CN101412589A - Method for preparing TiO2 compound film on surface of glass substrate - Google Patents
Method for preparing TiO2 compound film on surface of glass substrate Download PDFInfo
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- CN101412589A CN101412589A CNA2008102008106A CN200810200810A CN101412589A CN 101412589 A CN101412589 A CN 101412589A CN A2008102008106 A CNA2008102008106 A CN A2008102008106A CN 200810200810 A CN200810200810 A CN 200810200810A CN 101412589 A CN101412589 A CN 101412589A
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- glass substrate
- tio
- film
- deionized water
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Abstract
The invention relates to a method for preparing a TiO2 composite film on a surface of a glass substrate. The method comprises the following steps: soaking the glass substrate in a solution containing H2SO4 and H2O2 according to volume ratio of 70 to 30, treating the glass substrate for 1 hour at a temperature of 90 DEG C, after cleaning and drying the glass substrate, soaking the glass substrate in a benzene solution containing hydrosulfuryl silane the concentration of which is between 0.1 and 2.0 mmol per liter, standing for 6 to 8 hours, taking out and washing the glass substrate, drying the glass substrate by blowing nitrogen, placing the glass substrate in 30-60 mass percent nitric acid, reacting for 1 hour at a temperature of between 50 and 80 DEG C, taking out and washing the glass substrate, and obtaining the glass substrate the surface of which is adhered with a sulfonic silane film; and placing the substrate in TiO2 suspension, standing for 4 to 20 hours at a temperature of between 20 and 80 DEG C; and taking out and washing the glass substrate by a large amount of deionized water, drying the washed glass substrate by blowing the nitrogen, and obtaining the glass substrate the surface of which is deposited with a modified TiO2 composite film. The method has short film forming period, can reduce frictional coefficient from 0.8 to 0.1 without a film, and has quite remarkable antifriction function.
Description
Technical field
The present invention relates to a kind ofly prepare TiO at glass substrate surface
2The method of laminated film.
Background technology
Electromechanical integration, ultrapreciseization and microminiaturized trend appear in the modern mechanical the reach of science, the friction pair gap of many new and high technology devices etc. often is in nanometer scale, owing to be subjected to the influence of dimensional effect in the micromachine, micro friction wear and nano-scale thin film lubrication have become key issue, can prepare the self-assembled nanometer film with self-assembling method at present and solve this problem.Compare with other preparation thin film technique, the self-assembled film technology has operability, adaptability is strong, is with a wide range of applications.
TiO
2Be most typical monodimension nanometer material, have numerous excellent properties with its particular structure.TiO
2Have superpower mechanical property, good adsorption property, thereby caused very big attention in the material field.But, TiO
2Radial nano-grade size and high surface energy cause its easy reunion, and be dispersed relatively poor, reduced TiO
2Effective L D ratio.In addition, TiO
2Insoluble in most solvents, wet performance is poor, is difficult to be formed with effective adhesive with substrate.In order to improve TiO
2Dispersed and increase itself and the bonding force of substrate interface, must pass through TiO
2Surface modification and method such as substrate surface assembling active group, improve TiO
2And the interface combination degree between the substrate surface obtains the good composite membrane of tribological property.
Find that by literature search publication number is the Chinese invention patent of CN1358804A, has introduced a kind of preparation method of solid film surface fatty acid self-composed monomolecular ultrathin lubrication membrane, this method is the unimolecular layer at solid surface self-assembly one deck lipid acid.Choose the lipid acid that easily is adsorbed in solid surface, be mixed with dilute solution, the ceramic membrane that makes is immersed the lipid acid dilute solution that configures rapidly under room temperature, reacted 24～48 minutes.This method needs 24～96 hours time to prepare precursor solution in the process of preparation self-assembled film, make that so whole film forming period is long, and in the process that substrate is handled, do not relate to concrete grammar, and this method is to have prepared a kind of organic self-assembled film, does not relate to TiO
2Improvement and research to film performance.
Summary of the invention
The present invention discloses and a kind ofly prepares TiO at glass substrate surface
2The method of laminated film, it is long that its purpose is to overcome the prior art film forming period, and do not relate to concrete grammar in the process that substrate is handled, and especially do not relate at glass substrate surface to prepare TiO
2The method of laminated film; The present invention not only technology is simple, and film forming period is short, and the laminated film that is self-assembled into has good antifriction performance, can effectively solve the friction problem of micro mechanical system.
The present invention adopts the surface hydroxylated glass substrate of process as base material, adopt self-assembling method to prepare the hydrosulphonyl silane film on its surface, mercapto functional group with the hydrosulphonyl silane film surface under appropriate reaction conditions is oxidized to sulfonate functional groups, use N again, dinethylformamide (DMF) TiO
2Disperse night at silane surface preparation TiO
2Laminated film.
The present invention adopts following technical scheme to realize:
A kind ofly prepare TiO at glass substrate surface
2The method of laminated film is characterized in that comprising the steps:
1) pre-treatment of glass substrate:
A) earlier glass substrate being dipped in volume ratio is H
2SO
4: H
2O
2In=70: 30 the solution, handled 1 hour down in 90 ℃, dry with being placed on after the deionized water ultrasonic cleaning in the inherent baking oven of dust keeper;
B) to immerse hydrosulphonyl silane concentration be in the benzole soln of 0.1～2.0mmol/L to the glass substrate after will handling then, leaves standstill taking-ups in 6～8 hours, and flushing then dries up with nitrogen;
C) glass substrate being placed mass concentration is 30%～60% nitric acid again, 50～80 ℃ of reactions 1 hour down, takes out and use deionized water rinsing, obtains the glass substrate that the surface has the sulfonic silane film;
2) preparation TiO
2Dispersion liquid:
With TiO
2At room temperature put into N by 0.1～0.2mg/ml, the dinethylformamide dispersion agent, 40W ultrasonic dispersing 1～4 hour obtains steady suspension;
3) prepare TiO at glass substrate surface
2Laminated film:
There is the glass substrate of sulfonic silane film to immerse the TiO for preparing surface-assembled
2In the suspension, under 20～80 ℃, left standstill 4～20 hours; Take out a large amount of deionized water rinsings of glass substrate, the flushing back dries up with nitrogen, and obtaining surface deposition has modification TiO
2The glass substrate of laminated film.
The present invention prepares TiO at hydroxylated glass substrate upper surface
2Laminated film, because having carried out hydroxylation, handles glass substrate surface, contain hydrolyzable active group in the hydrosulphonyl silane molecule, can build Si-O by chemistry combines with the base material with active group Si-OH, form the silane self-assembled film that one deck has mercapto groups at substrate surface, with surface-assembled the hydrosulphonyl silane bottom substrate insert in the salpeter solution and leave standstill for some time, the mercapto groups of film surface is become sulfonic group by in-situ oxidation.Again it is inserted TiO
2Behind the suspension, substrate surface is with depositing Ti O
2
Technology of the present invention is simple, and film forming period is short, does not have problem of environmental pollution; TiO in the glass substrate surface preparation
2Laminated film can be with frictional coefficient 0.8 during from no film be reduced to about 0.1, have fairly obvious antifriction function.TiO in addition
2Laminated film also has good wear resistance, can become micromachine ideal boundary lubricant film.
Embodiment
Below in conjunction with embodiment the present invention is done to describe in further detail, but present embodiment is not limited to the present invention, every employing similarity method of the present invention and similar variation thereof all should be listed protection scope of the present invention in.
Embodiment 1:
At first, glass substrate adopts the hydroxylation pre-treatment, and treatment process: it is H that glass substrate is dipped in volume ratio
2SO
4: H
2O
2In the solution of=70: 30 (Pirahan), handled 1 hour down in 90 ℃, use a large amount of deionized water ultrasonic cleaning 20 minutes again, be placed in the inherent baking oven of a dust keeper dry, to leave standstill 6 hours in the glass substrate immersion hydrosulphonyl silane solution after handling, the component volumetric molar concentration of hydrosulphonyl silane solution is: 3-sulfydryl propyl group methyl dimethoxysilane 0.2mmol/L, solvent is a benzole soln.Use chloroform, acetone, deionized water rinsing after the taking-up respectively, remove the organic molecule of surface physics absorption, dry up with nitrogen again that to place weight concentration be 30% nitric acid, 80 ℃ of reaction taking-ups after 1 hour down, use a large amount of deionized water rinsings, so just end sulfydryl in-situ oxidation is become sulfonic group, obtain the glass substrate of surface with the sulfonic silane film.
At room temperature with TiO
2Put into N by 0.15mg/ml, dinethylformamide (DMF) dispersion agent, ultrasonic dispersing (40W) 2 hours obtains steady suspension.
There is the glass substrate of sulfonic silane film to immerse the TiO for preparing surface-assembled
2In the suspension, left standstill under 20 ℃ 4 hours, take out and use a large amount of deionized water rinsings, the flushing back dries up with nitrogen, and so just obtaining surface deposition has modification TiO
2The glass substrate of laminated film.
Adopt SPM-9500 atomic force microscope (AFM), JEM-2010 scanning electronic microscope (SEM) and PHI-5702 type X-photoelectron spectrograph (XPS) to characterize the surface topography and the chemical ingredients of the composite membrane that obtains.Adopt the little frictional behaviour survey meter of the pure slip of some contact to measure the composite membrane frictional coefficient.
The XPS collection of illustrative plates shows in the Silan-based Thin Films that glass substrate surface is self-assembled into mercapto groups; Behind the in-situ oxidation, high valence state element sulphur is arranged, illustrate that the in-situ oxidation of the mercapto groups success on the surperficial Silan-based Thin Films has become sulfonic group.The SEM picture is then clearly seen TiO
2Be deposited on the surface of glass substrate, formed TiO
2Laminated film.On a little frictional behaviour survey meter of the pure slip of contact, measure clean glass substrate and glass substrate surface TiO respectively
2The frictional coefficient of composite membrane.TiO in the glass substrate surface preparation
2Composite membrane can be with frictional coefficient 0.8 during from no film be reduced to 0.12, have fairly obvious antifriction function.
Embodiment 2:
At first, the hydroxylation pre-treatment of glass substrate: glass substrate is dipped in the Pirahan solution, handled 1 hour down in 90 ℃, use a large amount of deionized water ultrasonic cleaning 20 minutes again, be placed on drying in the inherent baking oven of a dust keeper, the glass substrate after handling is immersed in the hydrosulphonyl silane solution for preparing, left standstill 7 hours, the component volumetric molar concentration of hydrosulphonyl silane solution is: 3-sulfydryl propyl group methyl dimethoxysilane 1.0mmol/L, and solvent is a benzole soln; After removing the surface physics adsorbed organic matter with chloroform, acetone, deionized water rinsing respectively after the taking-up, dry up with nitrogen that to place mass concentration be 50% nitric acid, reacted 1 hour down at 65 ℃, take out and use a large amount of deionized water rinsings, so just end sulfydryl in-situ oxidation is become sulfonic group, obtain the glass substrate of surface with the sulfonic silane film.
At room temperature with TiO
2Put into N by 0.1mg/ml, dinethylformamide (DMF) dispersion agent, ultrasonic dispersing (40W) 3 hours obtains steady suspension.
There is the glass substrate of sulfonic silane film to immerse the TiO for preparing surface-assembled
2In the suspension, left standstill under 60 ℃ 6 hours, take out and use a large amount of deionized water rinsings, the flushing back dries up with nitrogen, and so just obtaining surface deposition has modification TiO
2The glass substrate of laminated film.
Adopt the characterization method among the embodiment 1 that film quality is estimated.
The XPS collection of illustrative plates shows and contains sulfonic group and Ce elements in the thin film layers different in the laminated film that glass substrate surface is self-assembled into, and do not observe the index of silicon-dioxide after the Silan-based Thin Films assembling.The SEM picture is then clearly seen TiO
2Be deposited on the surface of glass substrate, formed TiO
2Laminated film.TiO in the glass substrate surface preparation
2Laminated film can be with frictional coefficient 0.8 during from no film be reduced to about 0.11, have fairly obvious antifriction function.
Embodiment 3:
At first, the hydroxylation pre-treatment of glass substrate: glass substrate is dipped in the Pirahan solution, handled 1 hour down in 90 ℃, use a large amount of deionized water ultrasonic cleaning 20 minutes again, be placed on drying in the inherent baking oven of a dust keeper, the glass substrate after handling is immersed in the hydrosulphonyl silane for preparing, left standstill 8 hours, the component volumetric molar concentration of hydrosulphonyl silane solution is: 3-sulfydryl propyl trimethoxy silicane 2.0mmol/L, solvent are benzole soln; After using chloroform, acetone, deionized water rinsing respectively after the taking-up, dry up that to place mass concentration be 60% nitric acid 50 ℃ of reactions 1 hour down with nitrogen, take out and use a large amount of deionized water rinsings, so just end sulfydryl in-situ oxidation is become sulfonic group, obtain the glass substrate of surface with the sulfonic silane film.
At room temperature with TiO
2Put into N by 0.2mg/ml, dinethylformamide (DMF) dispersion agent, ultrasonic dispersing (40W) 4 hours obtains steady suspension.
There is the glass substrate of sulfonic silane film to immerse the TiO for preparing surface-assembled
2In the suspension, left standstill under 80 ℃ 20 hours, take out and use a large amount of deionized water rinsings, the flushing back dries up with nitrogen, and so just obtaining surface deposition has modification TiO
2The glass substrate of laminated film.
Adopt the characterization method among the embodiment 1 that film quality is estimated.The XPS collection of illustrative plates shows is successfully assembling the hydrosulphonyl silane film on the substrate surface, and mercapto groups is become sulfonic group by in-situ oxidation; The SEM picture is then clearly seen TiO
2Be deposited on the surface of glass substrate, formed TiO
2Laminated film.TiO in the glass substrate surface preparation
2Laminated film can be with frictional coefficient 0.8 during from no film be reduced to about 0.1, have fairly obvious antifriction function.
Claims (1)
1, a kind ofly prepares TiO at glass substrate surface
2The method of laminated film is characterized in that comprising the steps:
1) pre-treatment of glass substrate:
A) earlier glass substrate being dipped in volume ratio is H
2SO
4: H
2O
2In=70: 30 the solution, handled 1 hour down in 90 ℃, dry with being placed on after the deionized water ultrasonic cleaning in the inherent baking oven of dust keeper;
B) to immerse hydrosulphonyl silane concentration be in the benzole soln of 0.1～2.0mmol/L to the glass substrate after will handling then, leaves standstill taking-ups in 6～8 hours, and flushing then dries up with nitrogen;
C) glass substrate being placed mass concentration is 30%～60% nitric acid again, 50～80 ℃ of reactions 1 hour down, takes out and use deionized water rinsing, obtains the glass substrate that the surface has the sulfonic silane film;
2) preparation TiO
2Dispersion liquid:
With TiO
2At room temperature put into N by 0.1～0.2mg/ml, the dinethylformamide dispersion agent, 40W ultrasonic dispersing 1～4 hour obtains steady suspension;
3) prepare TiO at glass substrate surface
2Laminated film:
There is the glass substrate of sulfonic silane film to immerse the TiO for preparing surface-assembled
2In the suspension, under 20～80 ℃, left standstill 4～20 hours; Take out a large amount of deionized water rinsings of glass substrate, the flushing back dries up with nitrogen, and obtaining surface deposition has modification TiO
2The glass substrate of laminated film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008102008106A CN101412589A (en) | 2008-10-07 | 2008-10-07 | Method for preparing TiO2 compound film on surface of glass substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008102008106A CN101412589A (en) | 2008-10-07 | 2008-10-07 | Method for preparing TiO2 compound film on surface of glass substrate |
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| Publication Number | Publication Date |
|---|---|
| CN101412589A true CN101412589A (en) | 2009-04-22 |
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ID=40593359
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008102008106A Pending CN101412589A (en) | 2008-10-07 | 2008-10-07 | Method for preparing TiO2 compound film on surface of glass substrate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103257377A (en) * | 2012-02-21 | 2013-08-21 | 江苏华天通科技有限公司 | Coated CR39 resin lens |
| CN106323918A (en) * | 2016-05-31 | 2017-01-11 | 中国科学院苏州纳米技术与纳米仿生研究所 | Local plasma optical imaging ellipsometry biosensor and preparation method thereof |
-
2008
- 2008-10-07 CN CNA2008102008106A patent/CN101412589A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103257377A (en) * | 2012-02-21 | 2013-08-21 | 江苏华天通科技有限公司 | Coated CR39 resin lens |
| CN103257377B (en) * | 2012-02-21 | 2015-03-25 | 江苏视客光电新材料有限公司 | Coated CR39 resin lens |
| CN106323918A (en) * | 2016-05-31 | 2017-01-11 | 中国科学院苏州纳米技术与纳米仿生研究所 | Local plasma optical imaging ellipsometry biosensor and preparation method thereof |
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Open date: 20090422 |