CN103254762B - Preparation method of organosilicon sol-gel coating for magnesium alloy substrate surface corrosion resistance - Google Patents
Preparation method of organosilicon sol-gel coating for magnesium alloy substrate surface corrosion resistance Download PDFInfo
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Abstract
The present invention provides a preparation method of an organosilicon sol-gel coating for magnesium alloy substrate surface corrosion resistance. According to the preparation method, alkoxy silane is adopted as a precursor, a salt compound of a metal cerium and/or a salt compound of a metal lanthanum is adopted as a catalyst, and a hydrolysis-condensation reaction is performed to obtain an organosilicon sol-gel coating. Experiment results confirm that: compared with conventional acid catalysts, the catalyst of the present invention provides high catalytic hydrolysis capability on alkoxy silane, and has a metal corrosion slowing effect, such that the organosilicon sol-gel coating prepared by using the catalyst can provide a good corrosion resistance effect for magnesium alloys compared with the organosilicon sol-gel coating prepared by using the conventional acid catalyisi.
Description
Technical field
The present invention relates to field of metal surface treatment technology, be specifically related to the preparation method of the anticorrosion organic silicon sol-gel coat of a kind of magnesium alloy matrix surface.
Background technology
Magnesium alloy tool is famous with low density, is considered to the outstanding substitute of aluminium alloy and non-ferrous metal in the fields such as automotive industry.But the chemical property of magnesium alloy is active, and can form fine and close passivation layer on surface unlike aluminium alloy, therefore the non-constant of its erosion resistance, significantly limit its practical application.
In order to improve the service life of magnesium alloy, usually adopting and preparing coating at magnesium alloy matrix surface, and magnesium alloy substrate is carried out to the methods such as differential arc oxidation and protect.In recent years, organic silicon sol-gel coat is because having excellent heat-resisting, mechanical property, corrosion resistance and having excellent bonding force with metallic matrix and receive much concern.Organic silicon sol-gel coat generally adopts organoalkoxysilane to be precursor, and under hydrolyst existence condition, obtained by the hydrolysis-condensation reaction of presoma, hydrolysis reaction and condensation reaction occur simultaneously in this process, and its reactional equation is as follows:
There are some researches show, an acidic catalyst or basic catalyst all can use the hydrolyst of said hydrolyzed-condensation reaction, but hydrolysis reaction wherein has different dependencys from the pH value of condensation reaction to reaction system.When using an acidic catalyst, hydrolysis reaction is very fast, and condensation reaction is comparatively slow, so obtained organic silicon sol-gel is more stable.And when using basic catalyst, condensation reaction is very fast, and hydrolysis reaction is comparatively slow, so obtained organic silicon sol-gel stability is poor.Based on this, the many employings of organic silicon sol-gel coat are prepared under an acidic catalyst existence condition.But, for magnesium alloy substrate, because magnesium alloy has high reaction activity under sour environment, easily there is evolving hydrogen reaction, therefore can affect the corrosion resistance nature of organic silicon sol-gel coat on its surface.
Summary of the invention
Technical purpose of the present invention is for above-mentioned deficiency, provides the preparation method of the anticorrosion organic silicon sol-gel coat of a kind of magnesium alloy matrix surface, and the coating utilizing the method to obtain has excellent corrosionproof protection effect to magnesium alloy substrate.
Technical scheme of the present invention is: the preparation method of the anticorrosion organic silicon sol-gel coat of a kind of magnesium alloy matrix surface, being specially: employing organoalkoxysilane is precursor, being hydrolyzed preservative solution by obtaining organoalkoxysilane after presoma, organic solvent and hydrolyst Homogeneous phase mixing; Heat treated is carried out after this preservative solution being smeared, spray or is spin-coated on magnesium alloy matrix surface, organic silicon sol-gel coat is obtained after to be dried, or magnesium alloy substrate is immersed in certain hour in this preservative solution, carry out heat treated after taking-up, after to be dried, obtain organic silicon sol-gel coat; It is characterized in that: described catalyzer is the salt compounds of metallic cerium and/or the salt compounds of lanthanoid metal, in the salt compounds of described metallic cerium, cerium ion is Tricationic and/or quadrivalent cation.
The salt compounds of described metallic cerium includes but not limited to CeCl
3, Ce(NO
3)
3, Ce
2(SO
4)
3, Ce(SO
4)
2deng in one or more; The salt compounds of described lanthanoid metal includes but not limited to LaCl
3, La(NO
3)
3, La
2(SO
4)
3deng in one or more.
Described organoalkoxysilane is a compounds well-known to those skilled in the art, refers in molecule silicoorganic compound having a Si-OR unit at least and composition thereof, and wherein R is CH
3-, CH
3cH
2-, CH
3cH
2cH
2-, CH
3cH
2cH
2cH
2-,-CH(CH
3)
2deng in one.
Described organoalkoxysilane includes but not limited to tetramethoxy-silicane, methyl trimethoxy base oxosilane, vinyl trimethoxy, propyl trimethoxy silicane, phenyltrimethoxysila,e, dodecyltrimethoxysilane, mercaptopropyi Trimethoxy silane, methacryloxypropyl trimethoxy silane, glycidoxypropyltrime,hoxysilane, dimethyldimethoxysil,ne, tetraethoxysilane, organoalkoxysilane is tetraethoxysilane, methyl triethyl oxosilane, vinyl triethoxyl, propyl-triethoxysilicane, phenyl triethoxysilane, dodecyl triethoxysilane, Mercaptopropyltriethoxysilane, methacryloxypropyl, glycidoxypropyl group triethoxyl silane, at least one in dimethyldiethoxysilane etc.
Described organic solvent includes but not limited to methyl alcohol, ethanol, propyl alcohol, Virahol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diglyme, 1, one or more mixture in 3-dioxolane, dioxane, tetrahydrofuran (THF), acetone, acetonitrile, DMF, methyl-sulphoxide.
As preferably, described catalyst quality accounts for 10 of organoalkoxysilane quality
-6~ 0.1, more preferably 10
-5~ 10
-2.
As preferably, under certain temperature condition, by presoma, organic solvent and hydrolyst Homogeneous phase mixing, be hydrolyzed, obtain organoalkoxysilane hydrolysis preservative solution.This temperature is preferably 20 DEG C ~ 150 DEG C, more preferably 25 DEG C ~ 100 DEG C, most preferably is 27 DEG C ~ 80 DEG C.This hydrolysis time is preferably 10 minutes ~ 48 hours.
The preservative solution that the present invention is used for Mg alloy surface directly can use or re-use with after the dilution of suitable thinner, as coating magnesium alloys surface to prevent the supercoat corroded.During concrete use, preservative solution of the present invention is smeared, spray or blade coating at Mg alloy surface, or magnesium alloy be immersed in preservative solution of the present invention take out after certain hour; Finally, the Mg alloy surface after process is suitably carried out heat drying, obtains corrosion protection coating.
As preferably, described Heating temperature is 35 DEG C ~ 200 DEG C, more preferably 50 DEG C ~ 150 DEG C.
As preferably, described heat-up time is 10 minutes ~ 180 minutes, preferably 30 minutes ~ 90 minutes further.
In sum, the present invention adopts hydrolysis-condensation reaction to prepare organic silicon sol-gel coat at magnesium alloy matrix surface, and wherein adopt new catalyzer to replace conventional an acidic catalyst, this catalyzer is the salt of rare earth metal cerium and lanthanum, namely containing Ce
3+, Ce
4+, La
3+salt compound, compared with existing an acidic catalyst, this catalyzer tool has the following advantages:
(1) this catalyzer can promote silane hydrolyzate well, has high catalytic hydrolysis ability, avoid in addition use an acidic catalyst time low ph value to the disadvantageous effect of magnesium alloy substrate;
(2) this catalyzer itself is a metalloid inhibiter, adopts the organic silicon sol-gel coat of this catalyst preparing even can provide passivation effect for the magnesium alloy substrate of certain model, more improves the Corrosion Protection of this matrix;
Experiment confirms, when magnesium alloy matrix surface prepares organic silicon sol-gel coat, compared with the antiseptic property of the organic silicon sol-gel coat adopting existing catalyzer to obtain, the organic silicon sol-gel coat adopting the salt compounds of rare earth metal cerium provided by the invention and lanthanum to react obtained as catalyzer by hydrolysis-condensation can provide better anticorrosion ability for magnesium alloy.
Accompanying drawing explanation
Fig. 1 is tetraethoxysilane, mercaptopropyl trimethoxysilane and comparative example 1 and the infrared spectra of the hydrolyzed silane solution in embodiment 1;
The AZ91 that Fig. 2 is AZ91 magnesium alloy substrate, surface in comparative example 1 and embodiment 1 after process is covered with organic silicon sol-gel coat is the linear polarisation curves figure in the NaCl solution of 0.35% in concentration;
Fig. 3 is tetraethoxysilane, methyltrimethoxy silane and comparative example 2 and the infrared spectra of the hydrolyzed silane solution in embodiment 2;
Fig. 4 is AZ31 magnesium alloy, process AZ31 magnesium alloy that rear surface is covered with organic silicon sol-gel coat through comparative example 2 and embodiment 2 is polarization curve in the NaCl solution of 0.35% in concentration;
Fig. 5 is JDM21 magnesium alloy, process JDM2 magnesium alloy that rear surface is covered with organic silicon sol-gel coat through comparative example 3 and embodiment 3 is polarization curve in the NaCl solution of 0.35% in concentration.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, it is pointed out that the following stated embodiment is intended to be convenient to the understanding of the present invention, and any restriction effect is not play to it.
Comparative example 1:
The present embodiment is the comparative example of following examples 1.
In the present embodiment, magnesium alloy substrate is AZ91, prepares anticorrosion organic silicon sol-gel coat at this magnesium alloy matrix surface, this coating with mercaptopropyi Trimethoxy silane and tetraethoxysilane for precursor, adopt acid to be hydrolyzed-condensation reaction and obtaining for catalyzer, concrete steps are as follows:
(1) by 3.75g mercaptopropyi Trimethoxy silane, 1.25g tetraethoxysilane, 20g ethanol, and 5g0.5mol/L formic acid solution mixes, and at room temperature stirs 12 hours, obtains organoalkoxysilane hydrolyzate;
(2) Mg alloy AZ91 mechanical polishing, ultrasonic cleaning be placed in above-mentioned organoalkoxysilane hydrolyzate and soak 1 minute, after taking-up, thermal treatment 30 minutes at 120 DEG C, obtains the contrast AZ91 sample that surface is covered with organic silicon sol-gel coat after to be dried.
Embodiment 1:
In the present embodiment, magnesium alloy substrate is identical with above-mentioned comparative example 1, prepares anticorrosion organic silicon sol-gel coat at this magnesium alloy matrix surface, and this coating for precursor, adopts Ce(NO with mercaptopropyi Trimethoxy silane and tetraethoxysilane
3)
3for catalyzer is hydrolyzed-condensation reaction and obtaining, concrete steps are as follows:
(1) by 3.75g mercaptopropyi Trimethoxy silane, 1.25g tetraethoxysilane, 20g ethanol, and 5g concentration is the Ce(NO of 0.1%
3)
3solution mixes, and at room temperature stirs 12 hours, obtains organoalkoxysilane hydrolyzate;
(2) Mg alloy AZ91 mechanical polishing, ultrasonic cleaning be placed in above-mentioned organoalkoxysilane hydrolyzate and soak 1 minute, after taking-up, thermal treatment 30 minutes at 120 DEG C, obtains the enforcement AZ91 sample that surface is covered with organic silicon sol-gel coat after to be dried.
Respectively infrared test is carried out to the organoalkoxysilane hydrolyzate in above-mentioned comparative example 1 and embodiment 1 step (1), to characterize organoalkoxysilane, i.e. tetraethoxysilane and mercaptopropyi Trimethoxy silane, the hydrolysis situation under catalyst action.
Concrete testing method is: respectively by organoalkoxysilane, i.e. tetraethoxysilane and mercaptopropyi Trimethoxy silane, and the organoalkoxysilane hydrolysis in comparative example 1 and embodiment 1 directly drops on KBr salt sheet, adopts absorption mode record.
Infrared test result as shown in Figure 1, as can be seen from Figure 1:
(1) tetraethoxysilane, relevant to hydrolysis reaction in mercaptopropyi Trimethoxy silane is 967cm
-1si-OCH
2cH
3and 816cm
-1si-OCH
3absorption peak;
(2) in the infrared spectra of the organoalkoxysilane hydrolyzed solution in embodiment 1 and comparative example 1, these two peaks all disappear, and show that wherein alkoxy grp is substantially thoroughly hydrolyzed, an acidic catalyst namely in similar comparative example 1, the catalyzer Ce(NO in embodiment 1
3)
3there is the ability of good alkoxy silane catalyzed hydrolysis;
(3) in the infrared spectra of the organoalkoxysilane hydrolyzed solution in comparative example 1 and embodiment 1,1105cm
-1neighbouring broad peak is relevant to the vibration of Si-O-Si, namely relevant with condensation reaction, and the similar explanation of both peak shapes two kinds of organoalkoxysilane hydrolyzed solutions have close stability.
The contrast AZ91 sample of organic silicon sol-gel coat is covered with to the surface after process in above-mentioned AZ91 matrix, comparative example 1 and embodiment 1 step (2) and implements AZ91 sample and carry out linear polarisation curves measurement.Measuring method is: ionogen to be mass concentration be 0.35% NaCl solution, adopt three-electrode method, wherein reference electrode is mercurous chloride electrode, be platinum electrode to electrode, working electrode is AZ91 magnesium alloy, comparative example 1 step (2) is middle processes the contrast AZ91 sample that the surface obtained is covered with organic silicon sol-gel coat, and in embodiment 1 step (2), processing the enforcement AZ91 sample that the surface obtained is covered with organic silicon sol-gel coat, sweep velocity is 10mV/s.
Linear polarisation curves test result as shown in Figure 2, as can be seen from Figure 2:
(1) compared with the AZ91 sample not carrying out surface protection; corrosion current and the corrosion potential of the AZ91 sample after comparative example 1 processes all decrease, and the reduction of corrosion current shows that the organic silicon sol-gel coat obtained after comparative example 1 processes can provide certain isolated Cl for AZ91 magnesium alloy
-, water, O
2deng the ability of corrosion, the reduction of corrosion potential illustrates there is strong reactive behavior between AZ91 magnesium alloy substrate and this organic silicon sol-gel coat;
(2) with the AZ91 electrode not carrying out surface protection, and the contrast AZ91 sample after comparative example 1 processes is compared, and the corrosion current of the enforcement AZ91 sample after embodiment 1 processes is minimum, but corrosion potential is the highest; Minimum organic silicon sol-the gel coat showing to obtain after embodiment 1 processes of corrosion current can provide better isolated preservative effect for AZ91; Corrosion potential is the highest shows that organoalkoxysilane hydrolyzate obtained in embodiment 1 has certain passivation effect to AZ91 magnesium alloy substrate;
Therefore, can draw according to above-mentioned linear polarisation curves result: when organic silicon sol-gel coat is prepared on Mg alloy AZ91 surface, adopt Ce
3+be catalyzer ratio H
+the Corrosion Protection doing organic silicon sol-gel coat that catalyzer obtains is better.
Comparative example 2:
The present embodiment is the comparative example of following examples 2.
In the present embodiment, magnesium alloy substrate is AZ31 magnesium alloy, anticorrosion organic silicon sol-gel coat is prepared at this magnesium alloy matrix surface, this coating with methyltrimethoxy silane and tetraethoxysilane for precursor, adopt formic acid solution be catalyzer be hydrolyzed-condensation reaction obtains, concrete steps are as follows:
(1) by 8.16g methyltrimethoxy silane, 4.16g tetraethoxysilane, 7.02g ethanol, and 7.02g0.2mol/L formic acid solution mixes, and stirs 6 hours, obtain organoalkoxysilane hydrolyzate at 40 DEG C;
(2) mechanical polishing of AZ31 magnesium alloy electrode, ultrasonic cleaning be placed in organoalkoxysilane hydrolyzate and soak 1 minute, after taking-up, thermal treatment 1 hour at 100 DEG C, obtains the contrast AZ31 sample that surface is covered with organic silicon sol-gel coat after to be dried.
Embodiment 2:
In the present embodiment, magnesium alloy substrate is identical with above-mentioned comparative example 2, prepares anticorrosion organic silicon sol-gel coat at this magnesium alloy matrix surface, and this coating for precursor, adopts La(NO with methyltrimethoxy silane and tetraethoxysilane
3)
3make hydrolysis reaction catalyzer to be hydrolyzed-condensation reaction and obtaining, concrete steps are as follows:
(1) by 8.16g methyltrimethoxy silane, 4.16g tetraethoxysilane, 7.02g ethanol, and 7.02g0.1%La(NO
3)
3solution mixes, and stirs 6 hours, obtain organoalkoxysilane hydrolyzate at 40 DEG C;
(2) mechanical polishing of AZ31 magnesium alloy, ultrasonic cleaning be placed in organoalkoxysilane hydrolyzate and soak 1 minute, after taking-up, thermal treatment 1 hour at 100 DEG C, obtains the enforcement AZ31 sample that surface is covered with organic silicon sol-gel coat after to be dried.
Respectively infrared test is carried out to the organoalkoxysilane hydrolyzate in above-mentioned comparative example 2 and embodiment 2 step (1), to characterize organoalkoxysilane, i.e. tetraethoxysilane and trimethoxysilyl propyl methacrylate TMOS, the hydrolysis situation under catalyst action.Concrete testing method is identical with the testing method in above-described embodiment 1, that is: respectively by organoalkoxysilane, i.e. tetraethoxysilane and methyltrimethoxy silane, and the organoalkoxysilane hydrolyzate in comparative example 1 and embodiment 1 directly drops on KBr salt sheet, adopts absorption mode record.
Infrared test result as shown in Figure 3, as can be seen from Figure 3:
(1) tetraethoxysilane, relevant to hydrolysis reaction in methyltrimethoxy silane is 967cm
-1si-OCH
2cH
3and 848cm
-1si-OCH
3absorption peak;
(2) in the infrared spectra of the organoalkoxysilane hydrolyzed solution in embodiment 2 and comparative example 2, these two peaks all disappear, and show that wherein organoalkoxysilane is all thoroughly hydrolyzed, an acidic catalyst also in similar comparative example 2, the catalyzer La(NO in embodiment 2
3)
3there is the ability of good alkoxy silane catalyzed hydrolysis;
(3) in the infrared spectra of the organoalkoxysilane hydrolyzed solution in comparative example 2 and embodiment 2,1105cm
-1neighbouring broad peak is relevant to the vibration of Si-O-Si, that is relevant with condensation reaction, and the similar explanation of both peak shapes, two kinds of organoalkoxysilane hydrolyzed solutions have close stability.
The contrast AZ31 sample not protecting the surface in magnesium alloy AZ31 sample, comparative example 2 and embodiment 2 step (2) after process to be covered with organic silicon sol-gel coat to above-mentioned and implement AZ31 sample and carry out linear polarisation curves measurement.Measuring method is: ionogen to be mass concentration be 0.35% NaCl solution, adopt three-electrode method, wherein reference electrode is mercurous chloride electrode, be platinum electrode to electrode, working electrode is magnesium alloy AZ31 matrix, comparative example 2 step (2) is middle processes the contrast AZ31 sample that the surface obtained is covered with organic silicon sol-gel coat, and in embodiment 2 step (2), processing the enforcement AZ31 sample that the surface obtained is covered with organic silicon sol-gel coat, sweep velocity is 10mV/s.
Linear polarisation curves test result as shown in Figure 4, as can be seen from Figure 4 shows:
(1) compared with the AZ31 magnesium alloy sample not carrying out surface protection; corrosion current and the corrosion potential of the AZ31 magnesium alloy sample after comparative example 2 processes all decrease, and the reduction of corrosion current shows that the organic silicon sol-gel coat obtained after comparative example 2 processes can provide certain isolated Cl for AZ31 magnesium alloy
-, water, O
2etc. the antiseptic power of corrosion factor;
(2) with the AZ31 magnesium alloy electrode not carrying out surface protection, and the AZ31 magnesium alloy electrode after comparative example 2 processes is compared, and the corrosion current of the AZ31 magnesium alloy electrode after embodiment 2 processes is minimum; Minimum organic silicon sol-the gel coat showing to obtain after comparative example 2 processes of corrosion current can provide better isolated preservative effect for AZ31 magnesium alloy;
Therefore, can draw according to above-mentioned linear polarisation curves result: when organic silicon sol-gel coat is prepared on AZ31 surface, adopt La
3+be catalyzer ratio H
+the Corrosion Protection doing organic silicon sol-gel coat that catalyzer obtains is better.
Comparative example 3:
The present embodiment is the comparative example of following examples 3.
In the present embodiment, magnesium alloy substrate is JDM2 magnesium alloy electrode, prepares anticorrosion organic silicon sol-gel coat at this magnesium alloy matrix surface, and this coating take methyltrimethoxy silane as precursor, adopt formic acid solution be catalyzer be hydrolyzed-condensation reaction obtains, concrete steps are as follows:
(1) by 6g methyltrimethoxy silane, 21g ethanol, and 3g0.05mol/L formic acid solution mixes, and stirs 2 hours, obtain organoalkoxysilane hydrolyzate at 60 DEG C;
(2) mechanical polishing of JDM2 magnesium alloy electrode, ultrasonic cleaning be placed in organoalkoxysilane hydrolyzate and soak 1 minute, after taking-up, thermal treatment 90 minutes at 80 DEG C, obtains the contrast JDM2 sample that surface is covered with organic silicon sol-gel coat after to be dried.
Embodiment 3:
In the present embodiment, magnesium alloy substrate is identical with above-mentioned comparative example 3, prepares anticorrosion organic silicon sol-gel coat at this magnesium alloy matrix surface, and this coating take methyltrimethoxy silane as precursor, adopts Ce(NO
3)
3make hydrolysis reaction catalyzer to be hydrolyzed-condensation reaction and obtaining, concrete steps are as follows:
(1) by 6g methyltrimethoxy silane, 21g ethanol, and 3g0.1%Ce(NO
3)
3solution mixes, and stirs 2 hours, obtain organoalkoxysilane hydrolyzate at 60 DEG C;
(2) mechanical polishing of JDM2 magnesium alloy, ultrasonic cleaning be placed in organoalkoxysilane hydrolyzate and soak 1 minute, after taking-up, thermal treatment 90 minutes at 80 DEG C, obtains the enforcement JDM2 sample that surface is covered with organic silicon sol-gel coat after to be dried.
The contrast JDM2 sample not protecting the surface in magnesium alloy JDM2 sample, comparative example 3 and embodiment 3 step (2) after process to be covered with organic silicon sol-gel coat to above-mentioned and implement JDM2 sample and carry out linear polarisation curves measurement.Measuring method is: ionogen to be mass concentration be 0.35% NaCl solution, adopt three-electrode method, wherein reference electrode is mercurous chloride electrode, be platinum electrode to electrode, working electrode is magnesium alloy JDM2 matrix, comparative example 3 step (2) is middle processes the contrast AZ31 sample that the surface obtained is covered with organic silicon sol-gel coat, and in embodiment 3 step (2), processing the enforcement JDM2 sample that the surface obtained is covered with organic silicon sol-gel coat, sweep velocity is 10mV/s.
Linear polarisation curves test result as shown in Figure 5, as can be seen from Figure 5 shows:
(1) compared with the JDM2 sample not carrying out surface protection; corrosion current and the corrosion potential of the JDM2 sample after comparative example 1 processes all decrease, and the reduction of corrosion current shows that the organic silicon sol-gel coat obtained after contrast enforcement 3 processes can provide certain isolated Cl for JDM2 magnesium alloy
-, water, O
2deng the ability of corrosion, the reduction of corrosion potential illustrates there is strong reactive behavior between JDM2 magnesium alloy substrate and this organic silicon sol-gel coat;
(2) with the JDM2 electrode not carrying out surface protection, and the contrast JDM2 sample after comparative example 3 processes is compared, and the corrosion current of the enforcement JDM2 sample after embodiment 3 processes is minimum, but corrosion potential is the highest; Minimum organic silicon sol-the gel coat showing to obtain after embodiment 3 processes of corrosion current can provide better isolated preservative effect for JDM2; Corrosion potential is the highest shows that organoalkoxysilane hydrolyzate obtained in embodiment 3 has certain passivation effect to JDM2 magnesium alloy substrate;
Therefore, can draw according to above-mentioned linear polarisation curves result: when organic silicon sol-gel coat is prepared on magnesium alloy JDM2 surface, adopt Ce
3+be catalyzer ratio H
+the Corrosion Protection doing organic silicon sol-gel coat that catalyzer obtains is better.
Above-described embodiment has been described in detail technical scheme of the present invention; be understood that and the foregoing is only specific embodiments of the invention; be not limited to the present invention; all make in spirit of the present invention any amendment, supplement or equivalent to replace, all should be included within protection scope of the present invention.
Claims (14)
1. the preparation method of the anticorrosion organic silicon sol-gel coat of magnesium alloy matrix surface, employing organoalkoxysilane is precursor, is hydrolyzed preservative solution by obtaining organoalkoxysilane after presoma, organic solvent and hydrolyst Homogeneous phase mixing; Heat treated is carried out after this preservative solution being smeared, spray or is spin-coated on magnesium alloy matrix surface, organic silicon sol-gel coat is obtained after to be dried, or magnesium alloy substrate is immersed in certain hour in this preservative solution, carry out heat treated after taking-up, after to be dried, obtain organic silicon sol-gel coat; It is characterized in that: described catalyzer is the salt compounds of metallic cerium and/or the salt compounds of lanthanoid metal, in the salt compounds of described metallic cerium, cerium ion is Tricationic and/or quadrivalent cation.
2. the preparation method of the anticorrosion organic silicon sol-gel coat of magnesium alloy matrix surface according to claim 1, is characterized in that: the salt compounds of described metallic cerium comprises CeCl
3, Ce (NO
3)
3, Ce
2(SO
4)
3, Ce (SO
4)
2in one or more.
3. the preparation method of the anticorrosion organic silicon sol-gel coat of magnesium alloy matrix surface according to claim 1, is characterized in that: the salt compounds of described lanthanoid metal comprises LaCl
3, La (NO
3)
3, La
2(SO
4)
3in one or more.
4. the preparation method of the anticorrosion organic silicon sol-gel coat of magnesium alloy matrix surface according to claim 1, it is characterized in that: described organoalkoxysilane refers in molecule silicoorganic compound having a Si-OR unit at least and composition thereof, wherein R is CH
3-, CH
3cH
2-, CH
3cH
2cH
2-, CH
3cH
2cH
2cH
2-,-CH (CH
3)
2in one.
5. the preparation method of the anticorrosion organic silicon sol-gel coat of magnesium alloy matrix surface according to claim 1, it is characterized in that: described organoalkoxysilane comprises tetramethoxy-silicane, methyl trimethoxy base oxosilane, vinyl trimethoxy, propyl trimethoxy silicane, phenyltrimethoxysila,e, dodecyltrimethoxysilane, mercaptopropyi Trimethoxy silane, methacryloxypropyl trimethoxy silane, glycidoxypropyltrime,hoxysilane, dimethyldimethoxysil,ne, tetraethoxysilane, organoalkoxysilane is tetraethoxysilane, methyl triethyl oxosilane, vinyl triethoxyl, propyl-triethoxysilicane, phenyl triethoxysilane, dodecyl triethoxysilane, Mercaptopropyltriethoxysilane, methacryloxypropyl, glycidoxypropyl group triethoxyl silane, at least one in dimethyldiethoxysilane.
6. the preparation method of the anticorrosion organic silicon sol-gel coat of magnesium alloy matrix surface according to claim 1, it is characterized in that: described organic solvent comprises methyl alcohol, ethanol, propyl alcohol, Virahol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diglyme, 1, one or more mixture in 3-dioxolane, dioxane, tetrahydrofuran (THF), acetone, acetonitrile, DMF, methyl-sulphoxide.
7. the preparation method of the anticorrosion organic silicon sol-gel coat of the magnesium alloy matrix surface according to claim arbitrary in claim 1 to 6, is characterized in that: described catalyst quality accounts for 10 of organoalkoxysilane quality
-6~ 0.1.
8. the preparation method of the anticorrosion organic silicon sol-gel coat of the magnesium alloy matrix surface according to claim arbitrary in claim 1 to 6, is characterized in that: described catalyst quality accounts for 10 of organoalkoxysilane quality
-5~ 10
-2.
9. the preparation method of the anticorrosion organic silicon sol-gel coat of the magnesium alloy matrix surface according to claim arbitrary in claim 1 to 6, is characterized in that: presoma, organic solvent and hydrolyst are obtained organoalkoxysilane after Homogeneous phase mixing under temperature is 20 DEG C ~ 150 DEG C conditions and is hydrolyzed preservative solution.
10. the preparation method of the anticorrosion organic silicon sol-gel coat of the magnesium alloy matrix surface according to claim arbitrary in claim 1 to 6, is characterized in that: presoma, organic solvent and hydrolyst are obtained organoalkoxysilane after Homogeneous phase mixing under temperature is 25 DEG C ~ 100 DEG C conditions and is hydrolyzed preservative solution.
The preparation method of 11. anticorrosion organic silicon sol-gel coats of magnesium alloy matrix surface according to claim arbitrary in claim 1 to 6, is characterized in that: described Heating temperature is 35 DEG C ~ 200 DEG C.
The preparation method of 12. anticorrosion organic silicon sol-gel coats of magnesium alloy matrix surface according to claim arbitrary in claim 1 to 6, is characterized in that: described Heating temperature is 50 ~ 150 DEG C.
The preparation method of 13. anticorrosion organic silicon sol-gel coats of magnesium alloy matrix surface according to claim arbitrary in claim 1 to 6, is characterized in that: described heat-up time is 10 minutes ~ 180 minutes.
The preparation method of 14. anticorrosion organic silicon sol-gel coats of magnesium alloy matrix surface according to claim arbitrary in claim 1 to 6, is characterized in that: described heat-up time is 30 minutes ~ 90 minutes.
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| CN103484018A (en) * | 2013-09-24 | 2014-01-01 | 昆山凯诺尔金属制品有限公司 | Method for processing surface of magnesium product by using organosilicone liquid with mercapto group |
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| CN109722165A (en) * | 2017-10-31 | 2019-05-07 | 中国科学院宁波材料技术与工程研究所 | Modified graphene/sulfur-containing organosilicon composite anti-corrosive liquid, coating, preparation method and application |
| CN108587449B (en) * | 2018-04-27 | 2019-07-05 | 上海大学 | A kind of Cr@ZnO@TiO capsule of nano and preparation method thereof and a kind of gel coat high-strength steel |
| CN109136903B (en) * | 2018-09-07 | 2020-06-09 | 中南大学 | Silane composite film doped with rare earth salt and zeolite and preparation and application methods thereof |
| CN110845959A (en) * | 2019-11-29 | 2020-02-28 | 湖北环宇化工有限公司 | Self-atomization organic silicon resin and preparation method thereof |
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| CN115709158B (en) * | 2022-11-21 | 2023-09-26 | 中山大学 | Metal long-acting anti-corrosion phenolic amine modified sol-gel film and preparation method thereof |
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| KR100491951B1 (en) * | 2002-11-25 | 2005-05-30 | 한국화학연구원 | Non-chromic aqueous organic/inorganic sol-gel compositions for corrosion-resistance and anti-finger on metal and preparation method of thereof |
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| CN1079972A (en) * | 1986-10-03 | 1993-12-29 | Ppg工业公司 | Preparation hybrid polymer method |
| CN1970136A (en) * | 2006-10-27 | 2007-05-30 | 中国科学技术大学 | Organic-inorganic hybridized anion exchange membrane preparation method |
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