CN104357817B - Compound chrome-free tanning agent of magnesium alloy and preparation method thereof - Google Patents
Compound chrome-free tanning agent of magnesium alloy and preparation method thereof Download PDFInfo
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- CN104357817B CN104357817B CN201410639541.9A CN201410639541A CN104357817B CN 104357817 B CN104357817 B CN 104357817B CN 201410639541 A CN201410639541 A CN 201410639541A CN 104357817 B CN104357817 B CN 104357817B
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- magnesium alloy
- tanning agent
- molybdate
- free tanning
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- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 44
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 33
- 150000001875 compounds Chemical class 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- -1 phosphate ester Chemical class 0.000 claims abstract description 25
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 21
- 239000010452 phosphate Substances 0.000 claims abstract description 21
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical group [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims abstract description 18
- SRWKSFRBHIWJSD-UHFFFAOYSA-N 6-cyclohexylhexan-1-ol Chemical compound OCCCCCCC1CCCCC1 SRWKSFRBHIWJSD-UHFFFAOYSA-N 0.000 claims abstract description 17
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 17
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 claims abstract description 17
- 238000002454 metastable transfer emission spectrometry Methods 0.000 claims abstract description 17
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 17
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims abstract description 17
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 14
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 14
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000005642 Oleic acid Substances 0.000 claims abstract description 14
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 14
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 14
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011591 potassium Substances 0.000 claims abstract description 11
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 11
- 239000000470 constituent Substances 0.000 claims abstract description 10
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000015393 sodium molybdate Nutrition 0.000 claims abstract description 9
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 9
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical group [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001488 sodium phosphate Substances 0.000 claims abstract description 9
- 229910000162 sodium phosphate Inorganic materials 0.000 claims abstract description 9
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical group [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims abstract description 9
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 7
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims abstract description 7
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 7
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 7
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 7
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 7
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011701 zinc Substances 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- 238000002161 passivation Methods 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 abstract description 15
- 230000007797 corrosion Effects 0.000 abstract description 14
- 230000009849 deactivation Effects 0.000 abstract description 7
- 239000011651 chromium Substances 0.000 abstract description 5
- 231100000252 nontoxic Toxicity 0.000 abstract description 5
- 230000003000 nontoxic effect Effects 0.000 abstract description 5
- 229910000714 At alloy Inorganic materials 0.000 abstract description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052804 chromium Inorganic materials 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 206010010071 Coma Diseases 0.000 description 1
- 208000007217 Esophageal Stenosis Diseases 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 206010030194 Oesophageal stenosis Diseases 0.000 description 1
- 206010040943 Skin Ulcer Diseases 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000004532 chromating Methods 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Chemical class O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000002316 cosmetic surgery Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010892 electric spark Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- LQHZJYFIRFRDKF-UHFFFAOYSA-N gold magnesium Chemical compound [Mg].[Au] LQHZJYFIRFRDKF-UHFFFAOYSA-N 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011156 metal matrix composite Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 206010039083 rhinitis Diseases 0.000 description 1
- 231100000019 skin ulcer Toxicity 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 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
- C23C22/02—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 non-aqueous solutions
-
- 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
- C23C22/02—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 non-aqueous solutions
- C23C22/03—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 non-aqueous solutions containing phosphorus compounds
-
- 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
- C23C2222/20—Use of solutions containing silanes
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
The invention discloses a kind of compound chrome-free tanning agent of magnesium alloy and preparation method thereof, component and each constituent mass number are as follows: molybdate 4 ~ 10 parts, tungstates 2 ~ 6 parts, 1 ~ 3 part of potassium permanganate, ammonium titanium fluoride 2 ~ 5 parts, six phosphate ester of cyclohexanhexanol 6 ~ 15 parts, oleic acid 5 ~ 15 parts, MTES 1 ~ 5 part, tetraethyl orthosilicate 1 ~ 5 part.Also include phosphate 3 ~ 8 parts, 1 ~ 5 part of nitrate.Also include that siloxanes methylates 1 ~ 2 part of potassium.Described molybdate is sodium molybdate or ammonium molybdate.Described tungstates is sodium tungstate, artificial schellite or Zinc Tungstate.Described phosphate is sodium phosphate, and described nitrate is calcium nitrate.Passivator uses organic deactivation matter and mineral-type deactivation matter to proportion and forms compound chrome-free tanning agent, without chromium, safety non-toxic, environmentally safe, can form passivating film at alloy surface, improve the corrosion resistance of magnesium alloy.
Description
Technical field
The invention belongs to metal surface treatment chemical product technical field, be specifically related to a kind of compound chromium-free deactivation of magnesium alloy
Agent and preparation method thereof.
Background technology
Magnesium elements distribution on earth is extremely extensive, and reserves are huge, and magnesium alloy has a lot of characteristic, mainly has:
1, it is structural metallic materials the lightest in current all series alloys；2, electromagnetic wave shielding is good, is high-quality conductor；3, specific strength and
Specific stiffness is superior to iron and steel and aluminium alloy, is slightly poorer than best fibre reinforced plastics；4, processing characteristics is splendid, and with low cost；
5, absorb vibrations excellent performance, be conducive to the impact that reduction vibrations and noise are brought；6, high-termal conductivity, is better than aluminium alloy；7、
Performance nontoxic, recyclable is high, meets the requirement of sustainable development and environmental protection.Therefore during magnesium alloy is widely used in all trades and professions.
In highway vehicles field, the application of magnesium alloy mainly includes bicycle industry, auto industry and motorcycle
Industry etc..Magnesium alloy has great technological merit in combination property, from last century the nineties, Korea S, Japan and
American-European each high maneuver car produces commercial city and gradually Magnesium Alloys Components is incorporated on production line, is used for manufacturing control wheel, instrument
The parts such as dial plate, seat frame.
In war industry and aerospace field, magnesium alloy has obtained substantial amounts of application, its light weight, damping and noise reduction etc.
Feature, can very well meet the requirement to manufacturing material of this field.Currently it is mainly used in rocket, guided missile, aircraft, satellite
Parts produce and manufacture.There is the carbon of high specific strength, high ratio modulus and good thermal stability or the magnesium gold of graphite fibre enhancing
Metal-matrix composite material, is the preferable structural material of space industry, for artificial satellite wireless skeleton, bracing frame, reflecting mirror and sky
Between stand framework etc., structure efficiency is the highest.
In medical field, rustless steel is widely used in plastic surgery because of machinery and the corrosion resisting property of its excellence
Skeletal fixation, artificial joint and skeleton and the expandable stent etc. at esophageal stricture position, but need after physical recovery health
Carry out second operation to be extractd, bring another wound to health.Magnesium alloy itself has good mechanical performance, and magnesium unit
Element is one of necessary macroelement of human body, internal metabolic has been smoothed out irreplaceable positive role to raw.
Along with deepening continuously and New Processing fast development of magnesium alloy research, research and clinical practice for medical material bring
New opportunity, the emphasis that degradable magnesium alloy material has become present material science and field of biomedical materials receives much concern
And focus, have broad application prospects and business potential.
Manufacturing field at electric appliance and electronic, magnesium alloy not only has low, the excellent mechanics mechanical performance of lightweight, valency, well dissipates
Hot and recoverable, has outstanding electromagnetic wave shielding simultaneously, is eliminating mobile phone electromagnetic wave on Health Impact
There is positive effect, also comply with the 3C product exploitation demand to novel product.
Magnesium alloy has a lot of excellent performance, but decay resistance becomes a short slab in its many performance, limit
Make it extensively to apply.The corrosion of magnesium alloy occurs mainly on its surface contacted with media environment, corrosion rate mainly by
Surface and the medium of alloy are determined, therefore, the corrosion protection technology of magnesium alloy is typically all round media environment and alloy
Interface is carried out.The surfacecti proteon process of magnesium alloy can obtain extensive industrial applications for it and have weight with increasing the service life
The meaning wanted.Meanwhile, surface process is to improve with low cost, simple to operate in all multi-methods of corrosion stability of magnesium alloy but also capable having not only
The means of effect.Applying the most simple and effective in Corrosion Behaviors of Magnesium Alloys protective treatment at present is passivation of metal surfaces treatment technology, chromic acid
Salt is passivated as outstanding corrosion
Preparation is widely used in Treatment of Metal Surface.Chromating technique is the most ripe, but owing to Cr VI has
There is carcinogenecity, biological and human body can be produced fatal threat.Cr VI is the material that a kind of toxicity is the biggest simultaneously, and it is the most dirty
Dye environment, the symptom such as Long Term Contact can cause people to have a headache, goes into a coma, rhinitis, nasal perforation, skin ulcer and the various cancerations of initiation is right
Environmental and human health impacts is very harmful.Therefore, exploitation safety non-toxic free of contamination novel magnesium alloy passivator it is badly in need of.
Summary of the invention
It is an object of the invention to provide a kind of compound chrome-free tanning agent of magnesium alloy and preparation method thereof, passivator uses to be had
Machine class deactivation matter and mineral-type deactivation matter proportion and form compound chrome-free tanning agent, and without chromium, safety non-toxic, to ring
Border is pollution-free, can form passivating film at alloy surface, improve the corrosion resistance of magnesium alloy.
To achieve these goals, the technological means that the present invention uses is:
A kind of compound chrome-free tanning agent of magnesium alloy, component and each constituent mass number are as follows: molybdate 4 ~ 10 parts, tungsten
Hydrochlorate 2 ~ 6 parts, 1 ~ 3 part of potassium permanganate, ammonium titanium fluoride 2 ~ 5 parts, six phosphate ester of cyclohexanhexanol 6 ~ 15 parts, oleic acid 5 ~ 15 parts,
MTES 1 ~ 5 part, tetraethyl orthosilicate 1 ~ 5 part.
Also include phosphate 3 ~ 8 parts, 1 ~ 5 part of nitrate.
Also include that siloxanes methylates 1 ~ 2 part of potassium.
Described molybdate is sodium molybdate or ammonium molybdate.
Described tungstates is sodium tungstate, artificial schellite or Zinc Tungstate.
Described phosphate is sodium phosphate, and described nitrate is calcium nitrate.
The compound chrome-free tanning agent of magnesium alloy, component and each constituent mass number are as follows: molybdate 6 ~ 8 parts, tungstates 3
~ 5 parts, 2 parts of potassium permanganate, ammonium titanium fluoride 2.5 ~ 4.2 parts, phosphate 4 ~ 6 parts, 2 ~ 4 parts of nitrate, cyclohexanhexanol six phosphoric acid
Ester 8 ~ 12 parts, oleic acid 8 ~ 12 parts, MTES 2 ~ 4 parts, tetraethyl orthosilicate 2 ~ 4 parts, siloxanes methylates potassium
1.8 part.
The compound chrome-free tanning agent of magnesium alloy, component and each constituent mass number are as follows: molybdate 7 parts, tungstates 4
Part, 2 parts of potassium permanganate, ammonium titanium fluoride 3.6 parts, phosphate 5 parts, 3 parts of nitrate, six phosphate ester of cyclohexanhexanol 10 parts, oil
Acid 10 parts, MTES 3 parts, tetraethyl orthosilicate 3 parts, siloxanes methylates 1.8 parts of potassium.
The preparation method of the compound chrome-free tanning agent of magnesium alloy, mixes molybdate, tungstates, potassium permanganate, ammonium titanium fluoride
Close uniformly, obtain inorganic passivation；By six phosphate ester of cyclohexanhexanol, oleic acid, MTES, tetraethyl orthosilicate mixing
Uniformly, organic passivation thing is obtained；The most inorganic passivation is joined in organic passivation thing, be heated to 30 ~ 80 DEG C, stir
Mix uniformly, obtain compound chrome-free tanning agent.
Heating-up temperature is preferably 45 DEG C.
Beneficial effect: compound chrome-free tanning agent of magnesium alloy that the present invention provides and preparation method thereof, passivator uses to be had
Machine class deactivation matter and mineral-type deactivation matter proportion and form compound chrome-free tanning agent, and without chromium, safety non-toxic, to ring
Border is pollution-free, can form passivating film at alloy surface, improve the corrosion resistance of magnesium alloy.
Detailed description of the invention
Embodiment 1
A kind of compound chrome-free tanning agent of magnesium alloy, component and each constituent mass number are as follows: sodium molybdate 4 parts, Zinc Tungstate
2 parts, 1 part of potassium permanganate, ammonium titanium fluoride 2 parts, six phosphate ester of cyclohexanhexanol 6 parts, oleic acid 5 parts, MTES
1 part, tetraethyl orthosilicate 1 part.
By sodium molybdate, Zinc Tungstate, potassium permanganate, ammonium titanium fluoride mix homogeneously, obtain inorganic passivation；By cyclohexanhexanol six phosphorus
Acid esters, oleic acid, MTES, tetraethyl orthosilicate mix homogeneously, obtain organic passivation thing；The most before use by nothing
Machine passivation joins in organic passivation thing, is heated to 40 DEG C, stirs, and obtains compound chrome-free tanning agent.
Embodiment 2
A kind of compound chrome-free tanning agent of magnesium alloy, component and each constituent mass number are as follows: sodium molybdate 10 parts, Zinc Tungstate
6 parts, 3 parts of potassium permanganate, ammonium titanium fluoride 5 parts, six phosphate ester of cyclohexanhexanol 15 parts, oleic acid 15 parts, MTES 5
Part, tetraethyl orthosilicate 5 parts.
By sodium molybdate, Zinc Tungstate, potassium permanganate, ammonium titanium fluoride mix homogeneously, obtain inorganic passivation；By cyclohexanhexanol six phosphorus
Acid esters, oleic acid, MTES, tetraethyl orthosilicate mix homogeneously, obtain organic passivation thing；The most before use by nothing
Machine passivation joins in organic passivation thing, is heated to 40 DEG C, stirs, and obtains compound chrome-free tanning agent.
Embodiment 3
The compound chrome-free tanning agent of magnesium alloy, component and each constituent mass number are as follows: ammonium molybdate 6 parts, sodium tungstate 3
Part, 2 parts of potassium permanganate, ammonium titanium fluoride 2.5 parts, sodium phosphate 4 parts, calcium nitrate 2 parts, six phosphate ester of cyclohexanhexanol 8 parts, oil
Acid 8 parts, MTES 2 parts, tetraethyl orthosilicate 2 ~ 4 parts, siloxanes methylates 1.8 parts of potassium.
By ammonium molybdate, sodium tungstate, potassium permanganate, ammonium titanium fluoride, sodium phosphate, calcium nitrate mix homogeneously, obtain inorganic passivation；
Methylate potassium mix homogeneously by six phosphate ester of cyclohexanhexanol, oleic acid, MTES, tetraethyl orthosilicate, siloxanes,
Obtain organic passivation thing；The most inorganic passivation is joined in organic passivation thing, is heated to 50 DEG C, stirs,
Obtain compound chrome-free tanning agent.
Embodiment 4
The compound chrome-free tanning agent of magnesium alloy, component and each constituent mass number are as follows: ammonium molybdate 8 parts, sodium tungstate 5 parts,
2 parts of potassium permanganate, ammonium titanium fluoride 4.2 parts, sodium phosphate 6 parts, calcium nitrate 4 parts, six phosphate ester of cyclohexanhexanol 12 parts, oleic acid 12 parts,
MTES 2 ~ 4 parts, tetraethyl orthosilicate 4 parts, siloxanes methylates 1.8 parts of potassium.
By ammonium molybdate, sodium tungstate, potassium permanganate, ammonium titanium fluoride, sodium phosphate, calcium nitrate mix homogeneously, obtain inorganic passivation；
Methylate potassium mix homogeneously by six phosphate ester of cyclohexanhexanol, oleic acid, MTES, tetraethyl orthosilicate, siloxanes,
Obtain organic passivation thing；The most inorganic passivation is joined in organic passivation thing, is heated to 50 DEG C, stirs,
Obtain compound chrome-free tanning agent.
Embodiment 5
The compound chrome-free tanning agent of magnesium alloy, component and each constituent mass number are as follows: sodium molybdate 7 parts, artificial schellite 4
Part, 2 parts of potassium permanganate, ammonium titanium fluoride 3.6 parts, sodium phosphate 5 parts, calcium nitrate 3 parts, six phosphate ester of cyclohexanhexanol 10 parts, oil
Acid 10 parts, MTES 3 parts, tetraethyl orthosilicate 3 parts, siloxanes methylates 1.8 parts of potassium.
By sodium molybdate, artificial schellite, potassium permanganate, ammonium titanium fluoride, sodium phosphate and calcium nitrate mix homogeneously, obtain inorganic passivation
Thing；The potassium that six phosphate ester of cyclohexanhexanol, oleic acid, MTES, tetraethyl orthosilicate and siloxanes methylated mixing is all
Even, obtain organic passivation thing；The most inorganic passivation is joined in organic passivation thing, be heated to 30 ~ 80 DEG C, stirring
Uniformly, compound chrome-free tanning agent is obtained.
DK7732 type electric spark CNC wire-cut machine used for magnesium alloy is processed into specification is 13mm × 13mm × 5mm
Small pieces, polishing, until surface exposes metallic luster, smooth and no marking, as test sample, magnesium alloy is used reality
The compound chrome-free tanning agent executing example 1 ~ 5 is coated passivation, and coated weight is 5mL/g, and then 80 DEG C of dry 20min, then enter
Row performance test, the results are shown in Table 1.
With reference to machinery industry standard JB/T 6073-1992, use the compound chrome-free tanning agent of immersion corrosion test determination
The corrosion resisting property of coating is formed: taking sample and immerse immersion in 5% NaCl solution, sample plastic ties is hanged at Mg alloy surface
Hanging, upper end is away from liquid level more than 2cm, and solution pH value is 6.5, changes primary brine, uncovered placement, temperature 25 every six days
± 2 DEG C, recording each sample and the time of first red rust occur, the anti-corrosion time is as Evaluation of Corrosion Resistance result.
Neutral salt spray test:
Temperature in proof box is maintained at 35 DEG C, and compressed air to be preheating between 45 DEG C and be adjusted to enough pressure.
The mass concentration of sodium chloride solution is 5% ± 1%, and after condensation, the pH value of solution is between 6.5-7.2.During salt spray test,
Fall mist amount should control in following scope: every 80cm2In horizontal plane, between the fall mist amount average out to 1.0 ~ 2.0ml collected per hour,
Sample is placed in proof box and sprays continuously 72 hours, measure planar portions extent of corrosion.
Film adhesive is tested:
The film of test film is spaced 1mm and portrays the most vertical line, judge according to the size of gap slight crack extension
The fragility of film and the best to the adhesion property of this material.
Table 1:
Claims (6)
1. the compound chrome-free tanning agent of magnesium alloy, it is characterised in that component and each constituent mass number are as follows: molybdate 7
Part, tungstates 4 parts, 2 parts of potassium permanganate, ammonium titanium fluoride 3.6 parts, phosphate 5 parts, 3 parts of nitrate, cyclohexanhexanol six phosphorus
Acid esters 10 parts, oleic acid 10 parts, MTES 3 parts, tetraethyl orthosilicate 3 parts, siloxanes methylates 1.8 parts of potassium.
The compound chrome-free tanning agent of magnesium alloy the most according to claim 1, it is characterised in that: described molybdate be sodium molybdate or
Person's ammonium molybdate.
The compound chrome-free tanning agent of magnesium alloy the most according to claim 1, it is characterised in that: described tungstates be sodium tungstate,
Artificial schellite or Zinc Tungstate.
The compound chrome-free tanning agent of magnesium alloy the most according to claim 2, it is characterised in that: described phosphate is sodium phosphate,
Described nitrate is calcium nitrate.
5. the preparation method of the compound chrome-free tanning agent of magnesium alloy described in any one in claim 1 ~ 4, it is characterised in that: will
Molybdate, tungstates, potassium permanganate, ammonium titanium fluoride mix homogeneously, obtain inorganic passivation；By six phosphate ester of cyclohexanhexanol, oleic acid
, MTES, tetraethyl orthosilicate mix homogeneously, obtain organic passivation thing；The most inorganic passivation is added
Enter in organic passivation thing, be heated to 30 ~ 80 DEG C, stir, obtain compound chrome-free tanning agent.
The preparation method of the compound chrome-free tanning agent of magnesium alloy the most according to claim 5, it is characterised in that: heating-up temperature
It it is 45 DEG C.
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