CN103254762A - 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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- CN103254762A CN103254762A CN2013100416830A CN201310041683A CN103254762A CN 103254762 A CN103254762 A CN 103254762A CN 2013100416830 A CN2013100416830 A CN 2013100416830A CN 201310041683 A CN201310041683 A CN 201310041683A CN 103254762 A CN103254762 A CN 103254762A
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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 anticorrosion preparation method with organic silicon sol-gel coat of a kind of magnesium alloy matrix surface.
Background technology
The magnesium alloy tool is celebrated with low density, is considered to the outstanding substitute of aluminium alloy and non-ferrous metal in the fields such as automotive industry.Yet the chemical property of magnesium alloy is active, can form fine and close passivation layer on the surface unlike aluminium alloy, so the non-constant of its erosion resistance, has greatly limited its practical application.
Prepare coating in order to improve the service life of magnesium alloy, usually to adopt at magnesium alloy matrix surface, and magnesium alloy substrate is carried out methods such as differential arc oxidation protect.In recent years, organic silicon sol-gel coat receives much concern because having excellent heat-resisting, mechanical property, corrosion resistance and having good bonding force with metallic matrix.It is precursor that organic silicon sol-gel coat generally adopts organoalkoxysilane, and under the hydrolyst existence condition, the hydrolysis-condensation reaction by presoma makes, and hydrolysis reaction and condensation reaction take place simultaneously in this process, and its reactional equation is as follows:
There are some researches show that an acidic catalyst or basic catalyst be the hydrolyst of available said hydrolyzed-condensation reaction all, but wherein hydrolysis reaction and condensation reaction has different dependencys to the pH value of reaction system.When using an acidic catalyst, hydrolysis reaction is very fast, and condensation reaction is slower, so the organic silicon sol-gel that makes is more stable.And when using basic catalyst, condensation reaction is very fast, and hydrolysis reaction is slower, so the organic silicon sol-gel stability that makes is relatively poor.Based on this, adopt of organic silicon sol-gel coat prepares under an acidic catalyst existence condition more.Yet, for magnesium alloy substrate, because magnesium alloy has high reaction activity under sour environment, evolving hydrogen reaction takes place easily, therefore can influence organic silicon sol-gel coat at its surperficial corrosion resistance nature.
Summary of the invention
Technical purpose of the present invention is at above-mentioned deficiency, provides a kind of magnesium alloy matrix surface anticorrosion preparation method with organic silicon sol-gel coat, and the coating of utilizing this method to make has excellent corrosionproof protection effect to magnesium alloy substrate.
Technical scheme of the present invention is: the anticorrosion preparation method with organic silicon sol-gel coat of a kind of magnesium alloy matrix surface, be specially: the employing organoalkoxysilane is precursor, obtains organoalkoxysilane hydrolysis preservative solution with presoma, organic solvent and after hydrolyst evenly mixes; This preservative solution smeared, sprays or be spin-coated on magnesium alloy matrix surface after carry out heat treated, obtain organic silicon sol-gel coat after to be dried, perhaps magnesium alloy substrate is immersed in certain hour in this preservative solution, carry out heat treated after the taking-up, obtain organic silicon sol-gel coat after to be dried; It is characterized in that: described catalyzer is the salt compounds of metallic cerium and/or the salt compounds of lanthanoid metal, and cerium ion is Tricationic and/or quadrivalent cation in the salt compounds of described metallic cerium.
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) in waiting one or more.
Described organoalkoxysilane is a compounds well-known to those skilled in the art, refers to silicoorganic compound that have at least in the molecule Si-OR unit 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 a kind of.
Described organoalkoxysilane includes but not limited to tetramethoxy-silicane, methyl trimethoxy base oxosilane, vinyl trimethoxy, propyl trimethoxy silicane, phenyltrimethoxysila,e, the dodecyl Trimethoxy silane, the sulfydryl propyl trimethoxy silicane, methacryloxypropyl trimethoxy silane, glycidoxypropyltrime,hoxysilane, dimethyldimethoxysil,ne, tetraethoxysilane, organoalkoxysilane is tetraethoxysilane, methyl triethyl oxosilane, vinyl triethoxyl, propyl-triethoxysilicane, phenyl triethoxysilane, the dodecyl triethoxyl silane, the sulfydryl propyl-triethoxysilicane, the methacryloxypropyl triethoxyl silane, the glycidoxy propyl-triethoxysilicane, at least a in the 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, 1,3-dioxolane, dioxane, tetrahydrofuran (THF), acetone, acetonitrile, N, the mixture of one or more in N-2 methylformamide, the 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 the certain temperature condition, presoma, organic solvent are evenly mixed with hydrolyst, be hydrolyzed, obtain organoalkoxysilane hydrolysis preservative solution.This temperature is preferably 20 ℃～150 ℃, more preferably 25 ℃～100 ℃, most preferably is 27 ℃～80 ℃.This hydrolysis time is preferably 10 minutes～and 48 hours.
The preservative solution that the present invention is used for Mg alloy surface can directly use or with re-using after the suitable diluent dilution, as the supercoat of coating Mg alloy surface to prevent from corroding.During concrete the use, with preservative solution of the present invention smear, spraying or blade coating be at Mg alloy surface, perhaps magnesium alloy is immersed in the preservative solution of the present invention and takes out behind the certain hour; At last, the Mg alloy surface after handling is suitably carried out heat drying, obtain corrosion protection coating.
As preferably, described Heating temperature is 35 ℃～200 ℃, more preferably 50 ℃～150 ℃.
As preferably, be 10 minutes～180 minutes described heat-up time, further preferred 30 minutes～90 minutes.
In sum, the present invention adopts hydrolysis-condensation to be reflected at magnesium alloy matrix surface to prepare organic silicon sol-gel coat, wherein adopt new catalyzer to replace an acidic catalyst commonly used, and this catalyzer is the salt of rare earth metal cerium and lanthanum, namely contains Ce
3+, Ce
4+, La
3+Salt compound, compare with existing an acidic catalyst, this catalyzer has following advantage:
(1) this catalyzer can promote silane hydrolyzate well, has high catalytic hydrolysis ability, and low pH value is to the disadvantageous effect of magnesium alloy substrate when having avoided in addition using an acidic catalyst;
(2) this catalyst themselves is a metalloid inhibiter, adopts the organic silicon sol-gel coat of this Preparation of Catalyst even can provide passivation effect for the magnesium alloy substrate of certain model, has improved the Corrosion Protection of this matrix more;
Experiment confirm, when magnesium alloy matrix surface prepares organic silicon sol-gel coat, compare with the antiseptic property of the organic silicon sol-gel coat that adopts existing catalyzer to make, adopt the salt compounds of rare earth metal cerium provided by the invention and lanthanum to react resulting organic silicon sol-gel coat as catalyzer by hydrolysis-condensation and can provide better anticorrosion ability for magnesium alloy.
Description of drawings
Fig. 1 is the infrared spectra of the hydrolyzed silane solution among tetraethoxysilane, mercaptopropyl trimethoxysilane and comparative example 1 and the embodiment 1;
Fig. 2 is the AZ91 that is covered with organic silicon sol-gel coat of the surface after handling among AZ91 magnesium alloy substrate, comparative example 1 and the embodiment 1 in concentration is linear polarization graphic representation in 0.35% the NaCl solution;
Fig. 3 is the infrared spectra of the hydrolyzed silane solution among tetraethoxysilane, methyltrimethoxy silane and comparative example 2 and the embodiment 2;
Fig. 4 is the AZ31 magnesium alloy, handle AZ31 magnesium alloy that rear surfaces are covered with organic silicon sol-gel coat through comparative example 2 and embodiment 2 is polarization curve in 0.35% the NaCl solution in concentration;
Fig. 5 is the JDM21 magnesium alloy, handle JDM2 magnesium alloy that rear surfaces are covered with organic silicon sol-gel coat through comparative example 3 and embodiment 3 is polarization curve in 0.35% the NaCl solution in concentration.
Embodiment
Describe in further detail below in conjunction with the present invention of embodiment, it is pointed out that the following stated embodiment is intended to be convenient to the understanding of the present invention, and it is not played any restriction effect.
The comparative example 1:
Present embodiment is the comparative example of following examples 1.
In the present embodiment, magnesium alloy substrate is AZ91, prepares the anticorrosion organic silicon sol-gel coat of using at this magnesium alloy matrix surface, and this coating is precursor with sulfydryl propyl trimethoxy silicane and tetraethoxysilane, adopt acid for catalyzer be hydrolyzed-condensation reaction obtains, concrete steps are as follows:
(1) with 3.75g sulfydryl propyl trimethoxy silicane, 1.25g tetraethoxysilane, 20g ethanol, and the 5g0.5mol/L formic acid solution mixes, and at room temperature stirs 12 hours, obtains the organoalkoxysilane hydrolyzate;
(2) magnesium alloy AZ91 mechanical polishing, ultrasonic cleaning are placed in the above-mentioned organoalkoxysilane hydrolyzate and soaked 1 minute, take out the back 120 ℃ of following thermal treatments 30 minutes, obtain the contrast AZ91 sample that the surface is covered with organic silicon sol-gel coat after to be dried.
Embodiment 1:
In the present embodiment, magnesium alloy substrate and above-mentioned comparative example 1 are identical, prepare the anticorrosion organic silicon sol-gel coat of using at this magnesium alloy matrix surface, and this coating is precursor with sulfydryl propyl trimethoxy silicane and tetraethoxysilane, adopts Ce(NO
3)
3For catalyzer be hydrolyzed-condensation reaction obtains, concrete steps are as follows:
(1) with 3.75g sulfydryl propyl trimethoxy silicane, 1.25g tetraethoxysilane, 20g ethanol, and 5g concentration is 0.1% Ce(NO
3)
3Solution mixes, and at room temperature stirs 12 hours, obtains the organoalkoxysilane hydrolyzate;
(2) magnesium alloy AZ91 mechanical polishing, ultrasonic cleaning are placed in the above-mentioned organoalkoxysilane hydrolyzate and soaked 1 minute, take out the back 120 ℃ of following thermal treatments 30 minutes, obtain the enforcement AZ91 sample that the surface is covered with organic silicon sol-gel coat after to be dried.
Organoalkoxysilane hydrolyzate in above-mentioned comparative example 1 and embodiment 1 step (1) is carried out infrared test respectively, to characterize organoalkoxysilane, i.e. tetraethoxysilane and sulfydryl propyl trimethoxy silicane, the hydrolysis situation under catalyst action.
Concrete testing method is: respectively with organoalkoxysilane, i.e. and tetraethoxysilane and sulfydryl propyl trimethoxy silicane, and the organoalkoxysilane hydrolysis among comparative example 1 and the embodiment 1 directly drops on the KBr salt sheet employing absorption mode record.
The infrared test result as shown in Figure 1, as can be seen from Figure 1:
(1) tetraethoxysilane, relevant with hydrolysis reaction in the sulfydryl propyl trimethoxy silicane is 967cm
-1Si-OCH
2CH
3And 816cm
-1Si-OCH
3Absorption peak;
(2) these two peaks have all disappeared in the infrared spectra of the organoalkoxysilane hydrolyzed solution among embodiment 1 and the comparative example 1, show wherein the basic thoroughly hydrolysis of alkoxy grp, i.e. an acidic catalyst among the similar comparative example 1, the catalyzer Ce(NO among the embodiment 1
3)
3Ability with good alkoxy silane catalyzed hydrolysis;
(3) in the infrared spectra of the organoalkoxysilane hydrolyzed solution among comparative example 1 and the embodiment 1,1105cm
-1Near broad peak is relevant with the vibration of Si-O-Si, namely relevant with condensation reaction, and two kinds of organoalkoxysilane hydrolyzed solutions of the similar explanation of both peak shapes have close stability.
The contrast AZ91 sample and the enforcement AZ91 sample that surface after handling in above-mentioned AZ91 matrix, comparative example 1 and embodiment 1 step (2) are covered with organic silicon sol-gel coat carry out the linear polarization curved measurement.Measuring method is: ionogen is that mass concentration is 0.35% NaCl solution, adopt three-electrode method, wherein reference electrode is mercurous chloride electrode, counter electrode is platinum electrode, working electrode is to handle the contrast AZ91 sample that the surface that obtains is covered with organic silicon sol-gel coat in AZ91 magnesium alloy, comparative example's 1 step (2), and handle the enforcement AZ91 sample that the surface that obtains is covered with organic silicon sol-gel coat in embodiment 1 step (2), sweep velocity is 10mV/s.
Linear polarization curve test result as shown in Figure 2, as can be seen from Figure 2:
(1) compares with the AZ91 sample that does not carry out surface protection; corrosion current and the corrosion potential of the AZ91 sample after comparative example 1 handles all decrease, and the reduction of corrosion current shows that the organic silicon sol-gel coat that obtains can provide certain isolated Cl for the AZ91 magnesium alloy after comparative example 1 handles
-, water, O
2Deng the ability of corrosion, between the reduction of corrosion potential explanation AZ91 magnesium alloy substrate and this organic silicon sol-gel coat strong reactive behavior is arranged;
(2) with the AZ91 electrode that do not carry out surface protection, and the contrast AZ91 sample after comparative example 1 handles compares, and the corrosion current of the enforcement AZ91 sample after embodiment 1 handles is minimum, and still, corrosion potential is the highest; Minimum organic silicon sol-the gel coat that obtains after embodiment 1 handles that shows of corrosion current can provide better isolated preservative effect for AZ91; The organoalkoxysilane hydrolyzate that makes among the highest embodiment of showing 1 of corrosion potential has certain passivation effect to the AZ91 magnesium alloy substrate;
Therefore, can draw according to above-mentioned linear polarization curve result: when magnesium alloy AZ91 surface preparation organic silicon sol-gel coat, adopt Ce
3+Be catalyzer ratio H
+The Corrosion Protection of doing the resulting organic silicon sol-gel coat of catalyzer is better.
The comparative example 2:
Present embodiment is the comparative example of following examples 2.
In the present embodiment, magnesium alloy substrate is the AZ31 magnesium alloy, prepare anticorrosion with organic silicon sol-gel coat at this magnesium alloy matrix surface, this coating is precursor with methyltrimethoxy silane and tetraethoxysilane, adopt formic acid solution be catalyzer be hydrolyzed-condensation reaction obtains, concrete steps are as follows:
(1) with 8.16g methyltrimethoxy silane, 4.16g tetraethoxysilane, 7.02g ethanol, and the 7.02g0.2mol/L formic acid solution mixes, and stirs 6 hours down at 40 ℃, obtains the organoalkoxysilane hydrolyzate;
(2) mechanical polishing of AZ31 magnesium alloy electrode, ultrasonic cleaning are placed in the organoalkoxysilane hydrolyzate and soaked 1 minute, take out the back 100 ℃ of following thermal treatments 1 hour, obtain the contrast AZ31 sample that the surface is covered with organic silicon sol-gel coat after to be dried.
Embodiment 2:
In the present embodiment, magnesium alloy substrate and above-mentioned comparative example 2 are identical, prepare the anticorrosion organic silicon sol-gel coat of using at this magnesium alloy matrix surface, and this coating is precursor with methyltrimethoxy silane and tetraethoxysilane, adopts La(NO
3)
3Make the hydrolysis reaction catalyzer to be hydrolyzed-condensation reaction and obtaining, concrete steps are as follows:
(1) with 8.16g methyltrimethoxy silane, 4.16g tetraethoxysilane, 7.02g ethanol, and 7.02g0.1%La(NO
3)
3Solution mixes, and stirs 6 hours down at 40 ℃, obtains the organoalkoxysilane hydrolyzate;
(2) mechanical polishing of AZ31 magnesium alloy, ultrasonic cleaning are placed in the organoalkoxysilane hydrolyzate and soaked 1 minute, take out the back 100 ℃ of following thermal treatments 1 hour, obtain the enforcement AZ31 sample that the surface is covered with organic silicon sol-gel coat after to be dried.
Organoalkoxysilane hydrolyzate in above-mentioned comparative example 2 and embodiment 2 steps (1) is carried out infrared test respectively, to characterize organoalkoxysilane, i.e. tetraethoxysilane and trimethoxysilyl propyl methacrylate TMOS, the hydrolysis situation under catalyst action.Concrete testing method is identical with testing method in above-described embodiment 1, that is: respectively with organoalkoxysilane, be tetraethoxysilane and methyltrimethoxy silane, and the organoalkoxysilane hydrolyzate among comparative example 1 and the embodiment 1 directly drop on the KBr salt sheet employing absorption mode record.
The infrared test result as shown in Figure 3, as can be seen from Figure 3:
(1) tetraethoxysilane, relevant with hydrolysis reaction in the methyltrimethoxy silane is 967cm
-1Si-OCH
2CH
3And 848cm
-1Si-OCH
3Absorption peak;
(2) these two peaks have all disappeared in the infrared spectra of the organoalkoxysilane hydrolyzed solution among embodiment 2 and the comparative example 2, show wherein all thoroughly hydrolysis of organoalkoxysilane, the also an acidic catalyst among the similar comparative example 2, the catalyzer La(NO among the embodiment 2
3)
3Ability with good alkoxy silane catalyzed hydrolysis;
(3) in the infrared spectra of the organoalkoxysilane hydrolyzed solution among comparative example 2 and the embodiment 2,1105cm
-1Near broad peak is relevant with the vibration of Si-O-Si, that is relevant with condensation reaction, the similar explanation of both peak shapes, and two kinds of organoalkoxysilane hydrolyzed solutions have close stability.
Do not protect surface after handling in magnesium alloy AZ31 sample, comparative example 2 and embodiment 2 steps (2) to be covered with the contrast AZ31 sample of organic silicon sol-gel coat and implement the AZ31 sample and carry out the linear polarization curved measurement above-mentioned.Measuring method is: ionogen is that mass concentration is 0.35% NaCl solution, adopt three-electrode method, wherein reference electrode is mercurous chloride electrode, counter electrode is platinum electrode, working electrode is to handle the contrast AZ31 sample that the surface that obtains is covered with organic silicon sol-gel coat in magnesium alloy AZ31 matrix, comparative example's 2 steps (2), and handle the enforcement AZ31 sample that the surface that obtains is covered with organic silicon sol-gel coat in embodiment 2 steps (2), sweep velocity is 10mV/s.
Linear polarization curve test result as can be seen from Figure 4 shows as shown in Figure 4:
(1) compares with the AZ31 magnesium alloy sample that does not carry out surface protection; corrosion current and the corrosion potential of the AZ31 magnesium alloy sample after comparative example 2 handles all decrease, and the reduction of corrosion current shows that the organic silicon sol-gel coat that obtains can provide certain isolated Cl for the AZ31 magnesium alloy after comparative example 2 handles
-, water, O
2Antiseptic power etc. corrosion factor;
(2) with the AZ31 magnesium alloy electrode that do not carry out surface protection, and the AZ31 magnesium alloy electrode after comparative example 2 handles compares, and the corrosion current of the AZ31 magnesium alloy electrode after embodiment 2 handles is minimum; Minimum organic silicon sol-the gel coat that obtains after comparative example 2 handles that shows of corrosion current can provide better isolated preservative effect for the AZ31 magnesium alloy;
Therefore, can draw according to above-mentioned linear polarization curve result: when AZ31 surface preparation organic silicon sol-gel coat, adopt La
3+Be catalyzer ratio H
+The Corrosion Protection of doing the resulting organic silicon sol-gel coat of catalyzer is better.
The comparative example 3:
Present embodiment is the comparative example of following examples 3.
In the present embodiment, magnesium alloy substrate is JDM2 magnesium alloy electrode, prepares the anticorrosion organic silicon sol-gel coat of using at this magnesium alloy matrix surface, and this coating is precursor with the methyltrimethoxy silane, adopt formic acid solution be catalyzer be hydrolyzed-condensation reaction obtains, concrete steps are as follows:
(1) with 6g methyltrimethoxy silane, 21g ethanol, and the 3g0.05mol/L formic acid solution mixes, and stirs 2 hours down at 60 ℃, obtains the organoalkoxysilane hydrolyzate;
(2) mechanical polishing of JDM2 magnesium alloy electrode, ultrasonic cleaning are placed in the organoalkoxysilane hydrolyzate and soaked 1 minute, take out the back 80 ℃ of following thermal treatments 90 minutes, obtain the contrast JDM2 sample that the surface is covered with organic silicon sol-gel coat after to be dried.
Embodiment 3:
In the present embodiment, magnesium alloy substrate and above-mentioned comparative example 3 are identical, prepare the anticorrosion organic silicon sol-gel coat of using at this magnesium alloy matrix surface, and this coating is precursor with the methyltrimethoxy silane, adopts Ce(NO
3)
3Make the hydrolysis reaction catalyzer to be hydrolyzed-condensation reaction and obtaining, concrete steps are as follows:
(1) with 6g methyltrimethoxy silane, 21g ethanol,, and 3g0.1%La(NO
3)
3Solution mixes, and stirs 2 hours down at 60 ℃, obtains the organoalkoxysilane hydrolyzate;
(2) mechanical polishing of JDM2 magnesium alloy, ultrasonic cleaning are placed in the organoalkoxysilane hydrolyzate and soaked 1 minute, take out the back 80 ℃ of following thermal treatments 90 minutes, obtain the enforcement JDM2 sample that the surface is covered with organic silicon sol-gel coat after to be dried.
Do not protect surface after handling in magnesium alloy JDM2 sample, comparative example 3 and embodiment 3 steps (2) to be covered with the contrast JDM2 sample of organic silicon sol-gel coat and implement the JDM2 sample and carry out the linear polarization curved measurement above-mentioned.Measuring method is: ionogen is that mass concentration is 0.35% NaCl solution, adopt three-electrode method, wherein reference electrode is mercurous chloride electrode, counter electrode is platinum electrode, working electrode is to handle the contrast AZ31 sample that the surface that obtains is covered with organic silicon sol-gel coat in magnesium alloy JDM2 matrix, comparative example's 3 steps (2), and handle the enforcement JDM2 sample that the surface that obtains is covered with organic silicon sol-gel coat in embodiment 3 steps (2), sweep velocity is 10mV/s.
Linear polarization curve test result as can be seen from Figure 5 shows as shown in Figure 5:
(1) compares with the JDM2 sample that does not carry out surface protection; corrosion current and the corrosion potential of the JDM2 sample after comparative example 1 handles all decrease, and the reduction of corrosion current shows that organic silicon sol-gel coat of implementing to obtain after 3 processing through contrast can provide certain isolated Cl for the JDM2 magnesium alloy
-, water, O
2Deng the ability of corrosion, between the reduction of corrosion potential explanation JDM2 magnesium alloy substrate and this organic silicon sol-gel coat strong reactive behavior is arranged;
(2) with the JDM2 electrode that do not carry out surface protection, and the contrast JDM2 sample after comparative example 3 handles compares, and the corrosion current of the enforcement JDM2 sample after embodiment 3 handles is minimum, and still, corrosion potential is the highest; Minimum organic silicon sol-the gel coat that obtains after embodiment 3 handles that shows of corrosion current can provide better isolated preservative effect for JDM2; The organoalkoxysilane hydrolyzate that makes among the highest embodiment of showing 3 of corrosion potential has certain passivation effect to the JDM2 magnesium alloy substrate;
Therefore, can draw according to above-mentioned linear polarization curve result: when magnesium alloy JDM2 surface preparation organic silicon sol-gel coat, adopt Ce
3+Be catalyzer ratio H
+The Corrosion Protection of doing the resulting organic silicon sol-gel coat of catalyzer is better.
Above-described embodiment has been described in detail technical scheme of the present invention; be understood that the above only is specific embodiments of the invention; be not limited to the present invention; all any modifications of in principle scope of the present invention, making, replenish or be equal to replacement etc., all should be included within protection scope of the present invention.
Claims (10)
1. the anticorrosion preparation method with organic silicon sol-gel coat of magnesium alloy matrix surface, the employing organoalkoxysilane is precursor, obtains organoalkoxysilane hydrolysis preservative solution with presoma, organic solvent and after hydrolyst evenly mixes; This preservative solution smeared, sprays or be spin-coated on magnesium alloy matrix surface after carry out heat treated, obtain organic silicon sol-gel coat after to be dried, perhaps magnesium alloy substrate is immersed in certain hour in this preservative solution, carry out heat treated after the taking-up, obtain organic silicon sol-gel coat after to be dried; It is characterized in that: described catalyzer is the salt compounds of metallic cerium and/or the salt compounds of lanthanoid metal, and cerium ion is Tricationic and/or quadrivalent cation in the salt compounds of described metallic cerium.
2. the anticorrosion preparation method with organic silicon sol-gel coat of magnesium alloy matrix surface according to claim 1, it 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 anticorrosion preparation method with organic silicon sol-gel coat of magnesium alloy matrix surface according to claim 1, it is characterized in that: the salt compounds of described lanthanoid metal comprises LaCl
3, La(NO
3)
3, La
2(SO
4) in one or more.
4. the anticorrosion preparation method with organic silicon sol-gel coat of magnesium alloy matrix surface according to claim 1, it is characterized in that: described organoalkoxysilane refers to silicoorganic compound that have at least in the molecule Si-OR unit and composition thereof, and wherein R is CH
3-, CH
3CH
2-, CH
3CH
2CH
2-, CH
3CH
2CH
2CH
2-,-CH(CH
3)
2In a kind of.
5. the anticorrosion preparation method with 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, the dodecyl Trimethoxy silane, the sulfydryl propyl trimethoxy silicane, methacryloxypropyl trimethoxy silane, glycidoxypropyltrime,hoxysilane, dimethyldimethoxysil,ne, tetraethoxysilane, organoalkoxysilane is tetraethoxysilane, methyl triethyl oxosilane, vinyl triethoxyl, propyl-triethoxysilicane, phenyl triethoxysilane, the dodecyl triethoxyl silane, the sulfydryl propyl-triethoxysilicane, the methacryloxypropyl triethoxyl silane, the glycidoxy propyl-triethoxysilicane, at least a in the dimethyldiethoxysilane.
6. the anticorrosion preparation method with 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, 1,3-dioxolane, dioxane, tetrahydrofuran (THF), acetone, acetonitrile, N, the mixture of one or more in N-2 methylformamide, the methyl-sulphoxide.
7. according to the anticorrosion preparation method with organic silicon sol-gel coat of the described magnesium alloy matrix surface of arbitrary claim in the claim 1 to 6, it is characterized in that: described catalyst quality accounts for 10 of organoalkoxysilane quality
-6～0.1, be preferably 10
-5～10
-2
8. according to the anticorrosion preparation method with organic silicon sol-gel coat of the described magnesium alloy matrix surface of arbitrary claim in the claim 1 to 6, it is characterized in that: presoma, organic solvent are obtained organoalkoxysilane hydrolysis preservative solution with hydrolyst after temperature is evenly to mix under 20 ℃～150 ℃ conditions, preferred temperature is 25 ℃～100 ℃.
9. according to the anticorrosion preparation method with organic silicon sol-gel coat of the described magnesium alloy matrix surface of arbitrary claim in the claim 1 to 6, it is characterized in that: described Heating temperature is 35 ℃～200 ℃, is preferably 50～150 ℃.
10. according to the anticorrosion preparation method with organic silicon sol-gel coat of the described magnesium alloy matrix surface of arbitrary claim in the claim 1 to 6, it is characterized in that: be 10 minutes～180 minutes described heat-up time, preferred 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 |
| CN103556149A (en) * | 2013-11-06 | 2014-02-05 | 桂林理工大学 | Corrosion inhibition treatment method for inhibiting corrosion of magnesium alloy in sodium chloride solution |
| CN103695884A (en) * | 2013-12-10 | 2014-04-02 | 江苏正达炉料有限公司 | Passivating metal magnesium particles and passivating method thereof |
| CN105860829A (en) * | 2016-03-29 | 2016-08-17 | 东莞艾宝纳米科技有限公司 | Formula of super hard anti-corrosion coating material for magnesium alloy and preparation method of super hard anti-corrosion coating material for magnesium alloy |
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| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN103556149A (en) * | 2013-11-06 | 2014-02-05 | 桂林理工大学 | Corrosion inhibition treatment method for inhibiting corrosion of magnesium alloy in sodium chloride solution |
| CN103556149B (en) * | 2013-11-06 | 2016-01-13 | 桂林理工大学 | A kind of Corrosion inhibition treatment method suppressing magnesium alloy to corrode in sodium chloride solution |
| CN103695884A (en) * | 2013-12-10 | 2014-04-02 | 江苏正达炉料有限公司 | Passivating metal magnesium particles and passivating method thereof |
| CN103695884B (en) * | 2013-12-10 | 2017-05-24 | 江苏正达炉料有限公司 | Passivating metal magnesium particles and passivating method thereof |
| CN105860829A (en) * | 2016-03-29 | 2016-08-17 | 东莞艾宝纳米科技有限公司 | Formula of super hard anti-corrosion coating material for magnesium alloy and preparation method of super hard anti-corrosion coating material for magnesium alloy |
| CN107236422A (en) * | 2017-07-24 | 2017-10-10 | 杨洁磊 | A kind of preparation method of rare-earth sol type water paint |
| 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 |
| CN108587449A (en) * | 2018-04-27 | 2018-09-28 | 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 |
| CN109136903A (en) * | 2018-09-07 | 2019-01-04 | 中南大学 | A kind of the silane laminated film and its methods for making and using same of rare earth doped salt and zeolite |
| 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 |
| CN111117161A (en) * | 2019-12-29 | 2020-05-08 | 江苏江城电气有限公司 | Super weather-resistant bus for ships and ocean platforms |
| CN115709158A (en) * | 2022-11-21 | 2023-02-24 | 中山大学 | Metal long-acting anticorrosion phenolic amine modified sol-gel film and preparation method thereof |
| 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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