anode, be 0.8A/dm in current density2, temperature is that 40 DEG C, surface tension are less than under the condition of 85dyne/cm and carry out; Electrolyte chief component is: complexing agent 60g/L, copper sulphate 20g/L and wetting agent 0.5g/L;
13) follow-up electro-coppering, nickel, chromium etc.
The described inorganic acid salt of step (4) is niter cake, and organic acid is citric acid.
The described chromic salt of step (5) is chromium sulfate; Nitrate is sodium nitrate; Organic acid is citric acid.
The described organic acid of step (11) is citric acid.
Described Wax removal water adopts Atotech company that UniCleanSoakBCR Wax removal water is provided.
Described degreasing powder adopts Atotech company that UniClean151 degreasing powder is provided.
Embodiment 3 kirsite tap bases (labyrinth)
A kind of concrete steps of surface treatment method of kirsite are as follows:
1) kirsite good die casting is carried out to ultrasonic paraffin removal processing; Wax removal water 20mL/L, 65 DEG C of temperature, time 10min;
2) ultrasonic hot oil removing; Degreasing powder 30g/L, temperature 50 C, time 5min;
3) electrolytic degreasing: Na2CO315g/L，Na2SiO315g/L, surfactant 7.5mL/L, temperature 50 C, time 4min;
4) acid activation: inorganic acid salt 40g/L, organic acid 20mL/L, 35 DEG C of temperature, time 1min;
5) trivalent chromium passivation; Chromic salt 3g/L, nitrate 25g/L, organic acid 20mL/L, pH value 2, time 0.7min;
6) hot-air seasoning;
7) be transferred in vacuum coating equipment, be evacuated to 1 × 10-2Pa；
8) plasma aura activation; Ion gun power 7kW, dutycycle 75%, argon gas flow velocity 200SCCM, body of heater internal pressure 1.5Pa, 90 DEG C of temperature, aura time 7min;
9) plasma enhanced chemical vapor deposition (PECVD) SiO2Fine and close anticorrosive coat; 90 DEG C of furnace body temperatures, reactive material is tetramethylsilane or tetraethyl silane, O2120SCCM, Ar120SCCM, vacuum pressure 12Pa in body of heater, radio-frequency power is 200W, time 15min;
10) physical vapor deposition (PVD) metal conducting layer; Metal conducting layer comprises metal back layer and metal surface: metal back layer adopts Sputter Deposition of Chromium, chromium target power output 8kW, argon gas flow velocity 200sccm, furnace pressure 0.4Pa, plated film time 10min; Metal surface adopts sputter copper facing, copper target power output 10kW, argon gas flow velocity 200sccm, furnace pressure 0.4Pa, plated film time 20min;
11) turn plating, organic acid for activating; Organic acid: 35mL/L;
12) electroplate without cyanogen, without phosphorus alkali copper; Taking cathode copper as anode, be 0.6A/dm in current density2, temperature is that 37 DEG C, surface tension are less than under the condition of 85dyne/cm and carry out; Electrolyte chief component is: complexing agent 50g/L, copper sulphate 16g/L and wetting agent 0.3g/L;
13) follow-up electro-coppering, nickel, chromium etc.
The described inorganic acid salt of step (4) is sodium chloride, and organic acid is tartaric acid.
The described chromic salt of step (5) is chromium sulfate basic; Nitrate is ammonium nitrate; Organic acid is tartaric acid.
The described organic acid of step (11) is tartaric acid.
Described Wax removal water adopts Atotech company that UniCleanSoakBCR Wax removal water is provided.
Described degreasing powder adopts Atotech company that UniClean151 degreasing powder is provided.
The foregoing is only preferred embodiment of the present invention, all equalizations of doing according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (8)
1. the surface treatment method of a kirsite, it is characterized in that: first using plasma strengthens the fine and close anticorrosive coat of chemical vapour deposition (CVD), again using the mode depositing metal layers of physical vapour deposition (PVD) as prime coat, for follow-up plating provides the surface treatment method of the pre-plating layer with good combination power;
Concrete steps are as follows:
1) kirsite good die casting is carried out to ultrasonic paraffin removal processing;
2) ultrasonic hot oil removing;
3) electrolytic degreasing;
4) acid activation;
5) trivalent chromium passivation;
6) hot-air seasoning;
7) be transferred in vacuum coating equipment, be evacuated to 1 × 10-2Pa；
8) plasma aura activation;
9) plasma enhanced chemical vapor deposition SiO2Fine and close anticorrosive coat;
10) physical vapour deposition (PVD) metal conducting layer;
11) turn plating, organic acid for activating;
12) electroplate without cyanogen, without phosphorus alkali copper;
13) follow-up electro-coppering, nickel or chromium.
2. the surface treatment method of kirsite according to claim 1, is characterized in that: the acid activation that step (4) is described, mainly adopts inorganic acid salt and organic acid to mix; Wherein inorganic acid salt is the one in sodium sulphate, niter cake, sodium chloride; Organic acid is the one in pyrovinic acid, citric acid, tartaric acid, oxalic acid.
3. the surface treatment method of kirsite according to claim 1, is characterized in that: the trivalent chromium passivation that step (5) is described, mainly adopts chromic salt, nitrate and organic acid to mix; Wherein chromic salt is the one in chromium chloride, chromium sulfate, chromium sulfate basic; Nitrate is the one in potassium nitrate, sodium nitrate, ammonium nitrate, zinc nitrate; Organic acid is the one in oxalic acid, citric acid, tartaric acid.
4. the surface treatment method of kirsite according to claim 1, is characterized in that: the ion gun of step (8) is hall ion source or Kaufman ion source; Ion gun power 2-5kW, dutycycle 75%, argon gas flow velocity 100-300sccm, body of heater internal pressure 1.0-2.0Pa, temperature 80-100 DEG C, aura time 5-10min.
5. the surface treatment method of kirsite according to claim 1, is characterized in that: in step (9), vacuum furnace body temperature is 80-150 DEG C.
6. the surface treatment method of kirsite according to claim 1, is characterized in that: in step (9), key reaction material is tetramethylsilane or tetraethyl silane; Other gas: O2And Ar; In body of heater, vacuum pressure is 5-20Pa, and radio-frequency power is 100-300W, and the time is 5-15min.
7. the surface treatment method of kirsite according to claim 1, is characterized in that: step (10) mainly adopts multi-arc ion coating embrane method or sputter coating method; Wherein metal conducting layer comprises metal back layer and metal surface: metal back layer is one or both in titanium, zirconium, silver, chromium, nickel, stainless steel, nickel-vanadium alloy; Metal surface is the one in nickel, copper.
8. the surface treatment method of kirsite according to claim 1, is characterized in that: the described organic acid of step (11) is the one in oxalic acid, citric acid, tartaric acid.
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| CN105239071A (en) * | 2015-10-26 | 2016-01-13 | 维沃移动通信有限公司 | Method for manufacturing electronic equipment shell and electronic equipment |
| CN107227451B (en) * | 2017-06-26 | 2019-04-19 | 广东振华科技股份有限公司 | A kind of vacuum coating method and noble metal coated article of noble metal oxygen-proof film |
| CN107488848A (en) * | 2017-07-27 | 2017-12-19 | 泾县信达工贸有限公司 | A kind of preparation method of corrosion-resistant lid of electric cooking-vessel |
| TWI714284B (en) * | 2018-09-27 | 2020-12-21 | 日商Ｔｏｔｏ股份有限公司 | Faucet metal parts |
| CN111394734A (en) * | 2020-05-06 | 2020-07-10 | 苏州清飙科技有限公司 | Stripping polishing solution for die-casting zinc alloy and preparation method thereof |
| CN113193348A (en) * | 2021-04-25 | 2021-07-30 | 江门市德众泰工程塑胶科技有限公司 | Preparation method of antenna containing LCP (liquid Crystal Polymer) base material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1780931A (en) * | 2003-01-23 | 2006-05-31 | H.C.施塔克公司 | Pre-plating surface treatments for enhanced galvanic-corrosion resistance |
| CN101989571A (en) * | 2009-08-06 | 2011-03-23 | 中芯国际集成电路制造(上海)有限公司 | Forming method of contact plug and plating platform device |
| CN102543734A (en) * | 2010-12-08 | 2012-07-04 | 中国科学院微电子研究所 | MOS (metal oxide semiconductor) device with memory function and forming method of MOS device |
| TW201333229A (en) * | 2012-02-15 | 2013-08-16 | Hauzer Techno Coating Bv | A coated article of martensitic steel and a method of forming a coated article of steel |
-
2014
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1780931A (en) * | 2003-01-23 | 2006-05-31 | H.C.施塔克公司 | Pre-plating surface treatments for enhanced galvanic-corrosion resistance |
| CN101989571A (en) * | 2009-08-06 | 2011-03-23 | 中芯国际集成电路制造(上海)有限公司 | Forming method of contact plug and plating platform device |
| CN102543734A (en) * | 2010-12-08 | 2012-07-04 | 中国科学院微电子研究所 | MOS (metal oxide semiconductor) device with memory function and forming method of MOS device |
| TW201333229A (en) * | 2012-02-15 | 2013-08-16 | Hauzer Techno Coating Bv | A coated article of martensitic steel and a method of forming a coated article of steel |
| CN103252938A (en) * | 2012-02-15 | 2013-08-21 | 豪泽尔涂层技术有限公司 | Coated article of martensitic steel and method of forming coated article of steel |
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Address after: Tianfeng road in Jimei District of Xiamen City, Fujian Province, No. 69 361000 Patentee after: Runner (Xiamen) Corp. Address before: Tianfeng road in Jimei District of Xiamen City, Fujian Province, No. 69 361000 Patentee before: Xiamen Runner Industrial Corp. |
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