CN104388923B - A kind of preparation method of Graphene modified titanium oxide anti-corrosion of metal erosion resisting coating - Google Patents
A kind of preparation method of Graphene modified titanium oxide anti-corrosion of metal erosion resisting coating Download PDFInfo
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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
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- 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
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- 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
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Abstract
The invention discloses the preparation method of a kind of Graphene modified titanium oxide anti-corrosion of metal erosion resisting coating, it includes the preparation of Graphene precursor solution, the preparation of titanium oxide sol, the preparation of Graphene modified titanium oxide powder body, the preparation of silane sol, the preparation of composite coating and the preparation process of anti-corrosion of metal erosion resisting coating successively.Its erosion shield thickness is 200 500nm.The TiO in Graphene modified titanium oxide powder body obtained by the present invention2Particle size is the most homogeneous, and is evenly distributed on redox graphene lamella, and TiO2Crystalline structure be Anatase and brookite mixing crystal formation; the mixing crystal formation of this brockite and anatase constitutes compound band structure; be conducive to improving the efficiency of light energy utilization of titanium oxide; the migration path of electronics during prolongation photocatalytic titanium oxide cathodic protection; reduce the compound of electron hole, improve the photic cathodic protection effect of coating.
Description
Technical field
The present invention relates to the preparation method of a kind of titanium oxide anti-corrosion of metal erosion resisting coating, particularly relate to a kind of modified oxidized titanium of Graphene
Belong to the preparation method of erosion shield.
Background technology
Greatly, in air, salt and alkali component is complicated, concentration is high, the marine resources of high humidity for direct projection long-time for the sun, day and night temperature
Utilize related industries technical field, anti-corrosion of metal tool to be of great significance: the generation of metal erosion and aggravation, will significantly drop
The mechanical properties such as the intensity of low metal material, plasticity, toughness, destroy the geometry of hardware, increase the abrasion between part,
Deteriorate the physical properties such as electrical and optical, shorten the service life of equipment, even cause the catastrophic failure such as fire, blast.
In prior art, the anti-corrosion method of metal is broadly divided into three major types: the anodic protection of metal, metal cathodic protection with
And the nonmetal coating protection of metal surface.Wherein, cathodic protection coatings is the marine industry field gold of current widely studied application
Belong to corrosion protection technology.
Traditional cathodic protection is realized as sacrificing positive pole by zinc or aluminium, but this metal corrosion preventing method is along with zinc or aluminum sun
The consumption of pole, its protective effect can gradually be lost efficacy, thus be there is the congenital defect such as short, poor stability in service life.
Nano-titanium oxide photo-catelectrode protection coating is the novel cathode resist technology of Recent study and development.When being higher than oxygen with energy
Change titanium absorb threshold value light wave (λ≤380nm) irradiate time, due to photoelectric effect, its interior electronics from valence to conduction band shape
Become negative electricity electronics (e-) and positive electricity hole (h+).Under the effect of space charge layer, hole focuses on electrode surface, with solution
In electron donor water generation oxidation reaction；Electronics then arrives metal, makes the electrode potential of metal be reduced to below corrosion potential,
So that metal enters cathode protecting state.
Due to TiO2Photo-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, rustless steel, copper under illumination condition, and aoxidizes
Titanium has that chemical stability is good, avirulence, the advantage such as cheap, has potential application prospect.But, titanium dioxide can only
By ultraviolet excitation, and exciting the light induced electron of generation and hole to be easily combined, the actual light electrical efficiency making titanium dioxide is relatively low,
The electron amount that can arrive metallic matrix is the most less, and metal loses the risk of cathodic protection and improves.
If able to increase the express passway of an electron transfer in titanium oxide cathodic protection electrode, photo-excited electron is made to move rapidly
Move to the compound of metallic matrix, inhibited oxidation titanium electronics and hole, improve titanium dioxide electrodes photic cathodic protection effect by being
One feasible method.
Graphene (GO) has the electric conductivity of excellence, and it can be as the bridge of electron transfer.In recent years, lead in photocatalysis
There are reports in territory is prepared for Graphene modified titanium oxide powder body, and research shows that Graphene can improve the photocatalysis of titanium dioxide
Efficiency.
In prior art, the many employings of preparation method of Graphene/titanium oxide composite granule are first reduced, the two-step method of rear hydro-thermal:
Chinese patent application CN101658786B discloses a kind of electron beam irradiation and prepares graphene-based titanium dioxide composite photocatalyst
The method of agent, it, by adding graphene powder in titanium tetrafluoride solution, obtains suspension with after ultrasonic disperse；Then should
Suspension is placed in electron beam generating apparatus so that it is stand the electron beam irradiation of a customization amount, and irradiation dose is 70-280KGy；
Then put into after sealing in the baking oven of 60 DEG C and react 20 hours；Scrubbed, dry, final prepared graphene-based titanium dioxide is multiple
Close photocatalyst.
But this method complex process equipment, and the application of electron beam generating apparatus also improves cost prepared by powder body.
Chinese patent application CN101890344B discloses the preparation method of a kind of Graphene/titanium dioxide composite photocatalyst, step
Rapid as follows: graphite oxide is dissolved in organic solvent, and supersound process obtains graphene oxide dispersion；In graphene oxide dispersion
Middle addition titanium salt presoma, stirs；It is transferred to the dispersion liquid mixed at hydrothermal reaction kettle, 120-200 DEG C react 4-20
Hour；Obtained for reaction product is cleaned with deionized water with dehydrated alcohol respectively, is dried at vacuum 40-80 DEG C 8-24 hour and obtains
To Graphene/titanium dioxide composite photocatalyst.
This method that graphite oxide is dissolved in organic solvent can obtain high-quality Graphene, but Graphene productivity is low, its dispersion
The concentration of liquid is too low, is difficult to when carrying out titania addition modification freely regulate and control doping ratio.Chinese patent application
CN102553559A discloses the preparation method of a kind of graphene/nanometer titanium dioxide compound, its by by graphene oxide with
Titanium oxide powder mixes, and prepares Graphene-P25 composite after hydro-thermal reaction.
This method, directly with titanium oxide crystal as raw material, causes titanium oxide powder bad dispersibility in Graphene laminated structure,
This will weaken the mechanical property of coating, and be difficult to obtain uniform cathodic protection current, finally affect the actual antiseptic effect of metal.
Chinese patent application CN103337611A discloses the preparation method of a kind of Graphene and composite titania material, and it leads to
Cross and graphene solution is added in titanium precursors solution, through hydrolyzing, depositing, be dried, it is thus achieved that graphene oxide and amorphous titanium oxide
Composite, this mixing composite hydrothermal treatment carries out the reduction of graphene oxide and the crystallization of amorphous titanium oxide.
The preparation method technique of this technical scheme is simple, and titanium oxide is good dispersion on graphene film.But owing to have passed through amorphous hydrogen
The deposition of titanium oxide and dry run, titanium oxide is easily formed in crystallization process reunites and abnormal growth, will result in coating equally
Mechanical property and cathodic protection effect be difficult to ensure that.
And the technical scheme of above-mentioned patent application all merely relates to the preparation of Graphene/titanium oxide composite granule.
Based on the photic cathodic protection performance of titanium oxide, metallic matrix is prepared the photic negative electrode of Graphene modified titanium oxide and protects
Protecting coating, improve the cathodic protection performance of coating, prior art is all not directed to.
Summary of the invention
It is an object of the present invention to provide the preparation method of the modified photic cathodic protection coatings of titanium oxide of a kind of Graphene, its technique
Simply, low cost of manufacture, and the photic cathodic protection effect of titania coating can be significantly improved.Technology,
The present invention technical issues that need to address for achieving the above object are, how to obtain based on anatase and brockite structure
Crystalline phase forms, and how to obtain the Graphene modified titanium oxide coating that dispersive property is good, and then improves titanium oxide cathodic protection painting
The technical problem of the anti-corrosion protection efficiency of layer.
The present invention solves that above-mentioned technical problem be employed technical scheme comprise that, a kind of Graphene modified titanium oxide anticorrosive metal is coated with
The preparation method of layer, it is characterised 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, dehydrated alcohol 10-30 part that concentration is 2g/L respectively,
Mixing is placed on ultrasonic disperse in ultrasonic cleaner, prepares Graphene precursor solution；
Second step, the preparation steps of titanium oxide sol:
By volume number, measures analytical pure butyl 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 of analytical pure glacial acetic acid and dehydrated alcohol 10-20 part respectively, mixing
It is made into B solution；
Above-mentioned solution A is also mixed homogeneously by stirring with B solution, prepares titanium oxide sol；
3rd step, the preparation process of Graphene modified titanium oxide powder body:
While stirring Graphene precursor solution is slowly dropped in titanium oxide sol；
After continuing stirring 20 minutes, transfer to hydrothermal reaction kettle reacts 8-16 hour, after taking-up, natural cooling；Wherein,
Hydrothermal reaction kettle is placed in the baking oven of 100 DEG C；
Removing the supernatant, be centrifuged separating three times by lower floor's colloidal sol, period is the most neutral with distilled water wash centrifugation,
After will centrifugal after precipitate be placed in the baking oven of 90 DEG C dryings, prepared graphene oxide/titanium dioxide composite powder；
4th step, the preparation process of silane sol:
By volume number, measure respectively gamma-methyl allyl acyloxypropyl trimethoxysilane that 10 parts of concentration is 98%, 10 parts go
Ionized water and 80 parts of dehydrated alcohol, after mix homogeneously, after addition glacial acetic acid regulation pH value to 4, be aged 24 hours under room temperature,
Prepare silane sol；
5th step, the preparation process of graphene oxide/titanium dioxide composite coating:
Be 5-10g by the addition of graphene oxide/titanium dioxide composite powder in every liter of silane sol, by above-mentioned graphene oxide/
Titanium dioxide composite powder joins in above-mentioned silane sol, prepares mixing suspension, then by this mixing suspension ultrasonic disperse 1
Hour, prepare Graphene modified titanium oxide coating；
6th step, the preparation process of anti-corrosion of metal erosion resisting coating:
A. by smooth for metal 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 lifting technology the metal surface of preprocessed mistake, after drying at room temperature,
It is placed in 80 DEG C of baking ovens to continue to be dried 30 minutes；
C. according to the corrosion class requirement of metal material and specifically used environment, repeat the above steps b coats several times, directly
200-500nm is reached to coating layer thickness.
What technique scheme was directly brought has the technical effect that, on the one hand, the crystalline substance of the titanium oxide in the coating that said method is prepared
Phase composition is anatase and brockite structure, and, titanium oxide powder is dispersed to be attached on reduced graphene lamella, without group
Poly-；Therefore, the Graphene modified titanium oxide coating prepared by technique scheme, the photic negative electrode of titanium oxide can be effectively improved and protect
Electron transfer efficiency during protecting；
On the other hand, the anti-corrosion of metal erosion resisting coating obtained by above-mentioned preparation method, metallic matrix can be greatly improved at illumination condition
Under corrosion protection effect.Reason is, as cathodic protection coatings without the modified oxidized titanium coating of Graphene of sacrificial, it changes
Property agent Graphene has preferable electronic transmission performance, can improve the transfer efficiency of electronics in titanium oxide, and absorptivity is low,
Doping will not reduce the absorbing properties of titanium oxide.Therefore, coat the nano-titanium oxide coating layer of above-mentioned modification in metal surface, can
Improve the non-sacrificial photo-catelectrode protection effect of coating.
Being 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 the advantages that
The main body of the metal anti-corrosion protection coating of the present invention is titanium oxide, and its chemical stability is good, low cost；Especially as
Cathodic protection coatings is without sacrificial；Modifying agent used is Graphene, and it has preferable electronic transmission performance, can improve titanium oxide
The transfer efficiency of middle electronics；Preparation is simple for metal anti-corrosion protection coating, metallic matrix can be greatly improved at light
Corrosion protection effect under the conditions of according to.
Accompanying drawing explanation
Fig. 1 is Graphene/titanium dioxide composite powder (GO-TiO2) X-ray diffractogram (XRD)；
Fig. 2 is Graphene/titanium dioxide composite powder (GO-TiO2) transmission electron microscope photo (TEM).
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention will be described in detail.
Definition one: in present specification, GO-TiO2It is Graphene/titanium dioxide；
Definition two: in present specification, 0.8%GO-TiO2With 1.6%GO-TiO2Represent respectively: modifying agent Graphene is at graphite
Mass fraction in alkene/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, after mixing respectively
It is placed in ultrasonic disperse in ultrasonic cleaner, prepares Graphene precursor solution；
Second step, the preparation steps of titanium oxide sol:
By volume number, measures analytical pure butyl 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 of analytical pure glacial acetic acid and dehydrated alcohol 20 parts respectively, and mixing is made into
B solution；
Above-mentioned solution A is also mixed homogeneously by stirring with B solution, prepares titanium oxide sol；
3rd step, the preparation process of Graphene modified titanium oxide powder body:
While stirring Graphene precursor solution is slowly dropped in titanium oxide sol；
After continuing stirring 20 minutes, transfer to hydrothermal reaction kettle reacts 10 hours, after taking-up, natural cooling；Wherein, water
Thermal response still is placed in the baking oven of 100 DEG C；
Removing the supernatant to be centrifuged separating three times by lower floor's colloidal sol, period is the most neutral with distilled water wash centrifugation, finally
Precipitate after centrifugal is placed in the baking oven of 90 DEG C drying, prepares graphene oxide/titanium dioxide composite powder；
4th step, the preparation process of silane sol:
By volume number, measure respectively gamma-methyl allyl acyloxypropyl trimethoxysilane that 5 parts of concentration is 98%, 5 parts go from
Sub-water and 90 parts of dehydrated alcohol, after mix homogeneously, after addition glacial acetic acid regulation pH value to 4, be aged 24 hours under room temperature,
Prepare silane sol；
5th step, the preparation process of graphene oxide/titanium dioxide composite coating:
Be 5-10g by the addition of graphene oxide/titanium dioxide composite powder in every liter of silane sol, by above-mentioned graphene oxide/
Titanium dioxide composite powder joins in above-mentioned silane sol, prepares mixing suspension, then by this mixing suspension ultrasonic disperse 1
Hour, prepare Graphene modified titanium oxide coating；
6th step, the preparation process of anti-corrosion of metal erosion resisting coating:
A. by smooth for metal 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 lifting technology the metal surface of preprocessed mistake, after drying at room temperature,
It is placed in 80 DEG C of baking ovens to continue to be dried 30 minutes；
C. according to the corrosion class requirement of metal material and specifically used environment, repeat the above steps b coats several times, directly
200-500nm is reached to coating layer thickness.
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
Secondary.
Embodiment 2
The first step, in the preparation process of Graphene precursor solution, by volume number, measure dehydrated alcohol 10 parts；
Second step, in the preparation steps of titanium oxide sol, by volume mark, measure 40 parts of mixing of dehydrated alcohol and be made into solution A；
Measuring dehydrated alcohol 10 parts, mixing is made into B solution；
3rd step, in the preparation process of Graphene modified titanium oxide powder body, the response time in hydrothermal reaction kettle is 8 hours；
Remaining is all with embodiment 1.
Embodiment 3
The first step, in the preparation process of Graphene precursor solution, by volume number, measure the graphene oxide that concentration is 2g/L
Aqueous solution 15 parts, measures dehydrated alcohol 20 parts；
Second step, in the preparation steps of titanium oxide sol, by volume mark, measure 30 parts of mixing of dehydrated alcohol and be made into solution A；
Measuring dehydrated alcohol 20 parts, mixing is made into B solution；
3rd step, in the preparation process of Graphene modified titanium oxide powder body, the response time 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 in every liter of silane sol, the addition of graphene oxide/titanium dioxide composite powder is that 8g adds；
Remaining is all with embodiment 1.
Embodiment 4
The first step, in the preparation process of Graphene precursor solution, by volume number, measure the graphene oxide that concentration is 2g/L
Aqueous solution 20 parts, dehydrated alcohol 30 parts；
Second step, in the preparation steps of titanium oxide sol, by volume mark, measure 60 parts of mixing of dehydrated alcohol and be made into solution A；
Measuring dehydrated alcohol 10 parts, mixing is made into B solution；
3rd step, in the preparation process of Graphene modified titanium oxide powder body, the response time 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 in every liter of silane sol, the addition 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；
Remaining is all with embodiment 1.
Choose the graphene oxide/titanium dioxide composite powder obtained by embodiment 1 and embodiment 4 respectively and 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-TiO2Curve；Corresponding to embodiment 4 is 1.6%GO-TiO2
Curve.It can be seen that
Diffraction maximum corresponding for TiO2Anatase and brookite.
This and Graphene/titanium dioxide composite powder prepared by prior art, its TiO2Acquisition mostly is the result of Anatase and deposits
The most different.
Brockite is the unstable state transitional face of titanium oxide, and the mixing crystal formation of brockite and anatase constitutes compound band structure,
Be conducive to improving the efficiency of light energy utilization of titanium oxide, the migration path of electronics during prolongation photocatalytic titanium oxide cathodic protection, minimizing electronics-
Being combined of hole, improves the photic cathodic protection effect of coating.
Choose the graphene oxide/titanium dioxide composite powder obtained by embodiment 4 and carry out transmission electron microscope (TEM) observation, its knot
The most as shown in Figure 2:
As seen from Figure 2, the TiO of generation2Particle size is the most homogeneous, and is evenly distributed in redox graphene lamella
On.
And after long sonic oscillation, TiO2Particle does not splits away off from redox graphene synusia,
TiO is described2Particle is not to be simply attached on redox graphene lamella.
The analysis of causes: nano titanium oxide powder is under having water condition, and its surface is adsorbed with great amount of hydroxy group naturally, can be with graphene film
Oxygen-containing functional group (such as-OH ,-COOH) on layer interacts, thus defines the knot of graphene coated titanium dioxide
Conjunction mode, this combination makes during photo-catelectrode protection, TiO2Light induced electron be easier to transfer to reduction-oxidation graphite
On alkene synusia.
It is coated with Graphene modified titanium oxide (GO-TiO obtained by Example 1-42) stainless steel 304 of erosion shield,
Respectively with the TiO being coated with without Graphene modification2The stainless steel 304 and the 304 of uncoated any protective coating of protective coating
Rustless steel sample, is placed in the NaCl solution that mass percent concentration is 5% 15 days respectively under the conditions of Xenon light shining, utilizes
Nonyl phenol measures the content of iron ion in solution, characterizes sample weightless, and assay see table 1.
Table 1
From data shown in upper table 1 it can be seen that be coated with the rustless steel of the titanium oxide erosion shield of the Graphene modification of the present invention
304 samples, under illumination condition, because the iron ion content of corrosion dissolution substantially reduces, illustrate that coating of the present invention is to metal
Matrix has good corrosion protection effect.
It is coated with Graphene modified titanium oxide (GO-TiO obtained by Example 1-42) carbon steel of erosion shield, respectively with
It is coated with the TiO modified without Graphene2The carbon steel sample of protective coating and the carbon steel sample of uncoated any protective coating, point
It is not placed under the conditions of Xenon light shining in the NaCl solution that mass percent concentration is 5% 15 days, utilizes nonyl phenol to measure
The content of iron ion in solution, characterizes sample weightless, and assay approximates with the result of upper table 1.
That is: the stainless steel 304 sample of the titanium oxide erosion shield of the Graphene modification of the present invention it is coated with, under illumination condition,
Because the iron ion content of corrosion dissolution substantially reduces.
Choose the graphene oxide/titanium dioxide composite powder obtained by embodiment 2 and embodiment 3 respectively and carry out X-ray diffraction
(XRD) analyzing, its result is consistent with the result of Fig. 1, differs only in the strong and weak of each diffraction maximum and there is difference.
According to the photic cathodic 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 the Graphene modified titanium oxide anti-corrosion of metal erosion resisting coating of the present invention is prepared, it is not for
Other rustless steels outside rust steel 304, the most other kinds of metal or alloy, all will have good anticorrosion ability.
Claims (3)
1. the preparation method of a Graphene modified titanium oxide anti-corrosion of metal erosion resisting coating, it is characterised 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, dehydrated alcohol 10-30 part that concentration is 2g/L respectively,
Mixing is placed on ultrasonic disperse in ultrasonic cleaner, prepares Graphene precursor solution；
Second step, the preparation steps of titanium oxide sol:
By volume number, measures analytical pure butyl 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 of analytical pure glacial acetic acid and dehydrated alcohol 10-20 part respectively, mixing
It is made into B solution；
Above-mentioned solution A is also mixed homogeneously by stirring with B solution, prepares titanium oxide sol；
3rd step, the preparation process of Graphene modified titanium oxide powder body:
While stirring Graphene precursor solution is slowly dropped in titanium oxide sol；After continuing stirring 20 minutes, transfer to water
Thermal response still reacts 8-16 hour, after taking-up, natural cooling；Wherein, during hydrothermal reaction kettle is placed in the baking oven of 100 DEG C；
Removing the supernatant, be centrifuged separating three times by lower floor's colloidal sol, period is the most neutral with distilled water wash centrifugation,
After will centrifugal after precipitate be placed in the baking oven of 90 DEG C dryings, prepared graphene oxide/titanium dioxide composite powder；
4th step, the preparation process of silane sol:
By volume number, measure respectively gamma-methyl allyl acyloxypropyl trimethoxysilane that 10 parts of concentration is 98%, 10 parts go
Ionized water and 80 parts of dehydrated alcohol, after mix homogeneously, after addition glacial acetic acid regulation pH value to 4, be aged 24 hours under room temperature,
Prepare silane sol；
5th step, the preparation process of graphene oxide/titanium dioxide composite coating:
Be 5-10g by the addition of graphene oxide/titanium dioxide composite powder in every liter of silane sol, by above-mentioned graphene oxide/
Titanium dioxide composite powder joins in above-mentioned silane sol, prepares mixing suspension, then by this mixing suspension ultrasonic disperse 1
Hour, prepare Graphene modified titanium oxide coating；
6th step, the preparation process of anti-corrosion of metal erosion resisting coating:
A. by smooth for metal 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 lifting technology the metal surface of preprocessed mistake, after drying at room temperature,
It is placed in 80 DEG C of baking ovens to continue to be dried 30 minutes；
C. according to the corrosion class requirement of metal material and specifically used environment, repeat the above steps b coats several times, directly
200-500nm is reached to coating layer thickness.
The preparation method of Graphene modified titanium oxide anti-corrosion of metal erosion resisting coating the most according to claim 1, it is characterised in that described
Metal is carbon steel or stainless steel.
The preparation method of Graphene modified titanium oxide anti-corrosion of metal erosion resisting coating the most according to claim 1, it is characterised in that described
Coating number of times is 3-5 time.
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