CN101397191B - Method for producing thin membrane - Google Patents
Method for producing thin membrane Download PDFInfo
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- CN101397191B CN101397191B CN200710030719XA CN200710030719A CN101397191B CN 101397191 B CN101397191 B CN 101397191B CN 200710030719X A CN200710030719X A CN 200710030719XA CN 200710030719 A CN200710030719 A CN 200710030719A CN 101397191 B CN101397191 B CN 101397191B
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Abstract
The invention provides a method for preparing films, which comprises the following steps: the sol-gel technique is adopted, tetraethoxysilane, ethanol, deionized water and HCL with weight proportion of 20:25:3:2 are mixed for preparing the sol solution; then the sol solution is let stand for a while so as to form a stable colloid solution; the colloid solution and thinner are mixed according to proportion, so as to form a coating solution; finally the coating solution is coated on the matrix, dryness is carried out, so as to form the films. In the invention, by controlling the proportion of the collide solution and the thinner, control on the thickness of the films is realized, therefore the invention has simple operation, can be carried out at normal temperature, can control the thickness of films precisely, so as to form the demanded films, therefore being in favor of industrial application.
Description
Affiliated technical field
The present invention relates to a kind of method for preparing film, relate in particular to a kind of method for preparing film of adjusting the control film thickness.
Background technology
Sol-gel method (Sol-Gel method) is preparation SiO
2, TiO
2, ZrO
2Deng the domestic method of film, the chemical uniformity of the film through the preparation of this method is good, processing procedure is simple, easy to operate, cost is low, be suitable for various base materials and can coat on the large complicated matrix, therefore be widely used.Utilize the Prepared by Sol Gel Method film generally compositions such as metal alkoxide (precursor), solvent, catalyzer and water to be deployed into sol solution; Be hydrolyzed under the effect of catalyzer, after the reactions such as condensation, polymerization; Slowly formation gelating soln again, then with this solution coat on matrix and form film.
Yet the film that utilizes aforesaid method to form receives proportionlity, preparation condition and the Effect of Environmental of compositions such as metal alkoxide, solvent, catalyzer and water to be difficult to accomplish artificially accurately control the thickness that film forms owing to its thickness.Certainly; During with the method for preparing film; Also can reach the effect of control thickness through the ratio between adjustment metal alkoxide, solvent, catalyzer and the water; But above-mentioned metal alkoxide, solvent, catalyzer and water are to be mutually related and each composition all can have influence on the generation of film.If only adjust one of above-mentioned four shared amounts, then whole proportionlity all can change, and this makes the thickness of film be difficult to control.Have only and adjust metal alkoxide, solvent, catalyzer and water proportionlity each other simultaneously and just can reach control, but this operation is too complicated, be difficult for realizing film thickness.
Summary of the invention
The objective of the invention is provides easy the reaching of a kind of ability accurately to control the preparation film process that film generates thickness to the problem that above-mentioned prior art exists.
For realizing above-mentioned purpose, a kind of method for preparing film provided by the invention may further comprise the steps: adopting sol-gel method is 20: 25: 3 with weight ratio: sol solution is produced in the tetraethoxysilane of 2 ratio, ethanol, deionized water and HCL mixing; Then sol solution is left standstill for some time and form stable colloidal solution; Again colloidal solution is proportionally mixed the formation coating solution with thinner; At last coating solution is coated on the matrix and dry and form film.
In sum; The present invention is through increasing a step with mixing diluents in the operation of traditional Prepared by Sol Gel Method film; Through adjusting the proportionlity between this thinner and the above-mentioned colloidal solution, make the thickness of film change according to certain rules, thereby realize control film thickness according to the variation of aforementioned proportion relation; Thereby present method is easy and simple to handle, can carry out at normal temperatures, thickness that can the accuracy controlling film and form the thickness that needs, thereby be convenient to industrial application.
Description of drawings
In Figure of description:
Fig. 1 prepares the film thickness and the coating solution concentration (SiO of the method for film for the present invention
2Colloidal solution/coating solution) graph of a relation.
Embodiment
By specifying technology contents of the present invention, structural attitude, being reached purpose and effect, will combine embodiment and conjunction with figs. to specify below.
The method that the present invention prepares film is the basis with the sol-gel method; At first a certain proportion of precursor, solvent, deionized water and catalyst mix are prepared sol solution, the film that the kind of this precursor, solvent, catalyzer and shared separately ratio can prepare is as required selected.When preparing different films, employed precursor is inequality, and existing is example with the preparation silica membrane only, at least a silane compound that the general selecting type of its precursor (1) is represented.
R
nSiX
4-n (1)
Wherein, R representes a kind of organo-functional group, and X representes water-disintegrable functional group, and n is 0～2 integer, and when n=2, the organo-functional group that two R represent both can be the same or different.
For the compound of formula (1) expression, preferentially select tetraethoxysilane, tetramethoxy-silicane, three ethoxymethyl silane and three ethoxyethyl silane.
Because above-mentioned precursor is pure dissolubility, corresponding solvent can select a kind of or mixing in the alcohols such as methyl alcohol, ethanol or Virahol to use, and preferentially selects ethanol.
Above-mentioned catalyzer both can be that tart also can be alkaline, and an acidic catalyst can be selected HCl, HNO
3, oxalic acid etc., basic catalyst can be selected NH
4OH, NaOH etc.Adopt an acidic catalyst to make and react the hydrolysis rapid speed, and condensation rates is slower, the particle that is generated is less, and surfacing and structure are comparatively fine and close; And adopt basic catalyst to cause the speed of hydrolysis slower, and condensation rates is very fast, formed particle is in the majority with the big person of particle, and the surface is difficult for smooth.As for selecting which kind of catalyst then should determine that different catalyst can be brought different effects, general preferred HCl solution based on the kind of concrete product requirement and predecessor.
Precursor, solvent, water and catalyzer that the silica membrane of present embodiment preparation is selected are respectively tetraethoxysilane, ethanol, deionized water and HCl; At first ethanol, deionized water and HCl are together added in the same container; Add tetraethoxysilane afterwards again, above-mentioned tetraethoxysilane, ethanol, deionized water and HCl weight ratio are roughly 20: 25: 3: 2, because when adopting this ratio; Formed silica membrane stability and tack are good, the conveniently regulating and controlling film thickness.They are mixed at normal temperatures; The pH value of this mixed solution is approximately 3.9～4.0, makes mixed solution reaction 2～4 hours, utilizes the magnetite whisking appliance to be aided with magnetite in the reaction process and stirs; And measure the pH value of reaction solution with pH value measuration meter; Make the pH value of reaction solution approximately remain on 3.9～4.0, the sol solution that obtains is left standstill made its aging (Aging) in 12～24 hours then, just can obtain the colloidal solution that fully hydrolysis and polymerization are accomplished.
Above process mainly is to have used sol-gel method, and in the present invention for the thickness of accuracy controlling film, the thickness that formation needs has increased by one with above-mentioned colloidal solution and a kind of thinner blended step by a certain percentage.Because above-mentioned colloidal solution mainly is pure dissolubility; In order to reach the effect of dissolving each other; Thinner can be selected alcohols or some lipid solvent, and wherein alcoholic solvent can adopt a kind of or mixing in the alcohols such as methyl alcohol, ethanol or Virahol to use, and preferentially selects ethanol.The coating solution that obtains after colloidal solution and the mixing diluents is coated on the matrix, adopts the mode of heating to make coating solution accomplish gel and the dry gradually film that forms simultaneously.Can adopt methods such as dip coating or spin-coating method during coating, Heating temperature maintains 100～300 ℃ as far as possible.
The film that obtains thus; Its thickness mainly receives the influence of colloidal solution proportion (being the concentration of coating solution) in coating solution; The concentration of coating solution is big more, and the thickness of film is big more, roughly is the relation of quadratic function between the thickness of film and the concentration of coating solution.When not adding thinner, only there is the colloidal solution composition in the coating solution, this moment, the thickness of film was maximum.When colloidal solution shared ratio in coating solution was very little, the thickness of film can be very thin, yet this thickness of not representing film can be infinitely small; When arriving certain limit; It is inhomogeneous that the thickness of film will become, even not continuous, do not reach due effect.
Therefore; When the preparation film; No matter which kind of mixed precursor, solvent, deionized water and catalyzer adopt, as long as in the reasonable scope, and can be with colloidal solution that obtains and corresponding thinner proportional mixing; As long as preparation condition does not change, the thickness of film will be pressed the parabolical change in shape of a similar quadratic function with colloidal solution shared ratio in coating solution.As long as confirm in advance several groups of dispersive data just can make one be similar to film thickness shown in Figure 1 and coating solution concentration graph of a relation; Under the constant situation of the proportionlity of precursor, solvent, deionized water and catalyzer; Just can be according to this figure through adding the thinner of different ratios; The concentration of rational allocation coating solution is with the film of preparation respective thickness.
Following indefiniteness embodiment is used for further specifying the present invention.
Under the room temperature; With 1000g ethanol, 120g deionized water, 80g concentration is that 25% hydrochloric acid soln mixes; And measuring the pH value of reaction solution with pH value measuration meter, the pH value of solution approximately is in 3.9～4.0 at this moment, adds the 800g tetraethoxysilane then; Make above-mentioned reactant hybrid reaction 3 hours, utilize the magnetite whisking appliance to be aided with the even stirring reaction liquid of magnetite in the reaction process.The sol solution that obtains was left standstill 15 hours, make it obtain sufficient hydrolysis and polymerization forms a SiO
2Colloidal solution.
With this SiO
2Colloidal solution is separately as coating solution, and with SiO
2Colloidal solution and ethanol prepare the film of different thickness respectively by weight the coating solution that is the mixed dilution preparation of 1: 0.5,1: 1,1: 2,1: 3,1: 4 and 1: 5.
When using SiO
2Colloidal solution is got an amount of SiO during as coating solution
2Colloidal solution adopts dip coating that this coating solution is coated on the matrix equably, utilize simultaneously one fixedly thermal source heat, make coating solution evaporation drying formation film, carry out thickness measurement through sweep electron microscope, the thickness of this film is 57 microns.
When using SiO
2When colloidal solution and ethanol prepare film by weight the coating solution that is 1: 0.5 mixed dilution preparation, get 200g SiO
2It is 66.7% coating solution that colloidal solution and 100g ethanol (thinner) thorough mixing obtain concentration; Adopt dip coating to be coated on this coating solution on the matrix equably; Utilize simultaneously one fixedly thermal source heat; Make the coating solution evaporation drying form film, carry out thickness measurement through sweep electron microscope, the thickness of this film is 22 microns.
When using SiO
2When colloidal solution and ethanol prepare film by weight the coating solution that is 1: 1 mixed dilution preparation, get 200g SiO
2It is 50% coating solution that colloidal solution and 200g ethanol thorough mixing obtain concentration, adopts and aforementioned the same condition and method, obtains a thickness and be 17 microns film.
When using SiO
2When colloidal solution and ethanol prepare film by weight the coating solution that is 1: 2 mixed dilution preparation, get 200g SiO
2It is 33.3% coating solution that colloidal solution and 400g ethanol thorough mixing obtain concentration, adopts and aforementioned the same condition and method, obtains a thickness and be 7 microns film.
When using SiO
2When colloidal solution and ethanol prepare film by weight the coating solution that is 1: 3 mixed dilution preparation, get 200g SiO
2It is 25% coating solution that colloidal solution and 600g ethanol thorough mixing obtain concentration, adopts and aforementioned the same condition and method, obtains a thickness and be 4 microns film.
Use SiO
2When colloidal solution and ethanol prepare film by weight the coating solution that is 1: 4 mixed dilution preparation, get 200g SiO
2It is 20% coating solution that colloidal solution and 800g ethanol thorough mixing obtain concentration, adopts and aforementioned the same condition and method, obtains a thickness and be 2 microns film.
When using SiO
2When colloidal solution and ethanol prepare film by weight the coating solution that is 1: 5 mixed dilution preparation, get 200g SiO
2It is 16.7% coating solution that colloidal solution and 1000g ethanol thorough mixing obtain concentration, adopts and aforementioned the same condition and method, obtains a thickness and be 1.5 microns film.
After The above results gathered,, make a film thickness and coating solution concentration (SiO according to the data that gather
2Colloidal solution/coating solution) graph of a relation, as shown in Figure 1, thickness and coating solution concentration roughly are the relation of quadratic function.Behind the thickness of definite film that need prepare, can confirm the concentration of corresponding coating solution, through adjusting thinner for SiO according to Fig. 1
2The relative proportion of colloidal solution makes SiO
2Colloidal solution shared ratio in coating solution meets the concentration of above-mentioned coating solution, and under the constant situation of other filming condition, the thickness that obtains film is predetermined thickness.
In sum, the method that the present invention prepares film can realize prepared film thickness is controlled, thereby forms the film of one deck pre-determined thickness at matrix surface.The present invention increases a step with mixing diluents in the operation of traditional Prepared by Sol Gel Method film; Through adjusting the proportionlity between this thinner and the above-mentioned colloidal solution; Make the thickness of film change according to certain rules, thereby realize control film thickness according to the variation of aforementioned proportion relation.Present method is applicable to the film that adopts Prepared by Sol Gel Method, for example can prepare SiO
2, TiO
2, ZrO
2Deng film, present method equipment is simple, easy and simple to handle simultaneously, can carry out at normal temperatures, and the thickness of ability accuracy controlling film, the thickness that formation needs is convenient to industrial application.
Claims (4)
1. method for preparing film said method comprising the steps of:
Using sol-gel method is 20: 25: 3 with weight ratio: sol solution is produced in the tetraethoxysilane of 2 ratio, ethanol, deionized water and HCL mixing;
Said sol solution is left standstill for some time form stable colloidal solution;
Colloidal solution is proportionally mixed the formation coating solution with thinner;
Said coating solution is coated on the matrix and dry and form film.
2. the method for preparing film according to claim 1 is characterized in that: said sol solution was left standstill 12～24 hours.
3. the method for preparing film according to claim 1 is characterized in that: said tetraethoxysilane, ethanol, deionized water and HCL mix the back and under 15～30 ℃ sour environment, reacted 2～4 hours.
4. the method for preparing film according to claim 3 is characterized in that: the pH value of said sour environment is 3.9～4.0.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710030719XA CN101397191B (en) | 2007-09-28 | 2007-09-28 | Method for producing thin membrane |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710030719XA CN101397191B (en) | 2007-09-28 | 2007-09-28 | Method for producing thin membrane |
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| CN101397191A CN101397191A (en) | 2009-04-01 |
| CN101397191B true CN101397191B (en) | 2012-02-01 |
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| CN200710030719XA Expired - Fee Related CN101397191B (en) | 2007-09-28 | 2007-09-28 | Method for producing thin membrane |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI401702B (en) * | 2010-02-10 | 2013-07-11 | Cheng Uei Prec Ind Co Ltd | Making method of conductive thin film and product thereof |
| CN110845959A (en) * | 2019-11-29 | 2020-02-28 | 湖北环宇化工有限公司 | Self-atomization organic silicon resin and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1173390A (en) * | 1997-06-20 | 1998-02-18 | 清华大学 | Method for prepn. of ultra filtering silica membrane used for seawater desalination |
| US5948482A (en) * | 1995-09-19 | 1999-09-07 | University Of New Mexico | Ambient pressure process for preparing aerogel thin films reliquified sols useful in preparing aerogel thin films |
| CN1316975A (en) * | 1998-09-09 | 2001-10-10 | 诺瓦拉技术股份有限公司 | Process for preparing silica or silica-based thick vitreous films according to sol-gel technique and thick films thereby obtained |
| CN1544324A (en) * | 2003-11-20 | 2004-11-10 | 中国科学院上海技术物理研究所 | Silica dioxide aerogel membrane material preparation method |
| CN1712478A (en) * | 2004-06-14 | 2005-12-28 | 中国科学院过程工程研究所 | Nanometer multifunctional composite thin-membrane, its production and use |
-
2007
- 2007-09-28 CN CN200710030719XA patent/CN101397191B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5948482A (en) * | 1995-09-19 | 1999-09-07 | University Of New Mexico | Ambient pressure process for preparing aerogel thin films reliquified sols useful in preparing aerogel thin films |
| CN1173390A (en) * | 1997-06-20 | 1998-02-18 | 清华大学 | Method for prepn. of ultra filtering silica membrane used for seawater desalination |
| CN1316975A (en) * | 1998-09-09 | 2001-10-10 | 诺瓦拉技术股份有限公司 | Process for preparing silica or silica-based thick vitreous films according to sol-gel technique and thick films thereby obtained |
| CN1544324A (en) * | 2003-11-20 | 2004-11-10 | 中国科学院上海技术物理研究所 | Silica dioxide aerogel membrane material preparation method |
| CN1712478A (en) * | 2004-06-14 | 2005-12-28 | 中国科学院过程工程研究所 | Nanometer multifunctional composite thin-membrane, its production and use |
Non-Patent Citations (2)
| Title |
|---|
| JP特开2001-139321A 2001.05.22 |
| JP特开平10-300995A 1998.11.13 |
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