CN103469195B - A kind of method using TEOS organosilicon liquid to process magnesium product surface - Google Patents
A kind of method using TEOS organosilicon liquid to process magnesium product surface Download PDFInfo
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- CN103469195B CN103469195B CN201310449205.3A CN201310449205A CN103469195B CN 103469195 B CN103469195 B CN 103469195B CN 201310449205 A CN201310449205 A CN 201310449205A CN 103469195 B CN103469195 B CN 103469195B
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- magnesium
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- organosilicon liquid
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 63
- 239000011777 magnesium Substances 0.000 title claims abstract description 63
- 239000007788 liquid Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 41
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 230000008569 process Effects 0.000 title claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 25
- 239000010703 silicon Substances 0.000 claims abstract description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical class N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000019257 ammonium acetate Nutrition 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 18
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 8
- 239000005695 Ammonium acetate Substances 0.000 claims description 7
- 229940043376 ammonium acetate Drugs 0.000 claims description 7
- 244000137852 Petrea volubilis Species 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000003921 oil Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 230000003111 delayed effect Effects 0.000 claims 1
- 238000004080 punching Methods 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 22
- 230000007797 corrosion Effects 0.000 abstract description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 8
- 229920001296 polysiloxane Polymers 0.000 abstract description 8
- 230000007062 hydrolysis Effects 0.000 abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 6
- -1 rare earth metal salt Chemical class 0.000 abstract description 6
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 4
- 239000012530 fluid Substances 0.000 abstract description 2
- 150000002910 rare earth metals Chemical class 0.000 abstract 1
- 238000009835 boiling Methods 0.000 description 12
- 238000010907 mechanical stirring Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 229910000861 Mg alloy Inorganic materials 0.000 description 8
- 238000011049 filling Methods 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- 238000007711 solidification Methods 0.000 description 5
- 230000008023 solidification Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910000838 Al alloy Inorganic materials 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 208000035126 Facies Diseases 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000013016 damping Methods 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Landscapes
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The invention discloses a kind of method using TEOS organosilicon liquid to process magnesium product surface.The method includes: 4～6 parts of TEOS, 10～30 parts of ethanol and 2～5 parts of ammonium acetates will be hydrolyzed in the basic conditions by (1) according to mass fraction；(2) in organosilicon liquid, rare earth metal salt is added；(3) magnesium goods are inserted and described rare earth organic silicon solution impregnates 2～6min；(3) 35～60min will be toasted at 90～115 DEG C through organosilicon liquid impregnated magnesium goods.The present invention is obtained organosilicon liquid containing the linear oligomer of holding silicone hydroxyl by TEOS by hydrolysis by dipped for surface, then in this silicone fluid, add rare earth metal salt, at high temperature film-forming, it is netted organic/inorganic composite film to form molecular structure at magnesium product surface, this organic/inorganic composite film is comparatively dense, improves the corrosion resistance of magnesium goods.
Description
Technical field
The present invention relates to the technical field that surface of metal product processes, particularly relate to a kind of employing TEOS organic
Silicon liquid processes the method for magnesium product surface.
Background technology
Magnesium is a kind of argenteous alkali metal, and it is again structural metal that is the lightest and that the most easily process.Magnesium alloy has
There are specific strength and specific stiffness high, the advantages such as damping, anti-acoustic capability are good.The tensile strength of magnesium alloy and aluminium alloy
Close, but specific strength is higher than aluminium alloy and some high strength steel.So, available magnesium alloy replace aluminium alloy and
Steel, alleviate the weight of hardware.The elastic modelling quantity of magnesium alloy is low, and damping property is good, can bear bigger
Shock loading, be suitable to manufacture the parts bearing strenuous vibration.The plasticity ratio aluminum of magnesium metal is low, under room temperature
Plastic deformation is little, can only should not carry out cold presswork 235 DEG C of pressure processing carried out above.But magnesium alloy
Cutting ability is very good, dimensional stability is high, can carry out various machine cut, it is also possible to carry out hydrogen arc
Weldering and the welding of other techniques.The fusing point relatively low (648.8 DEG C) of magnesium, forgeability are good, its good low temperature properties
Can be suitably used for manufacturing the parts of low operating temperatures.The heat dispersion of magnesium alloy is not only high than plastics, but also
It is better than aluminium alloy.Magnesium alloy has the highest shielding electromagnetic interference performance, it is adaptable to do the shell of electronic equipment.
It addition, it also has superconductivity and hydrogen storage property.The reclaiming of magnesium alloy is good, cheap,
Meet environmental requirement, the works such as military project, automobile, aircraft, mobile phone, computer, dynamo-electric five metals can be widely used in
On industry articles for use.
Though magnesium possesses above-mentioned series of advantages, but the electrode potential of magnesium the lowest (being-2.37V), even if at big compression ring
Border also can be formed oxide-film, and the PBR value of this oxide-film is less than 1 (being 0.99), constant temperature oxidation kinetics
Curve is linear.Therefore, the natural oxide film of magnesium is loose porous easy to fall off, it is impossible to plays protection matrix and exempts from
The effect weathered;The galvanic corrosion also having the second phase within alloy or impurity to cause, is susceptible to spot corrosion,
The corrosion resistance causing magnesium and alloy thereof is very poor, and application is restricted.The surface of magnesium goods is processed by prior art
Method has chemical composition coating, plating, chemical plating.These methods are the finest and close at the protecting film formed,
There is fault of construction, cause the corrosion resistance of surface treated magnesium goods compared to non-surface treated magnesium
Goods are not greatly improved.
Summary of the invention
In view of this, the present invention provides a kind of method using TEOS organosilicon liquid to process magnesium product surface,
The method can form the Organic inorganic film of densification at magnesium product surface, thus improves the corrosion-resistant of magnesium goods
Property.
A kind of method using TEOS organosilicon liquid to process magnesium product surface, comprises the following steps:
(1) according to mass fraction, 4～6 parts of TEOS, 10～30 parts of ethanol and 2～5 parts of ammonium acetates are added
Enter to water formation mixed liquor, the pH value regulating this mixed liquor is 8～11, at 50～65 DEG C disperse 1.5～
3h prepares organosilicon liquid；
(2) in described organosilicon liquid, Ce (NO is added3)3、(NH4)2S2O8And fluoride, fully dissolve shape
Become containing 5～15g/L Ce (NO3)3, 2～6g/L (NH4)2S2O8, 1～rare earth-the organosilicon of 4g/L fluoride
Solution.
(3) magnesium goods are inserted and described rare earth-organic silicon solution impregnates 2～6min；
(4) 35～60min will be toasted at 90～115 DEG C through rare earth-organosilicon liquid impregnated magnesium goods.
Wherein, in described step (1), the mass fraction of water is 60～90 parts.
Wherein, TEOS, ethanol and ammonium acetate are added by described step (1) in water particularly as follows: first
Ethanol and ammonium acetate are dissolved in the water, then by TEOS in the water being dissolved with ethanol and ammonium acetate slowly
Dropping, the time of described dropping is 30～60min.
Wherein, the mechanical agitation that in described step (1), the dispersion of mixed liquor uses rotating speed to be 150～400rpm.
Wherein, in described step (3), the number of times of dipping is 1～5 time.
Wherein, according to by first to after order, the most also include magnesium goods are carried out before described step (3)
With mechanical grinding, chemistry alkali liquor oil removing and distilled water flushing.
Wherein, described chemistry alkali liquor oil removing particularly as follows: insert the chemical bases that temperature is 70～80 DEG C by magnesium goods
Liquid impregnates 20～40min.
Wherein, described chemistry alkali liquor includes 40～60g/L NaOH, 50～70g/L Na3PO4, 20～30g/L
Na2CO3, 5～10g/L Na2SiO3。
Wherein, described mechanical grinding is particularly as follows: first slightly polish with 200 mesh sand paper thinner with 600 mesh sand paper
Polishing.
In above technical scheme, in step (1), TEOS is the English abbreviation of tetraethyl orthosilicate, and it is a kind of
Silane coupler, it is in the basic conditions with ethanol for catalyst generation hydrolysis.The mistake of this hydrolysis
Journey is divided into the three below stage: (1) ring opening hydrolysis becomes silanol；(2) reaction of shrinking between silanol generates linear
Product is the oligomer of main end silicone hydroxyl；(3) silicone hydroxyl of oligomer and oxidation on metal surface thing or hydration
The hydroxyl of thing forms hydrogen bond.In aforesaid three phases, sol particles nucleation and sol particles growth.Step
What the ammonium acetate suddenly added in (1) can improve hydrolysis carries out degree.The feed way of each reactive component is adopted
Use organic silicon monomer dripping method, i.e. TEOS to be slowly added dropwise in water, organic silicon monomer so can be made to be in " hungry
Starve " state, thus improve the conversion ratio of organic silicon monomer.
With Ce (NO in step (2)3)3As rare earth metal salt, relatively CeCl3For, the former strengthens magnesium goods
The effect of corrosion resistance more preferable.With (NH4)2S2O8As oxidation accelerator, film-forming temperature can be reduced, carry
High rate of film build.Using fluoride as stabilizer.
Step (4) will be to make organosilicon liquid at magnesium goods through the baking of organosilicon liquid impregnated magnesium goods
Film-forming.During this film-forming, the silicone hydroxyl of the oligomer of aforementioned linear crosslinks and forms
Tridimensional network.The silicone hydroxyl of oligomer and the hydroxyl of substrate surface generate more that bond energy relatively hydrogen bond is more simultaneously
Big covalent bond.The composite membrane that film is organic and inorganic phase formed after solidification, against magnesium surface in this composite membrane
Be have siliconoxygen bond be bonded with metallic atom formation inorganic phase, this inorganic phase away from magnesium surface by netted
The organic facies that macromolecular chain containing silica segment is constituted, organo-silicon coupling agent passes through siloxanes as reaction
Avtive spot, plays " bridge " effect between inorganic phase and organic facies, and Organic inorganic film is at organic net
Network introduces inorganic particle, improves network structure, enhance the mechanical performance of film, improve heat stability,
Improve the pore structure with modified membrane and distribution, adjustment apertures rate and adjustment hydrophilic-hydrophobic balance, improve film
Permeability and separation selectivity.
The present invention is obtained linear oligomer containing end silicone hydroxyl by TEOS by hydrolysis by dipped for surface
Organosilicon liquid, then in this silicone fluid add rare earth metal salt, at high temperature film-forming, with
Forming molecular structure at magnesium product surface is netted Organic inorganic film, and this Organic inorganic film is more
Densification, improves the corrosion resistance of magnesium goods.
Detailed description of the invention
The present invention is described in further detail the most in conjunction with the embodiments.
Magnesium goods to aftermentioned embodiment and comparative example carry out pretreatment in accordance with the following methods:
Magnesium goods are polished, first slightly polishes with 200 mesh sand paper, carefully beat with 600 mesh sand paper subsequently
Mill, is polishing to magnesium product surface and exposes metallic luster.The magnesium goods polished are inserted temperature is 70～80 DEG C
Chemical alkali liquor in impregnate and 20～40min with oil removing, the composition of this chemistry alkali liquor be: 40～60g/L NaOH,
50～70g/L Na3PO4, 20～30g/L Na2CO3, 5～10g/L Na2SiO3.By the magnesium goods of oil removing
Dry up with distilled water flushing and with nitrogen, with standby.
Embodiment 1
In terms of mass parts, by 10 parts of ethanol, 2 parts of ammonium acetates with add to filling four mouthfuls of 60 parts of deionized waters
Being sufficiently stirred in flask making it dissolve, the pH value regulating this solution is 8.Then four-hole boiling flask is inserted digital display
In formula thermostat water bath, and be respectively mounted on four mouths on four-hole boiling flask mechanical stirring device, thermometer,
Constant pressure funnel and condensing tube, below the liquid level of thermometer flask to be inserted.4 parts of TEOS are loaded perseverance
Pressure Dropping funnel, opens mechanical stirring device, and control rotating speed is 150rpm.The reading treating thermometer is 50 DEG C
After, open the valve of constant pressure funnel so that it is interior liquid uniform speed slow drips, control the time of dropping
For 30min.After treating the liquid dropping in constant pressure funnel, constant temperature 3h, prepare organosilicon liquid.
Ce (NO is added in described organosilicon liquid3)3、(NH4)2S2O8And fluoride, fully dissolve formation and contain
There is 5g/L Ce (NO3)3、2g/L(NH4)2S2O8, the rare earth-organic silicon solution of 1g/L fluoride.Will be through pre-place
The magnesium goods of reason are inserted and are impregnated 2min, the operation of repeated impregnations 5 times in the rare earth-organic silicon solution of aforementioned preparation.
To insert through organosilicon liquid impregnated magnesium goods makes its film-forming, hardening time be at 90 DEG C in baking oven
60min。
Embodiment 2
In terms of mass parts, by 30 parts of ethanol, 5 parts of ammonium acetates with add to filling four mouthfuls of 90 parts of deionized waters
Being sufficiently stirred in flask making it dissolve, the pH value regulating this solution is 9.Then four-hole boiling flask is inserted digital display
In formula thermostat water bath, and be respectively mounted on four mouths on four-hole boiling flask mechanical stirring device, thermometer,
Constant pressure funnel and condensing tube, below the liquid level of thermometer flask to be inserted.6 parts of TEOS are loaded perseverance
Pressure Dropping funnel, opens mechanical stirring device, and control rotating speed is 400rpm.The reading treating thermometer is 65 DEG C
After, open the valve of constant pressure funnel so that it is interior liquid uniform speed slow drips, control the time of dropping
For 60min.After treating the liquid dropping in constant pressure funnel, constant temperature 2.5h, prepare organosilicon liquid.
Ce (NO is added in described organosilicon liquid3)3、(NH4)2S2O8And fluoride, fully dissolve formation and contain
There is 15g/L Ce (NO3)3、6g/L(NH4)2S2O8, the rare earth-organic silicon solution of 4g/L fluoride.Will be through in advance
The magnesium goods processed are inserted and are impregnated 6min, the operation 1 of repeated impregnations in the rare earth-organic silicon solution of aforementioned preparation
Secondary.To insert through organosilicon liquid impregnated magnesium goods and baking oven make at 115 DEG C its film-forming, during solidification
Between be 35min.
Embodiment 3.
In terms of mass parts, by 20 parts of ethanol, 3.5 parts of ammonium acetates and addition to filling the four of 75 parts of deionized waters
Being sufficiently stirred for making it dissolve in mouth flask, the pH value regulating this solution is 9.5.Then four-hole boiling flask is inserted
In digital display type thermostat water bath, and it is respectively mounted mechanical stirring device, temperature on four mouths on four-hole boiling flask
Degree meter, constant pressure funnel and condensing tube, below the liquid level of thermometer flask to be inserted.By 5 parts of TEOS
Loading constant pressure funnel, open mechanical stirring device, control rotating speed is 350rpm.Treat the reading of thermometer
After being 60 DEG C, open the valve of constant pressure funnel so that it is interior liquid uniform speed slow drips, control dropping
Time be 45min.After treating the liquid dropping in constant pressure funnel, constant temperature 165min, prepare and have
Machine silicon liquid.
Ce (NO is added in described organosilicon liquid3)3、(NH4)2S2O8And fluoride, fully dissolve formation and contain
There is 10g/L Ce (NO3)3、4g/L(NH4)2S2O8, the rare earth-organic silicon solution of 2.5g/L fluoride.Will be through in advance
The magnesium goods processed are inserted and are impregnated 4min, the operation 3 of repeated impregnations in the rare earth-organic silicon solution of aforementioned preparation
Secondary.To insert through organosilicon liquid impregnated magnesium goods and baking oven make at 105 DEG C its film-forming, during solidification
Between be 47min.
Embodiment 4
In terms of mass parts, by 15 parts of ethanol, 3 parts of ammonium acetates with add to filling four mouthfuls of 70 parts of deionized waters
Being sufficiently stirred in flask making it dissolve, the pH value regulating this solution is 10.Then four-hole boiling flask is inserted number
In explicit thermostat water bath, and it is respectively mounted mechanical stirring device, temperature on four mouths on four-hole boiling flask
Meter, constant pressure funnel and condensing tube, below the liquid level of thermometer flask to be inserted.By 4.5 parts of TEOS dresses
Entering constant pressure funnel, open mechanical stirring device, control rotating speed is 300rpm.The reading treating thermometer is
After 55 DEG C, open the valve of constant pressure funnel so that it is interior liquid uniform speed slow drips, control dropping
Time is 35min.After treating the liquid dropping in constant pressure funnel, constant temperature 175min, prepare organic
Silicon liquid.
Ce (NO is added in described organosilicon liquid3)3、(NH4)2S2O8And fluoride, fully dissolve formation and contain
There is 8g/L Ce (NO3)3、3g/L(NH4)2S2O8, the rare earth-organic silicon solution of 2g/L fluoride.Will be through pre-place
The magnesium goods of reason are inserted and are impregnated 3min, the operation of repeated impregnations 4 times in the rare earth-organic silicon solution of aforementioned preparation.
To insert through organosilicon liquid impregnated magnesium goods makes its film-forming, hardening time be at 100 DEG C in baking oven
40min。
Embodiment 5
In terms of mass parts, by 25 parts of ethanol, 4 parts of ammonium acetates with add to filling four mouthfuls of 85 parts of deionized waters
Being sufficiently stirred in flask making it dissolve, the pH value regulating this solution is 11.Then four-hole boiling flask is inserted number
In explicit thermostat water bath, and it is respectively mounted mechanical stirring device, temperature on four mouths on four-hole boiling flask
Meter, constant pressure funnel and condensing tube, below the liquid level of thermometer flask to be inserted.By 5 parts of TEOS dresses
Entering constant pressure funnel, open mechanical stirring device, control rotating speed is 250rpm.The reading treating thermometer is
After 60 DEG C, open the valve of constant pressure funnel so that it is interior liquid uniform speed slow drips, control dropping
Time is 50min.After treating the liquid dropping in constant pressure funnel, constant temperature 160min, prepare organic
Silicon liquid.
Ce (NO is added in described organosilicon liquid3)3、(NH4)2S2O8And fluoride, fully dissolve formation and contain
There is 12g/L Ce (NO3)3、4.5g/L(NH4)2S2O8, the rare earth-organic silicon solution of 3.5g/L fluoride.Will be through
The magnesium goods of pretreatment are inserted and are impregnated 5min, the operation of repeated impregnations in the rare earth-organic silicon solution of aforementioned preparation
2 times.To insert through organosilicon liquid impregnated magnesium goods and baking oven will make at 110 DEG C its film-forming, solidification
Time is 52min.
Embodiment 6
In terms of mass parts, by 20 parts of ethanol, 3.5 parts of ammonium acetates and addition to filling the four of 90 parts of deionized waters
Being sufficiently stirred for making it dissolve in mouth flask, the pH value regulating this solution is 10.5.Then four-hole boiling flask is inserted
In digital display type thermostat water bath, and it is respectively mounted mechanical stirring device, temperature on four mouths on four-hole boiling flask
Degree meter, constant pressure funnel and condensing tube, below the liquid level of thermometer flask to be inserted.By 5 parts of TEOS
Loading constant pressure funnel, open mechanical stirring device, control rotating speed is 250rpm.Treat the reading of thermometer
After being 63 DEG C, open the valve of constant pressure funnel so that it is interior liquid uniform speed slow drips, control dropping
Time be 40min.After treating the liquid dropping in constant pressure funnel, constant temperature 170min, prepare and have
Machine silicon liquid.
Ce (NO is added in described organosilicon liquid3)3、(NH4)2S2O8And fluoride, fully dissolve formation and contain
There is 10g/L Ce (NO3)3、3.5g/L(NH4)2S2O8, the rare earth-organic silicon solution of 3g/L fluoride.Will be through in advance
The magnesium goods processed are inserted and are impregnated 5min, the operation 1 of repeated impregnations in the rare earth-organic silicon solution of aforementioned preparation
Secondary.To insert through organosilicon liquid impregnated magnesium goods and baking oven make at 105 DEG C its film-forming, during solidification
Between be 50min.
Comparative example
Undressed magnesium goods.
A small amount of water is instilled the copper product surface that method surface as described in embodiment and comparative example processes, treats water droplet
After the abundant drawout in surface, use Germany's dataphysics company OCA20 type contact angle measurement that water is connect
Feeler is tested.
Use BAS company 2323 of Japan type potentiostat to above example and the corrosion potential of comparative example
Test.Specifically, use three electrodes, i.e. using saturated calomel electrode as reference electrode, make with platinum electrode
For auxiliary electrode, test is at room temperature carried out.The NaCI solution that solution medium selects mass fraction to be 3.5%,
Measure with the scanning speed of 180mV/min, before test, sample soaked in this solution medium 20min,
So that etchant solution uniformly, stably immerses in sample measured surface.According to gathering and processing the electric current obtained
Tafel polarization curve with potential change.This polarization curve is analyzed just by the software carried with equipment
Available corrosion potential.
The magnesium goods processed through above example and comparative example are carried out corrosion weight loss test.Employing complete immersion loses
Weight test method, immerses sample in the NaOH solution of 20wt% and the NaCl solution of 3.5wt% respectively,
The corrosion experiment persistent period is respectively 240h and 340h, and keep corrosive medium temperature is 40 DEG C simultaneously, then
Weightlessness after corroding it measures, and tries to achieve corrosion rate.Before and after corrosion, sample all rushes through deionized water
Wash, EtOH Sonicate cleans, be vacuum dried, four steps of weighing.Corrosion rate calculates according to below equation:
Corrosion rate=(quality after quality-corrosion before corrosion)/(etching time × corrosion surface amasss).
The above test result of embodiment and comparative example is as follows:
As can be seen from the above table, 10wt%NaOH, 3.5wt%NaCl of embodiment surface treated magnesium goods
Corrosion weight loss rate significantly reduce compared with comparative example the most surface treated magnesium goods；Embodiment is surface treated
The negativity of the corrosion potential of magnesium goods significantly diminishes compared with comparative example the most surface treated magnesium goods, and this all says
The surface of the bright embodiment of the present invention processes the corrosion resistance enhancing magnesium goods largely.Embodiment is through table
The contact angle relatively comparative example of the magnesium goods that face processes has substantially change big, magnesium goods after this explanation surface treated
Hydrophobicity is greatly improved.
It should be noted that and understand, in the spirit without departing from appended claims the present invention for required protection
In the case of scope, it is possible to the present invention of foregoing detailed description is made various modifications and improvements.Therefore,
The scope of claimed technical scheme is not limited by given any specific exemplary teachings.
Applicant states, the present invention illustrates detailed process equipment and the technique of the present invention by above-described embodiment
Flow process, but the invention is not limited in above-mentioned detailed process equipment and technological process, i.e. do not mean that the present invention
Have to rely on above-mentioned detailed process equipment and technological process could be implemented.Person of ordinary skill in the field should
This understands, any improvement in the present invention, and the equivalence of raw material each to product of the present invention is replaced and auxiliary element
Interpolation, concrete way choice etc., within the scope of all falling within protection scope of the present invention and disclosure.
Claims (8)
1. one kind use TEOS organosilicon liquid process magnesium product surface method, it is characterised in that include with
Lower step:
(1) according to mass fraction, 4～6 parts of TEOS, 10～30 parts of ethanol and 2～5 parts of ammonium acetates are added
Entering to 60～90 parts of water formation mixed liquor, the pH value regulating this mixed liquor is 8～11, at 50～65 DEG C
Lower dispersion 1.5～3h prepares organosilicon liquid, TEOS, ethanol and ammonium acetate are added in water particularly as follows: first
First ethanol and ammonium acetate are dissolved in the water, then TEOS are delayed in the water being dissolved with ethanol and ammonium acetate
Slow dropping, the time of described dropping is 30～60min；
(2) in described organosilicon liquid, Ce (NO is added3)3、(NH4)2S2O8And fluoride, fully dissolve shape
Become containing 5～15g/L Ce (NO3)3, 2～6g/L (NH4)2S2O8, 1～rare earth-the organosilicon of 4g/L fluoride
Solution；
(3) magnesium goods are inserted and described rare earth-organic silicon solution impregnates 2～6min；
(4) will through described rare earth-organic silicon solution impregnated magnesium goods toast at 90～115 DEG C 35～
60min。
Method the most according to claim 1, it is characterised in that mixed liquor in described step (1)
The mechanical agitation that dispersion uses rotating speed to be 150～400rpm.
Method the most according to claim 1, it is characterised in that in described step (3), dipping is secondary
Number is 1～5 time.
Method the most according to claim 1, it is characterised in that described fluoride is NaF and/or KF.
Method the most according to claim 1, it is characterised in that according to by first to after order, described
The most also include before step (3) magnesium goods being carried out with mechanical grinding, chemistry alkali liquor oil removing and distilled water punching
Wash.
Method the most according to claim 5, it is characterised in that described chemistry alkali liquor oil removing particularly as follows:
Magnesium goods are inserted the chemical alkali liquor that temperature is 70～80 DEG C impregnates 20～40min.
Method the most according to claim 5, it is characterised in that described chemistry alkali liquor includes 40～60g/L
NaOH, 50～70g/L Na3PO4, 20～30g/L Na2CO3, 5～10g/L Na2SiO3。
Method the most according to claim 5, it is characterised in that described mechanical grinding is particularly as follows: first use
200 mesh sand paper are slightly polished, more carefully polish with 600 mesh sand paper.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101161869A (en) * | 2007-11-23 | 2008-04-16 | 哈尔滨工业大学 | Method for preparing rear earth corrosion resistant film on metal matrix composite surface |
| CN101717931A (en) * | 2009-12-22 | 2010-06-02 | 上海大学 | Rare-earth ion compound passivant used for copper surface passivation and preparation method thereof |
| CN102703893A (en) * | 2012-05-28 | 2012-10-03 | 武汉永正科技发展有限公司 | Environmental protection passivation solution for galvanized part and preparation method thereof |
| CN103173838A (en) * | 2013-04-11 | 2013-06-26 | 江西科技师范大学 | Magnesium alloy micro-arc oxidation electrolyte and micro-arc oxidation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4183489B2 (en) * | 2001-11-21 | 2008-11-19 | 日本ペイント株式会社 | Magnesium and / or magnesium alloy surface treatment method and magnesium and / or magnesium alloy product |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101161869A (en) * | 2007-11-23 | 2008-04-16 | 哈尔滨工业大学 | Method for preparing rear earth corrosion resistant film on metal matrix composite surface |
| CN101717931A (en) * | 2009-12-22 | 2010-06-02 | 上海大学 | Rare-earth ion compound passivant used for copper surface passivation and preparation method thereof |
| CN102703893A (en) * | 2012-05-28 | 2012-10-03 | 武汉永正科技发展有限公司 | Environmental protection passivation solution for galvanized part and preparation method thereof |
| CN103173838A (en) * | 2013-04-11 | 2013-06-26 | 江西科技师范大学 | Magnesium alloy micro-arc oxidation electrolyte and micro-arc oxidation method |
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