CN104388923A - Making method of graphene modified titanium oxide metal anticorrosion coating - Google Patents
Making method of graphene modified titanium oxide metal anticorrosion coating Download PDFInfo
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- CN104388923A CN104388923A CN201410550450.8A CN201410550450A CN104388923A CN 104388923 A CN104388923 A CN 104388923A CN 201410550450 A CN201410550450 A CN 201410550450A CN 104388923 A CN104388923 A CN 104388923A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1254—Sol or sol-gel processing
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
Abstract
The invention discloses a making method of a graphene modified titanium oxide metal anticorrosion coating. The method comprises the following steps: preparing a graphene precursor solution, preparing a titanium oxide sol, preparing graphene modified titanium oxide powder, preparing a silane sol, making a composite coating, and making the metal anticorrosion coating. The thickness of the anticorrosion coating is 200-500nm. TiO2 particles in the graphene modified titanium oxide powder have uniform scales, and are uniformly distributed on a reduced graphene oxide layer, the crystal form structure of TiO2 is an anatase phase and brookite mixed crystal form, and the anatase phase and brookite mixed crystal form forms a compound energy zone structure, so the luminous energy utilization rate of titanium oxide is improved, the transfer path of electrons in the titanium oxide photocathode protection process is prolonged, the electron-hole recombination is reduced, and the photoinduced cathode protection effect of the coating is improved.
Description
Technical field
The present invention relates to a kind of preparation method of titanium oxide anti-corrosion of metal erosion resisting coating, particularly relate to a kind of preparation method of Graphene modified titanium oxide anti-corrosion of metal erosion resisting coating.
Background technology
Large for the long-time direct projection of the sun, day and night temperature, in air, salt and alkali component complexity, concentration oceanic resources that are high, high humidity utilize related industries technical field, anti-corrosion of metal tool is of great significance: the generation of metallic corrosion and aggravation, to significantly reduce the mechanical property such as intensity, plasticity, toughness of metallic substance, destroy the geometrical shape of hardware, increase the wearing and tearing between part, worsen the physicals such as electricity and optics, in the work-ing life of shortening equipment, even cause the catastrophic failure such as fire, blast.
In prior art, the anti-corrosion method of metal is mainly divided into three major types: the nonmetal coating protection of the anodic protection of metal, the galvanic protection of metal and metallic surface.Wherein, cathodic protection coatings is the marine industry field metallic corrosion guard technology of extensively research application at present.
Traditional galvanic protection is realized as sacrificing positive pole by zinc or aluminium, but this metal corrosion preventing method is along with the consumption of zinc or aluminum anode, and its provide protection can be lost efficacy gradually, thus there is the congenital defect such as short, poor stability in work-ing life.
Nano-titanium oxide photo-catelectrode protection coating is the novel cathode resist technology of Recent study and development.When with energy higher than titanium oxide absorb the light wave (λ≤380nm) of threshold value irradiate time, due to photovoltaic effect, the electronics in it forms negative electricity electronics (e-) and positive electricity hole (h+) from valence to conduction band.Under the effect of space charge layer, hole focuses on electrode surface, with the electron donor water generation oxidizing reaction in solution; Electronics then arrives metal, makes the electropotential of metal be reduced to below corrosion potential, thus makes metal enter cathode protecting state.
Due to TiO
2photo-catelectrode protection is non-sacrificial, thus which overcomes the timeliness problem of conventional cathode protection.Research shows, titania coating all can provide effective photo-catelectrode protection to metals such as carbon steel, stainless steel, copper under illumination condition, and titanium oxide has that chemical stability is good, nontoxicity, the advantage such as cheap, has potential application prospect.But titanium dioxide by ultraviolet excitation, and can only excite the easy compound of the light induced electron of generation and hole, and make the actual light electrical efficiency of titanium dioxide lower, the electron amount that can arrive metallic matrix is also less, the risk that metal loses galvanic protection improves.
If the rapid passage of a transfer transport can be increased in titanium oxide galvanic protection electrode; photo-excited electron is made to migrate to metallic matrix rapidly; the compound in inhibited oxidation titanium electronics and hole, improves the feasible method of of titanium dioxide electrodes photic galvanic protection effect by being.
Graphene (GO) has excellent conductivity, and it can as the bridge of transfer transport.In recent years, in photocatalysis field, there are reports has prepared Graphene modified titanium oxide powder, and research shows that Graphene can improve the photocatalysis efficiency of titanium dioxide.
In prior art, the many employings of preparation method of Graphene/titanium oxide composite granule are first reduced, the two-step approach of rear hydro-thermal:
Chinese patent application CN101658786B discloses a kind of method of preparing graphene-based titanium dioxide composite photocatalyst by radiation of electron beams, and it, by adding graphene powder in titanium tetrafluoride solution, obtains suspension with after ultrasonic disperse; Then this suspension is placed in electron beam generating apparatus, make it stand the electron beam irradiation of a customization amount, irradiation dose is 70-280KGy; Then the baking oven putting into 60 DEG C after sealing reacts 20 hours; Through washing, drying, finally obtained graphene-based titanium dioxide composite photocatalyst.
But this method complex process equipment, and the application of electron beam generating apparatus also improves cost prepared by powder.
Chinese patent application CN101890344B discloses a kind of preparation method of Graphene/titanium dioxide composite photocatalyst, and step is as follows: graphite oxide is dissolved in organic solvent, and supersound process obtains graphene oxide dispersion; In graphene oxide dispersion, add titanium salt presoma, stir; The dispersion liquid mixed is transferred to hydrothermal reaction kettle, at 120-200 DEG C, reacts 4-20 hour; Product that reaction obtains is used dehydrated alcohol and washed with de-ionized water respectively, and at vacuum 40-80 DEG C, dry 8-24 hour obtains Graphene/titanium dioxide composite photocatalyst.
This method graphite oxide being dissolved in organic solvent can obtain high-quality Graphene, but Graphene productive rate is low, and the concentration of its dispersion liquid is too low, is difficult to freely regulate and control doping ratio when carrying out titania addition modification.Chinese patent application CN102553559A discloses a kind of preparation method of graphene/nanometer titanium dioxide compound, and it is by mixing graphene oxide with titanium oxide powder, obtained Graphene-P25 matrix material after hydro-thermal reaction.
This method directly with titanium oxide crystal for raw material, cause titanium oxide powder in the structural bad dispersibility of Graphene sheet, this will weaken the mechanical property of coating, and be difficult to obtain uniform cathodic protection current, finally affect the actual preservative effect of metal.
Chinese patent application CN103337611A discloses the preparation method of a kind of Graphene and composite titania material, it is by adding in titanium precursors solution by graphene solution, through hydrolysis, deposition, drying, obtain graphene oxide and amorphous oxide titanium composite material, this hybrid composite carries out the reduction of graphene oxide and the crystallization of amorphous titanium oxide through hydrothermal treatment consists.
Preparation method's technique of this technical scheme is simple, and titanium oxide is good dispersity on graphene film.But due to the deposition that have passed through amorphous titanium hydroxide and drying process, titanium oxide is easily formed in crystallisation process reunites and abnormal growth, and the mechanical property of coating and galvanic protection effect will be caused equally to be difficult to ensure.
And the technical scheme of above-mentioned patent application all only relates to the preparation of Graphene/titanium oxide composite granule.
Based on the photic galvanic protection performance of titanium oxide, metallic matrix is prepared the photic cathodic protection coatings of Graphene modified titanium oxide, improve the galvanic protection performance of coating, prior art does not all relate to.
Summary of the invention
The object of the invention is, a kind of preparation method of the photic cathodic protection coatings of titanium oxide of Graphene modification is provided, its technique is simple, low cost of manufacture, and the photic galvanic protection effect of titania coating can be significantly improved.Technology,
The present invention for achieving the above object technical issues that need to address is; how to obtain the crystalline phase composition based on anatase octahedrite and brookite structure; and how to obtain the good Graphene modified titanium oxide coating of dispersing property, and then the technical problem of the anti-corrosion protection efficiency of raising titanium oxide cathodic protection coatings.
The present invention for solving the problems of the technologies described above adopted technical scheme is, a kind of preparation method of Graphene modified titanium oxide anti-corrosion of metal erosion resisting coating, is characterized in that, comprise the steps:
The first step, the preparation process of Graphene precursor solution:
By volume number, measures graphene oxide water solution 10-20 part that concentration is 2g/L, dehydrated alcohol 10-30 part respectively, and mixing is placed on ultrasonic disperse in ultrasonic cleaner, obtained Graphene precursor solution;
Second step, the preparation steps of titanium oxide sol:
By volume number, measures analytical pure butyl (tetra) titanate 10 parts and dehydrated alcohol 30-60 part respectively, and mixing is made into solution A;
By volume number, measures deionized water 10 parts, 10 parts, analytical pure Glacial acetic acid and dehydrated alcohol 10-20 part respectively, and mixing is made into B solution;
Stir and above-mentioned solution A is mixed with B solution, obtained titanium oxide sol;
3rd step, the preparation process of Graphene modified titanium oxide powder:
While stirring Graphene precursor solution is slowly added drop-wise in titanium oxide sol;
Continue stirring after 20 minutes, transfer in hydrothermal reaction kettle and react 8-16 hour, after taking-up, naturally cooling; Wherein, hydrothermal reaction kettle is placed in the baking oven of 100 DEG C;
Remove supernatant liquid, lower floor's colloidal sol is carried out centrifugation three times, period, the baking oven finally throw out after centrifugal being placed in 90 DEG C was dried, obtained graphene oxide/titanium dioxide composite powder with distilled water wash centrifugation to neutral;
4th step, the preparation process of silane sol:
By volume number, measuring 10 parts of concentration is respectively the gamma-methyl allyl acyloxypropyl trimethoxysilane of 98%, 10 parts of deionized waters and 80 parts of dehydrated alcohols, after mixing, after adding Glacial acetic acid adjust ph to 4, ageing 24 hours under room temperature, obtained silane sol;
5th step, the preparation process of graphene oxide/titanium dioxide composite coating:
Be 5-10g by the add-on of graphene oxide/titanium dioxide composite powder in often liter of silane sol, above-mentioned graphene oxide/titanium dioxide composite powder is joined in above-mentioned silane sol, obtained mixing suspension, again by this mixing suspension ultrasonic disperse 1 hour, obtained Graphene modified titanium oxide coating;
6th step, the preparation process of anti-corrosion of metal erosion resisting coating:
A. by level and smooth for metallic surface polishing, first use deionized water ultrasonic cleaning, then dry with washes of absolute alcohol;
B. Graphene modified titanium oxide coating slip is coated in through pretreated metallic surface with lift technology, after drying at room temperature, is placed in 80 DEG C of baking ovens and continues dry 30 minutes;
C. according to the corrosion class requirement of metal material and concrete environment for use, repeat above-mentioned steps b and carry out several times coating, until coat-thickness reaches 200-500nm.
The technique effect that technique scheme is directly brought is, on the one hand, the crystalline phase of the titanium oxide in the coating that aforesaid method is prepared consists of anatase octahedrite and brookite structure, and titanium oxide powder is dispersed to be attached on reduced graphene lamella, soilless sticking; Therefore, the Graphene modified titanium oxide coating prepared by technique scheme, effectively can improve the electron transfer efficiency in the photic galvanic protection process of titanium oxide;
On the other hand, the anti-corrosion of metal erosion resisting coating obtained by above-mentioned preparation method, significantly can improve the corrosion protection effect of metallic matrix under illumination condition.Reason is; as the Graphene modified oxidized titanium coating of cathodic protection coatings without sacrificial, its properties-correcting agent Graphene has good electronic transmission performance, can improve the transfer efficiency of electronics in titanium oxide; and absorptivity is low, doping can not reduce the absorbing properties of titanium oxide.Therefore, apply the nano-titanium oxide coating layer of above-mentioned modification in metallic surface, the non-sacrificial photo-catelectrode protection effect of coating can be improved.
Be preferably, above-mentioned metal is steel or stainless steel.
Further preferably, above-mentioned coating number of times is 3-5 time.
The present invention, relative to prior art, has following beneficial effect:
The main body of metal anti-corrosion protection coating of the present invention is titanium oxide, and its chemical stability is good, cost is low; Especially as cathodic protection coatings without sacrificial; Properties-correcting agent used is Graphene, and it has good electronic transmission performance, can improve the transfer efficiency of electronics in titanium oxide; Preparation is simple for metal anti-corrosion protection coating, significantly can improve the corrosion protection effect of metallic matrix under illumination condition.
Accompanying drawing explanation
Fig. 1 is Graphene/titanium dioxide composite powder (GO-TiO
2) X-ray diffractogram (XRD);
Fig. 2 is Graphene/titanium dioxide composite powder (GO-TiO
2) transmission electron microscope photo (TEM).
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention will be described in detail.
Definition one: in present specification, GO-TiO
2be Graphene/titanium dioxide;
Definition two: in present specification, 0.8%GO-TiO
2with 1.6%GO-TiO
2represent respectively: the massfraction of properties-correcting agent Graphene in Graphene/titanium dioxide composite powder is 0.8% and 1.6%.
Embodiment 1
The preparation method of Graphene modified titanium oxide anti-corrosion of metal erosion resisting coating, comprises the steps:
The first step, the preparation process of Graphene precursor solution:
By volume number, measures graphene oxide water solution 10 parts, dehydrated alcohol 30 parts that concentration is 2g/L respectively, and mixing is placed on ultrasonic disperse in ultrasonic cleaner, obtained Graphene precursor solution;
Second step, the preparation steps of titanium oxide sol:
By volume number, measures analytical pure butyl (tetra) titanate 10 parts and dehydrated alcohol 50 parts respectively, and mixing is made into solution A;
By volume number, measures deionized water 10 parts, 10 parts, analytical pure Glacial acetic acid and dehydrated alcohol 20 parts respectively, and mixing is made into B solution;
Stir and above-mentioned solution A is mixed with B solution, obtained titanium oxide sol;
3rd step, the preparation process of Graphene modified titanium oxide powder:
While stirring Graphene precursor solution is slowly added drop-wise in titanium oxide sol;
Continue stirring after 20 minutes, transfer in hydrothermal reaction kettle and react 10 hours, after taking-up, naturally cooling; Wherein, hydrothermal reaction kettle is placed in the baking oven of 100 DEG C;
Remove supernatant liquid and lower floor's colloidal sol is carried out centrifugation three times, period, the baking oven finally throw out after centrifugal being placed in 90 DEG C was dried, obtained graphene oxide/titanium dioxide composite powder with distilled water wash centrifugation to neutral;
4th step, the preparation process of silane sol:
By volume number, measuring 5 parts of concentration is respectively the gamma-methyl allyl acyloxypropyl trimethoxysilane of 98%, 5 parts of deionized waters and 90 parts of dehydrated alcohols, after mixing, after adding Glacial acetic acid adjust ph to 4, ageing 24 hours under room temperature, obtained silane sol;
5th step, the preparation process of graphene oxide/titanium dioxide composite coating:
Be 5-10g by the add-on of graphene oxide/titanium dioxide composite powder in often liter of silane sol, above-mentioned graphene oxide/titanium dioxide composite powder is joined in above-mentioned silane sol, obtained mixing suspension, again by this mixing suspension ultrasonic disperse 1 hour, obtained Graphene modified titanium oxide coating;
6th step, the preparation process of anti-corrosion of metal erosion resisting coating:
A. by level and smooth for metallic surface polishing, first use deionized water ultrasonic cleaning, then dry with washes of absolute alcohol;
B. Graphene modified titanium oxide coating slip is coated in through pretreated metallic surface with lift technology, after drying at room temperature, is placed in 80 DEG C of baking ovens and continues dry 30 minutes;
C. according to the corrosion class requirement of metal material and concrete environment for use, repeat above-mentioned steps b and carry out several times coating, until coat-thickness reaches 200-500nm.
Above-mentioned metal is respectively carbon steel and stainless steel 304; The coating number of times of Graphene modified titanium oxide anti-corrosion of metal erosion resisting coating is 3 times.
Embodiment 2
The first step, in the preparation process of Graphene precursor solution, by volume number, measures dehydrated alcohol 10 parts;
Second step, in the preparation steps of titanium oxide sol, by volume mark, measures dehydrated alcohol 40 parts of mixing and is made into solution A; Measure dehydrated alcohol 10 parts, mixing is made into B solution;
3rd step, in the preparation process of Graphene modified titanium oxide powder, the reaction times in hydrothermal reaction kettle is 8 hours; All the other are all with embodiment 1.
Embodiment 3
The first step, in the preparation process of Graphene precursor solution, by volume number, measures the graphene oxide water solution 15 parts that concentration is 2g/L, measures dehydrated alcohol 20 parts;
Second step, in the preparation steps of titanium oxide sol, by volume mark, measures dehydrated alcohol 30 parts of mixing and is made into solution A; Measure dehydrated alcohol 20 parts, mixing is made into B solution;
3rd step, in the preparation process of Graphene modified titanium oxide powder, the reaction times in hydrothermal reaction kettle is 12 hours;
5th step, in the preparation process of graphene oxide/titanium dioxide composite coating, graphene oxide/titanium dioxide composite powder is by often liter of silane sol, and the add-on of graphene oxide/titanium dioxide composite powder is that 8g adds;
All the other are all with embodiment 1.
Embodiment 4
The first step, in the preparation process of Graphene precursor solution, by volume number, measures the graphene oxide water solution 20 parts that concentration is 2g/L, dehydrated alcohol 30 parts;
Second step, in the preparation steps of titanium oxide sol, by volume mark, measures dehydrated alcohol 60 parts of mixing and is made into solution A; Measure dehydrated alcohol 10 parts, mixing is made into B solution;
3rd step, in the preparation process of Graphene modified titanium oxide powder, the reaction times in hydrothermal reaction kettle is 12 hours;
5th step, in the preparation process of graphene oxide/titanium dioxide composite coating, graphene oxide/titanium dioxide composite powder is by often liter of silane sol, and the add-on of graphene oxide/titanium dioxide composite powder is that 8g adds;
The coating number of times of Graphene modified titanium oxide anti-corrosion of metal erosion resisting coating is 5 times;
All the other are all with embodiment 1.
Graphene oxide/the titanium dioxide composite powder chosen respectively obtained by embodiment 1 and embodiment 4 carry out X-ray diffraction (XRD) analyze, its result as shown in Figure 1:
In Fig. 1, corresponding to embodiment 1 is 0.8%GO-TiO
2curve; Corresponding to embodiment 4 is 1.6%GO-TiO
2curve.Can find out:
That diffraction peak is corresponding is TiO
2anatase and brookite.
This and the Graphene/titanium dioxide composite powder prepared by prior art, its TiO
2obtaining the result mostly being Anatase exists significantly different.
Brookite is the unstable state transition phase of titanium oxide; the mixing crystal formation of brookite and anatase octahedrite constitutes compound energy band structure; be conducive to the efficiency of light energy utilization improving titanium oxide; extend the migration path of electronics in photocatalytic titanium oxide galvanic protection process; reduce the compound of electron-hole, improve the photic galvanic protection effect of coating.
Graphene oxide/the titanium dioxide composite powder chosen obtained by embodiment 4 carry out transmission electron microscope (TEM) observation, its result as shown in Figure 2:
As seen from Figure 2, the TiO of generation
2particle size is comparatively homogeneous, and is evenly distributed on redox graphene lamella.
Even and if after long sonic oscillation, TiO
2particle does not split away off from redox graphene synusia, and TiO is described
2particle is not be simply attached on redox graphene lamella.
The analysis of causes: nano titanium oxide powder is having under water condition; its surface is adsorbed with great amount of hydroxy group naturally; can with the oxygen-containing functional group on graphene sheet layer (as-OH;-COOH) interact; thus define the combination of graphene coated titanium dioxide; this combination makes in photo-catelectrode protection process, TiO
2light induced electron more easily transfer on redox graphene synusia.
Graphene modified titanium oxide (GO-TiO is coated with obtained by Example 1-4
2) stainless steel 304 of erosion shield, respectively with the TiO be coated with without Graphene modification
2the stainless steel 304 of supercoat and 304 stainless steel samples of uncoated any supercoat; the NaCl solution 15 days that mass percent concentration is 5% is placed in respectively under Xenon light shining condition; nonyl phenol is utilized to measure the content of iron ion in solution; characterization sample is weightless, and assay sees the following form 1.
Table 1
As can be seen from data shown in upper table 1; be coated with the stainless steel 304 sample of the titanium oxide erosion shield of Graphene modification of the present invention; under illumination condition, because the iron ion content of corrosion dissolution obviously reduces, illustrate that coating of the present invention has good corrosion protection effect to metallic matrix.
Graphene modified titanium oxide (GO-TiO is coated with obtained by Example 1-4
2) carbon steel of erosion shield, respectively with the TiO be coated with without Graphene modification
2the carbon steel sample of supercoat and the carbon steel sample of uncoated any supercoat; the NaCl solution 15 days that mass percent concentration is 5% is placed in respectively under Xenon light shining condition; nonyl phenol is utilized to measure the content of iron ion in solution; characterization sample is weightless, and the result of assay and upper table 1 is similar to.
That is: the stainless steel 304 sample of the titanium oxide erosion shield of Graphene modification of the present invention is coated with, under illumination condition, because the iron ion content of corrosion dissolution obviously reduces.
Graphene oxide/the titanium dioxide composite powder chosen respectively obtained by embodiment 2 and embodiment 3 carries out X-ray diffraction (XRD) analysis, and its result is consistent with the result of Fig. 1, and it is different that difference is only that the power of each diffraction peak exists.
According to the photic galvanic protection anticorrosion mechanism of anti-corrosion of metal erosion resisting coating of the present invention; those skilled in the art has reason to believe: the anti-corrosion of metal erosion resisting coating that the preparation method of Graphene modified titanium oxide anti-corrosion of metal erosion resisting coating of the present invention prepares; it is for other stainless steels outside stainless steel 304; or even the metal or alloy of other kinds, all will have good anticorrosion ability.
Claims (3)
1. a preparation method for Graphene modified titanium oxide anti-corrosion of metal erosion resisting coating, is characterized in that, comprise the steps:
The first step, the preparation process of Graphene precursor solution:
By volume number, measures graphene oxide water solution 10-20 part that concentration is 2g/L, dehydrated alcohol 10-30 part respectively, and mixing is placed on ultrasonic disperse in ultrasonic cleaner, obtained Graphene precursor solution;
Second step, the preparation steps of titanium oxide sol:
By volume number, measures analytical pure butyl (tetra) titanate 10 parts and dehydrated alcohol 30-60 part respectively, and mixing is made into solution A;
By volume number, measures deionized water 10 parts, 10 parts, analytical pure Glacial acetic acid and dehydrated alcohol 10-20 part respectively, and mixing is made into B solution;
Stir and above-mentioned solution A is mixed with B solution, obtained titanium oxide sol;
3rd step, the preparation process of Graphene modified titanium oxide powder:
While stirring Graphene precursor solution is slowly added drop-wise in titanium oxide sol; Continue stirring after 20 minutes, transfer in hydrothermal reaction kettle and react 8-16 hour, after taking-up, naturally cooling; Wherein, hydrothermal reaction kettle is placed in the baking oven of 100 DEG C;
Remove supernatant liquid, lower floor's colloidal sol is carried out centrifugation three times, period, the baking oven finally throw out after centrifugal being placed in 90 DEG C was dried, obtained graphene oxide/titanium dioxide composite powder with distilled water wash centrifugation to neutral;
4th step, the preparation process of silane sol:
By volume number, measuring 10 parts of concentration is respectively the gamma-methyl allyl acyloxypropyl trimethoxysilane of 98%, 10 parts of deionized waters and 80 parts of dehydrated alcohols, after mixing, after adding Glacial acetic acid adjust ph to 4, ageing 24 hours under room temperature, obtained silane sol;
5th step, the preparation process of graphene oxide/titanium dioxide composite coating:
Be 5-10g by the add-on of graphene oxide/titanium dioxide composite powder in often liter of silane sol, above-mentioned graphene oxide/titanium dioxide composite powder is joined in above-mentioned silane sol, obtained mixing suspension, again by this mixing suspension ultrasonic disperse 1 hour, obtained Graphene modified titanium oxide coating;
6th step, the preparation process of anti-corrosion of metal erosion resisting coating:
A. by level and smooth for metallic surface polishing, first use deionized water ultrasonic cleaning, then dry with washes of absolute alcohol;
B. Graphene modified titanium oxide coating slip is coated in through pretreated metallic surface with lift technology, after drying at room temperature, is placed in 80 DEG C of baking ovens and continues dry 30 minutes;
C. according to the corrosion class requirement of metal material and concrete environment for use, repeat above-mentioned steps b and carry out several times coating, until coat-thickness reaches 200-500nm.
2. the preparation method of Graphene modified titanium oxide anti-corrosion of metal erosion resisting coating according to claim 1, it is characterized in that, described metal is steel or stainless steel.
3. the preparation method of Graphene modified titanium oxide anti-corrosion of metal erosion resisting coating according to claim 1, it is characterized in that, described coating number of times is 3-5 time.
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