CN101660147A - Method for preparing TiO2 film by utilizing sol-gelatin method - Google Patents
Method for preparing TiO2 film by utilizing sol-gelatin method Download PDFInfo
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- CN101660147A CN101660147A CN200910023997A CN200910023997A CN101660147A CN 101660147 A CN101660147 A CN 101660147A CN 200910023997 A CN200910023997 A CN 200910023997A CN 200910023997 A CN200910023997 A CN 200910023997A CN 101660147 A CN101660147 A CN 101660147A
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Abstract
The invention discloses a method for preparing TiO2 film by utilizing a sol-gelatin method. The method comprises the following steps: (1) dissolving Ti (OC4H9) in ethylene glycol monoemethyl ether, then adding acetylacetic ether and methanamide, adding a pH regulator solution after stirring, continuously stirring the mixture to obtain uniform and transparent TiO2 sol with light yellow color, standing and maturing the mixture for later use; (2) dropwise adding the TiO2 sol after maturing to the surface of a substrate to be coated for film coating, putting the substrate in drying cabinet for predrying, putting the substrate in a cabinet-type high temperature resistance furnace for heat treatment, naturally cooling the substrate to a room temperature, putting an obtained film in a high temperature steam kettle for treatment, and then putting the film in boiling water for treatment to obtain the TiO2 film. In the invention, cross-linking agent formamide is added to a sol precursor solution; steam and hydrothermal joint treatment is carried out on the TiO2 film after heat treatment, therefore, internal stress and surface checkmarks of the TiO2 film prepared by the sol-gelatin method areeliminated or weakened, and the film has the advantages of more smooth and compact surface, complete coverage, favorable surface uniformity, uniform thickness and better practical use performance.
Description
Technical field
The present invention relates to a kind of TiO
2The preparation method of film particularly relates to the TiO that a kind of sol-gel method preparation is used for surface anticorrosion, modification or the active bio of metallic matrix, inorganic materials matrix and various component thereof
2The method of film.
Background technology
Sol-gel technology is the preparation method of a kind of thin-film material of growing up in the sixties in last century.Its primary process be the metallic compound (inorganic salt or metal alkoxide) of some facile hydrolysiss in certain solvent with water and mixing such as different acid and complexing agent, make stable sols through stirring, reaction and ageing, then with dipping lift, methods such as spin coating or spraying impose on matrix surface through clean with colloidal sol, postprocessing working procedures such as last drying roasting form thin film at matrix surface.Specific embodiment is: prepare the colloidal sol of associated metal earlier, and suitably regulate the viscosity and the surface tension of colloidal sol, then by spin coating or impregnating method with sol deposition on substrate, obtain wet film.Through super-dry, remove lower boiling solvent again, obtain dry film.The three-dimensional network of gel still exists in the dry film, also has a large amount of organic compositions in the film.Dry film is decomposed under higher temperature, make the organic composition decomposition combustion in the film, just obtain inorganic noncrystal membrane.Repeat above step, increase the thickness of film.Also noncrystal membrane must be annealed under higher temperature if obtain the crystalline film, rely on the crystalline nucleation that diffuses into of atom.Dry, decomposition and annealed process must be very careful, avoid that gel shrinks, crackle appearred in too fast, the stress concentration of volume change when organic composition decomposed.Because each composition is the mixing of molecular level in the gel, atoms metal need not the long-range diffusion and gets final product nucleation, thereby Tc significantly reduces than solid state reaction temperature.
Difference according to using raw material can be divided into sol-gel method two kinds of aqua-solution method and alkoxide process.The raw material of aqua-solution method generally is the aqueous solution of metal-salt, and the formation of its colloidal sol is mainly finished by the hydrolysis of metallic cation:
M
n++nH
2O-M(OH)n+nH
+
The alkoxide process raw material is a metal alkoxide solution, relates generally to two processes of hydrolysis, polymerization of alkoxide.Do not exist tangible colloidal sol to form step for this method, but hydrolysis and polymerization have caused the formation of gel simultaneously finally.
TiO based on sol-gel method
2Method for manufacturing thin film is to study more titanium deoxid film preparation method at present, and concrete reaction process is as follows:
Ti (OR)
4+ xH
2O → Ti (OR)
4-x(OH) x+xROH (hydrolysis reaction)
-Ti-OH+HO-Ti-→-Ti-O-Ti-+H
2O (dehydration polycondensation)
-Ti-OR+RO-Ti-→-Ti-O-Ti-+ROH (losing pure polycondensation)
R can be the groups of different sizes such as Me, Et, Pr, Bu in the formula.
In a single day hydrolysis reaction in the said process takes place, and dehydration polycondensation and the pure polycondensation of mistake are promptly carried out in succession.The hydrolysis rate of titanium alkoxide is very fast, and a lot of researchs think that these characteristics are relevant with the spontaneous alcoholization process of titanium alkoxide in different groups solvents:
Ti(OR)n+xR′OH＝Ti(OR′)n-x+xROH
Because titanium ion is variable valency metal ions, the hexa-coordinate constructional feature of titanium ion make its can with form the coordinations relation more than four alkoxy grps, therefore can be in the solvent that is different from titanium alkoxide groups spontaneous the alcoholization.When alcoholization reaction carried out, hydrolysis reaction was easy to take place, thereby makes the hydrolysis rate of titanium alkoxide fast especially.And titanium ion four-coordination structure makes it can not spontaneously carry out alcoholization reaction, and its alcoholization must have the catalyzer existence to take place, so hydrolysis rate is very slow when not having catalyzer.An acidic catalyst plays restraining effect to the hydrolysis of titanium alkoxide: water-content increases in the solution, and the hydrolytie polycondensation process is accelerated.Solvent in the titanium alkoxide solution, water content and potential of hydrogen are not only influential to the sol-gel process of hydrolytie polycondensation, and to formed TiO
2Crystalline structure is relevant.
The Sol-gel film surface generally all can have small crackle, results from film drying and heat treatment stages, and analyzing mainly is following four reasons: (1) colloidal sol, gel film and during thermal treatment evaporation rate too fast; (2) film (gel) is different with the shrinking percentage of matrix, gel is a kind of organic mixture, volatilization is very fast when heating, shrink rapidly, shrinking percentage is very big, but matrix is a metal alloy, shrinking percentage is very little comparatively speaking, and the coefficient of thermal expansion of this gel and matrix differs greatly, and also can produce stress during the heating cooling, and film will crack when high-temperature heat treatment like this; (3) top layer of gel can be solidified owing to contact with air at once, form one deck duricrust, and the gel inside solidification is very slow, and when thermal treatment, gel organism major part can become gas, thereby when gases are heated, they expand breaks through the top layer duricrust, cracks; (4) during roasting because the destruction of organic volatilization and polymeric skeleton easily causes the film be full of cracks crack to occur.
Summary of the invention
The objective of the invention is provides a kind of sol-gel method to prepare TiO in order to overcome the deficiencies in the prior art
2The method of film.Can go out the good TiO of surface quality at metal or ceramic surface preparation by this method
2Film.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of sol-gel method prepares TiO
2The method of film is characterized in that, this method may further comprise the steps:
Step 1, TiO
2The preparation of colloidal sol and ageing
Earlier with chemical pure Ti (OC
4H
9) be dissolved in analytically pure CH
3OCH
2CH
2Among the OH, then add analytically pure CH
3COCH
2COOC
2H
5With dry anticracking agent HCONH
2On constant temperature blender with magnetic force, carry out first time magnetic agitation under the room temperature and get mixing solutions, add pH regulator solution toward described mixing solutions again, add pH regulator solution 1ml～3ml in every 100ml mixing solutions, and add in the mode that drips, carry out the light yellow TiO that magnetic agitation for the second time obtains homogeneous transparent after pH regulator solution dropwises
2Colloidal sol, still aging back is standby; Wherein, Ti (OC
4H
9): CH
3OCH
2CH
2OH: CH
3COCH
2COOC
2H
5: HCONH
2Volume ratio be 10: 50: 2～6: 1～4;
Step 2, TiO
2The preparation of film
The plated film matrix that cleans up is put into sol evenning machine, then with the TiO after the ageing
2Colloidal sol drips at the plated film matrix surface, connecting the sol evenning machine power supply begins to film, the plated film matrix that to film is then put into loft drier, speed with 2 ℃/min slowly is warming up to 100 ℃～150 ℃, and closes the loft drier power supply after being incubated 4～8 hours, is cooled to room temperature, and then put into box high temperature resistance furnace and slowly be warming up to 500 ℃～800 ℃ with the speed of 2 ℃/min, be incubated 1 hour, in stove, naturally cool to room temperature, promptly obtain TiO
2Film.
Also comprise TiO
2The aftertreatment of film: with the TiO in the step 2
2Film is put into the high-temperature steam pot and is handled 15～25min, and treatment temp is 130 ℃～150 ℃, again with TiO
2Film is put into boiling water and is handled 8～15min.
The time of magnetic agitation is 40min for the first time described in the above-mentioned steps one.
The time of magnetic agitation is 3-4 hour for the second time described in the above-mentioned steps one.
The aged time described in the above-mentioned steps one is 30 hours.
TiO described in the above-mentioned steps one
2Temperature when colloidal sol preparation and ageing is controlled at 5～25 ℃.
PH regulator solution is by HNO described in the above-mentioned steps one
3Formulated with distilled water, the pH value of pH regulator solution is 1～3.
The rotating speed of sol evenning machine described in the above-mentioned steps two is 5000r/min, and the time of filming is 30 seconds.
Plated film matrix described in the above-mentioned steps two is metallic matrix or inorganic materials matrix; Described metallic matrix is multiple solid metals such as pure titanium or titanium alloy, and the inorganic materials matrix is multiple nonmetal, on-macromolecular materials such as glasswork or silicon chip.
In order to reduce even to eliminate TiO
2The film crackle, spy of the present invention adds an amount of dry anticracking agent HCONH in colloidal sol
2, it can form firm spacial framework in colloidal sol, gel, and it is too fast to avoid gel to shrink when thermal treatment, and weakens the impact fracture of high-temperature gas to the gel top layer.And the gained film is carried out high-temperature steam processing and two step of hydro-thermal subsequent disposal, eliminate the film surface internal stress, weaken even healed cracks, improve the film surface quality with part.
The present invention compared with prior art has the following advantages:
1, the coatingsurface crackle seldom covers more completely, and surface quality is better.
2, the TiO of this method preparation
2There is functional group in film surface, has certain activity.
The invention will be further described below in conjunction with specific embodiment, and embodiment is just to explanation of the present invention and non-limiting.
Embodiment
The present invention relates to a kind of sol-gel method and prepare TiO
2The method of film may further comprise the steps:
Step 1, TiO
2The preparation of colloidal sol
With chemical pure Ti (OC
4H
9) as TiO
2The precursor of colloidal sol adds analytically pure ethylene glycol monoemethyl ether CH
3OCH
2CH
2OH is as solvent, in order to delay Ti (OC
4H
9) intense hydrolysis, in solution, add an amount of analytically pure methyl aceto acetate (CH
3COCH
2COOC
2H
5), add analytically pure dry anticracking agent methane amide (HCONH simultaneously
2); The concrete operations step is: elder generation is with the Ti (OC of 10ml
4H
9) be dissolved in the CH of 50ml
3OCH
2CH
2Among the OH, then add the CH of 2ml～6ml
3COCH
2COOC
2H
5And the HCONH of 1ml～4ml
2, on constant temperature blender with magnetic force, stir 40min under the room temperature and get mixing solutions, (pH regulator solution is by HNO to add pH regulator solution again
3With the distilled water preparation, pH is 1～3), add pH regulator solution 1ml～3ml in every 100ml mixing solutions, and add in the mode that drips, pH regulator solution dropwises the back and continued magnetic agitation 3-4 hour, obtains even, transparent light yellow TiO
2Colloidal sol, standby after still aging 30 hours; Temperature when colloidal sol preparation and ageing is controlled at 5～25 ℃;
Step 2, TiO
2The preparation of film and subsequent disposal thereof
201, TiO
2The preparation of film
The plated film matrix that cleans up is put into sol evenning machine, then the colloidal sol after the ageing is dripped at the plated film matrix surface, connecting the sol evenning machine power supply begins to film, the sol evenning machine rotating speed is 5000r/min, the time of filming is 30 seconds, the plated film matrix that to film is then put into loft drier, speed with 2 ℃/min slowly is warming up to 100 ℃～150 ℃, and close the loft drier power supply after being incubated 4～8 hours, be cooled to room temperature, and then put into box high temperature resistance furnace and slowly be warming up to 500 ℃～800 ℃, be incubated 1 hour with the speed of 2 ℃/min, in stove, naturally cool to room temperature, promptly obtain TiO
2Film;
202, TiO
2The aftertreatment of film
With the TiO in the step 201
2Film is put into the high-temperature steam pot and is handled 15min～25min, and treatment temp is 130 ℃～150 ℃; Again with TiO
2Film is put into clean beaker, adds 3/5 place of distilled water to beaker, is heated to boiling, and handles 8min～15min in boiling water.After above-mentioned processing, can obtain the good TiO of surface quality
2Film.
TiO in following examples
2Temperature when colloidal sol preparation and ageing all is controlled at 5～25 ℃.
Embodiment 1
Elder generation is with the Ti (OC of 10ml
4H
9) be dissolved in the CH of 50ml
3OCH
2CH
2Among the OH, then add the CH of 4ml
3COCH
2COOC
2H
5With 2ml HCONH
2On constant temperature blender with magnetic force, stir 40min under the room temperature.Add pH regulator solution (pH regulator solution is by nitric acid and distilled water preparation, and pH is 2) again, add-on is to add pH regulator solution 2ml in every 100ml mixing solutions, and adds in the mode that drips.PH regulator solution dropwises the back and continued magnetic agitation 3 hours, obtains even, transparent light yellow TiO
2Colloidal sol.Colloidal sol is standby after still aging 30 hours.The plated film matrix that cleans up is put into sol evenning machine, and the plated film matrix is metallic matrix or inorganic materials matrix, and then that ageing is good colloidal sol drips at specimen surface.Start power supply, rotating speed is 5000r/min, and the time is 30 seconds.Then sample is put into immediately the baking oven under the room temperature, slowly be warming up to 100 ℃ with the speed of 2 ℃/min, and 100 ℃ of insulations 8 hours.The box high temperature resistance furnace of putting into temperature then and be 100 ℃ slowly is warming up to 500 ℃ of insulations 1 hour with the speed of 2 ℃/min, naturally cools to room temperature in stove, can obtain TiO
2Film.At last the gained film is put into the high-temperature steam pot earlier and handled 15min for 150 ℃, in 100 ℃ of boiling water, handle 10min again.
Embodiment 2
Elder generation is with the Ti (OC of 10ml
4H
9) be dissolved in the CH of 50ml
3OCH
2CH
2OH then adds the CH of 4ml
3COCH
2COOC
2H
5HCONH with 2ml
2On constant temperature blender with magnetic force, stir 40min under the room temperature.Add pH regulator solution (pH regulator solution is by nitric acid and distilled water preparation, and pH is 2) again, add-on is to add pH regulator solution 2ml in every 100ml mixing solutions, and adds in the mode that drips.PH regulator solution dropwises the back and continued magnetic agitation 3 hours, obtains even, transparent light yellow TiO
2Colloidal sol.Colloidal sol is standby after still aging 30 hours.The plated film matrix sample that cleans up is put into sol evenning machine, and the plated film matrix is metallic matrix or inorganic materials matrix, and then that ageing is good colloidal sol drips at pure titanium specimen surface.Start power supply, rotating speed is 5000r/min, and the time is 30 seconds.Then sample is put into immediately the baking oven under the room temperature, slowly be warming up to 150 ℃ with the speed of 2 ℃/min, and 150 ℃ of insulations 4 hours.The box high temperature resistance furnace of putting into temperature then and be 100 ℃ slowly is warming up to 600 ℃ of insulations 1 hour with the speed of 2 ℃/min, naturally cools to room temperature in stove, can obtain TiO
2Film.At last the gained film is put into the high-temperature steam pot earlier and handled 22min for 140 ℃, in 100 ℃ of boiling water, handle 12min again.
Embodiment 3
Elder generation is with the Ti (OC of 10ml
4H
9) be dissolved in the CH of 50ml
3OCH
2CH
2Among the OH, then add the CH of 4ml
3COCH
2COOC
2H
5HCONH with 2ml
2On constant temperature blender with magnetic force, stir 40min under the room temperature.Add pH regulator solution (pH regulator solution is by nitric acid and distilled water preparation, and pH is 2) again, add-on is to add pH regulator solution 2ml in every 100ml mixing solutions, and adds in the mode that drips.PH regulator solution dropwises the back and continued magnetic agitation 3 hours, obtains even, transparent light yellow TiO
2Colloidal sol.Colloidal sol is standby after still aging 30 hours.The plated film matrix sample that cleans up is put into sol evenning machine, and the plated film matrix is metallic matrix or inorganic materials matrix, and then that ageing is good colloidal sol drips at specimen surface.Start power supply, rotating speed is 5000r/min, and the time is 30 seconds.Then sample is put into immediately the baking oven under the room temperature, slowly be warming up to 120 ℃ with the speed of 2 ℃/min, and 120 ℃ of insulations 6 hours.The box high temperature resistance furnace of putting into temperature then and be 100 ℃ slowly is warming up to 700 ℃ of insulations 1 hour with the speed of 2 ℃/min, naturally cools to room temperature in stove, can obtain TiO
2Film.At last the gained film is put into the high-temperature steam pot earlier and handled 25min for 130 ℃, in 100 ℃ of boiling water, handle 15min again.
Embodiment 4
Elder generation is with the Ti (OC of 10ml
4H
9) be dissolved in the CH of 50ml
3OCH
2CH
2Among the OH, then add the CH of 4ml
3COCH
2COOC
2H
5HCONH with 2ml
2On constant temperature blender with magnetic force, stir 40min under the room temperature.Add pH regulator solution (pH regulator solution is by nitric acid and distilled water preparation, and pH is 2) again, add-on is to add pH regulator solution 2ml in every 100ml mixing solutions, and adds in the mode that drips.PH regulator solution dropwises the back and continued magnetic agitation 3 hours, obtains even, transparent light yellow TiO
2Colloidal sol.Colloidal sol is standby after still aging 30 hours.The pure titanium sample that cleans up is put into sol evenning machine, and then that ageing is good colloidal sol drips at specimen surface.Start power supply, rotating speed is 5000r/min, and the time is 30 seconds.Then sample is put into immediately the baking oven under the room temperature, slowly be warming up to 100 ℃ with the speed of 2 ℃/min, and 100 ℃ of insulations 6 hours.The box high temperature resistance furnace of putting into temperature then and be 100 ℃ slowly is warming up to 800 ℃ of insulations 1 hour with the speed of 2 ℃/min, naturally cools to room temperature in stove, can obtain TiO
2Film.At last the gained film is put into the high-temperature steam pot earlier and handled 25min for 150 ℃, in 100 ℃ of boiling water, handle 8min again.
Embodiment 5
Elder generation is with the Ti (OC of 10ml
4H
9) be dissolved in the CH of 50ml
3OCH
2CH
2Among the OH, then add the CH of 5ml
3COCH
2COOC
2H
5HCONH with 2ml
2On constant temperature blender with magnetic force, stir 40min under the room temperature.Add pH regulator solution (pH regulator solution is by nitric acid and distilled water preparation, and pH is 2) again, add-on is to add pH regulator solution 3ml in every 100ml mixing solutions, and adds in the mode that drips.PH regulator solution dropwises the back and continued magnetic agitation 3 hours, obtains even, transparent light yellow TiO
2Colloidal sol.Colloidal sol is standby after still aging 30 hours.The plated film matrix sample that cleans up is put into sol evenning machine, and the plated film matrix is metallic matrix or inorganic materials matrix, and then that ageing is good colloidal sol drips at specimen surface.Start power supply, rotating speed is 5000r/min, and the time is 30 seconds.Then sample is put into immediately the baking oven under the room temperature, slowly be warming up to 100 ℃ with the speed of 2 ℃/min, and 100 ℃ of insulations 6 hours.The box high temperature resistance furnace of putting into temperature then and be 100 ℃ slowly is warming up to 500 ℃ of insulations 1 hour with the speed of 2 ℃/min, naturally cools to room temperature in stove, can obtain TiO
2Film.At last the gained film is put into the high-temperature steam pot earlier and handled 25min for 150 ℃, in 100 ℃ of boiling water, handle 10min again.
Embodiment 6
Elder generation is with the Ti (OC of 10ml
4H
9) be dissolved in the CH of 50ml
3OCH
2CH
2Among the OH, then add the CH of 4ml
3COCH
2COOC
2H
5HCONH with 4ml
2On constant temperature blender with magnetic force, stir 40min under the room temperature.Add pH regulator solution (pH regulator solution is by nitric acid and distilled water preparation, and pH is 2) again, add-on is to add pH regulator solution 1ml in every 100ml mixing solutions, and adds in the mode that drips.PH regulator solution dropwises the back and continued magnetic agitation 3 hours, obtains even, transparent light yellow TiO
2Colloidal sol.Colloidal sol is standby after still aging 30 hours.The titanium alloy sample that cleans up is put into sol evenning machine, and then that ageing is good colloidal sol drips at specimen surface.Start power supply, rotating speed is 5000r/min, and the time is 30 seconds.Then sample is put into immediately the baking oven under the room temperature, slowly be warming up to 100 ℃ with the speed of 2 ℃/min, and 100 ℃ of insulations 6 hours.The box high temperature resistance furnace of putting into temperature then and be 100 ℃ slowly is warming up to 500 ℃ of insulations 1 hour with the speed of 2 ℃/min, naturally cools to room temperature in stove, can obtain TiO
2Film.At last the gained film is put into the high-temperature steam pot earlier and handled 25min for 150 ℃, in 100 ℃ of boiling water, handle 10min again.
Embodiment 7
Elder generation is with the Ti (OC of 10ml
4H
9) be dissolved in the CH of 50ml
3OCH
2CH
2Among the OH, then add the CH of 2ml
3COCH
2COOC
2H
5HCONH with 1ml
2On constant temperature blender with magnetic force, stir 40min under the room temperature.Add pH regulator solution (pH regulator solution is by nitric acid and distilled water preparation, and pH is 2) again, add-on is to add pH regulator solution 2ml in every 100ml mixing solutions, and adds in the mode that drips.PH regulator solution dropwises the back and continued magnetic agitation 4 hours, obtains even, transparent light yellow TiO
2Colloidal sol.Colloidal sol is standby after still aging 30 hours.The silicon chip sample that cleans up is put into sol evenning machine, and then that ageing is good colloidal sol drips at specimen surface.Start power supply, rotating speed is 5000r/min, and the time is 30 seconds.Then sample is put into immediately the baking oven under the room temperature, slowly be warming up to 100 ℃ with the speed of 2 ℃/min, and 100 ℃ of insulations 6 hours.The box high temperature resistance furnace of putting into temperature then and be 100 ℃ slowly is warming up to 600 ℃ of insulations 1 hour with the speed of 2 ℃/min, naturally cools to room temperature in stove, can obtain TiO
2Film.At last the gained film is put into the high-temperature steam pot earlier and handled 25min for 150 ℃, in 100 ℃ of boiling water, handle 10min again.
Embodiment 8
Elder generation is with the Ti (OC of 10ml
4H
9) be dissolved in the CH of 50ml
3OCH
2CH
2Among the OH, then add the CH of 4ml
3COCH
2COOC
2H
5HCONH with 2ml
2On constant temperature blender with magnetic force, stir 40min under the room temperature.Add pH regulator solution (pH regulator solution is by nitric acid and distilled water preparation, and pH is 2) again, add-on is to add pH regulator solution 2ml in every 100ml mixing solutions, and adds in the mode that drips.PH regulator solution dropwises the back and continued magnetic agitation 3 hours, obtains even, transparent light yellow TiO
2Colloidal sol.Colloidal sol is standby after still aging 30 hours.The glasswork that cleans up is put into sol evenning machine, and then that ageing is good colloidal sol drips at specimen surface.Start power supply, rotating speed is 5000r/min, and the time is 30 seconds.Then sample is put into immediately the baking oven under the room temperature, slowly be warming up to 100 ℃ with the speed of 2 ℃/min, and 100 ℃ of insulations 8 hours.The box high temperature resistance furnace of putting into temperature then and be 100 ℃ slowly is warming up to 500 ℃ of insulations 1 hour with the speed of 2 ℃/min, naturally cools to room temperature in stove, can obtain TiO
2Film.At last the gained film is put into the high-temperature steam pot earlier and handled 25min for 150 ℃, in 100 ℃ of boiling water, handle 10min again.
Embodiment 9
Elder generation is with the Ti (OC of 10ml
4H
9) be dissolved in the CH of 50ml
3OCH
2CH
2Among the OH, then add the CH of 6ml
3COCH
2COOC
2H
5HCONH with 3ml
2On constant temperature blender with magnetic force, stir 40min under the room temperature.Add pH regulator solution (pH regulator solution is by nitric acid and distilled water preparation, and pH is 1) again, add-on is to add pH regulator solution 2ml in every 100ml mixing solutions, and adds in the mode that drips.PH regulator solution dropwises the back and continued magnetic agitation 3 hours, obtains even, transparent light yellow TiO
2Colloidal sol.Colloidal sol is standby after still aging 30 hours.The plated film matrix sample that cleans up is put into sol evenning machine, and the plated film matrix is metallic matrix or inorganic materials matrix, and then that ageing is good colloidal sol drips at specimen surface.Start power supply, rotating speed is 5000r/min, and the time is 30 seconds.Then sample is put into immediately the baking oven under the room temperature, slowly be warming up to 100 ℃ with the speed of 2 ℃/min, and 100 ℃ of insulations 6 hours.The box high temperature resistance furnace of putting into temperature then and be 100 ℃ slowly is warming up to 500 ℃ of insulations 1 hour with the speed of 2 ℃/min, naturally cools to room temperature in stove, can obtain TiO
2Film.At last the gained film is put into the high-temperature steam pot earlier and handled 25min for 150 ℃, in 100 ℃ of boiling water, handle 10min again.
Embodiment 10
Elder generation is with the Ti (OC of 10ml
4H
9) be dissolved in the CH of 50ml
3OCH
2CH
2Among the OH, then add the CH of 4ml
3COCH
2COOC
2H
5HCONH with 2ml
2On constant temperature blender with magnetic force, stir 40min under the room temperature.Add pH regulator solution (pH regulator solution is by nitric acid and distilled water preparation, and pH is 2) again, add-on is to add pH regulator solution 1ml in every 100ml mixing solutions, and adds in the mode that drips.PH regulator solution dropwises the back and continued magnetic agitation 3 hours, obtains even, transparent light yellow TiO
2Colloidal sol.Colloidal sol is standby after still aging 30 hours.The plated film matrix sample that cleans up is put into sol evenning machine, and the plated film matrix is metallic matrix or inorganic materials matrix, and then that ageing is good colloidal sol drips at specimen surface.Start power supply, rotating speed is 5000r/min, and the time is 30 seconds.Then sample is put into immediately the baking oven under the room temperature, slowly be warming up to 120 ℃ with the speed of 2 ℃/min, and 100 ℃ of insulations 6 hours.The box high temperature resistance furnace of putting into temperature then and be 100 ℃ slowly is warming up to 500 ℃ of insulations 1 hour with the speed of 2 ℃/min, naturally cools to room temperature in stove, can obtain TiO
2Film.At last the gained film is put into the high-temperature steam pot earlier and handled 25min for 150 ℃, in 100 ℃ of boiling water, handle 10min again.
Embodiment 11
Elder generation is with the Ti (OC of 10ml
4H
9) be dissolved in the CH of 50ml
3OCH
2CH
2Among the OH, then add the CH of 4ml
3COCH
2COOC
2H
5HCONH with 2ml
2On constant temperature blender with magnetic force, stir 40min under the room temperature.Add pH regulator solution (pH regulator solution is by nitric acid and distilled water preparation, and pH is 2) again, add-on is to add pH regulator solution 2ml in every 100ml mixing solutions, and adds in the mode that drips.PH regulator solution dropwises the back and continued magnetic agitation 3.5 hours, obtains even, transparent light yellow TiO
2Colloidal sol.Colloidal sol is standby after still aging 30 hours.The plated film matrix sample that cleans up is put into sol evenning machine, and the plated film matrix is metallic matrix or inorganic materials matrix, and then that ageing is good colloidal sol drips at specimen surface.Start power supply, rotating speed is 5000r/min, and the time is 30 seconds.Then sample is put into immediately the baking oven under the room temperature, slowly be warming up to 120 ℃ with the speed of 2 ℃/min, and 120 ℃ of insulations 6 hours.The box high temperature resistance furnace of putting into temperature then and be 100 ℃ slowly is warming up to 500 ℃ of insulations 1 hour with the speed of 2 ℃/min, naturally cools to room temperature in stove, can obtain TiO
2Film.At last the gained film is put into the high-temperature steam pot earlier and handled 25min for 150 ℃, in 100 ℃ of boiling water, handle 15min again.
Claims (10)
1. a sol-gel method prepares TiO
2The method of film is characterized in that, this method may further comprise the steps:
Step 1, TiO
2The preparation of colloidal sol and ageing
Earlier with chemical pure Ti (OC
4H
9) be dissolved in analytically pure CH
3OCH
2CH
2Among the OH, then add analytically pure CH
3COCH
2COOC
2H
5With dry anticracking agent HCONH
2On constant temperature blender with magnetic force, carry out first time magnetic agitation under the room temperature and get mixing solutions, add pH regulator solution toward described mixing solutions again, add pH regulator solution 1ml～3ml in every 100ml mixing solutions, and add in the mode that drips, carry out the light yellow TiO that magnetic agitation for the second time obtains homogeneous transparent after pH regulator solution dropwises
2Colloidal sol, still aging back is standby; Wherein, Ti (OC
4H
9): CH
3OCH
2CH
2OH: CH
3COCH
2COOC
2H
5: HCONH
2Volume ratio be 10: 50: 2～6: 1～4;
Step 2, TiO
2The preparation of film
The plated film matrix that cleans up is put into sol evenning machine, then with the TiO after the ageing
2Colloidal sol drips at the plated film matrix surface, connecting the sol evenning machine power supply begins to film, the plated film matrix that to film is then put into loft drier, speed with 2 ℃/min slowly is warming up to 100 ℃～150 ℃, and closes the loft drier power supply after being incubated 4～8 hours, is cooled to room temperature, and then put into box high temperature resistance furnace and slowly be warming up to 500 ℃～800 ℃ with the speed of 2 ℃/min, be incubated 1 hour, in stove, naturally cool to room temperature, promptly obtain TiO
2Film.
2. a kind of sol-gel method according to claim 1 prepares TiO
2The method of film is characterized in that, also comprises TiO
2The aftertreatment of film: with the TiO in the step 2
2Film is put into the high-temperature steam pot and is handled 15～25min, and treatment temp is 130 ℃～150 ℃, again with TiO
2Film is put into boiling water and is handled 8～15min.
3. a kind of sol-gel method according to claim 1 and 2 prepares TiO
2The method of film is characterized in that, the time of magnetic agitation is 40min for the first time described in the step 1.
4. a kind of sol-gel method according to claim 1 and 2 prepares TiO
2The method of film is characterized in that, the time of magnetic agitation is 3-4 hour for the second time described in the step 1.
5. a kind of sol-gel method according to claim 1 and 2 prepares TiO
2The method of film is characterized in that, the aged time described in the step 1 is 30 hours.
6. a kind of sol-gel method according to claim 1 and 2 prepares TiO
2The method of film is characterized in that, TiO described in the step 1
2Temperature when colloidal sol preparation and ageing is controlled at 5～25 ℃.
7. a kind of sol-gel method according to claim 1 and 2 prepares TiO
2The method of film is characterized in that, the solution of pH regulator described in the step 1 is by HNO
3Formulated with distilled water, the pH value of pH regulator solution is 1～3.
8. a kind of sol-gel method according to claim 1 and 2 prepares TiO
2The method of film is characterized in that, the rotating speed of sol evenning machine described in the step 2 is 5000r/min, and the time of filming is 30 seconds.
9. a kind of sol-gel method according to claim 1 and 2 prepares TiO
2The method of film is characterized in that, the matrix of plated film described in the step 2 is metallic matrix or inorganic materials matrix.
10. a kind of sol-gel method according to claim 9 prepares TiO
2The method of film is characterized in that, described metallic matrix is pure titanium or titanium alloy, and the inorganic materials matrix is glasswork or silicon chip.
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