CN1184016C - Method for preparing zirconium oxide porcelain coating on self assembled functional organosilane single layer film - Google Patents
Method for preparing zirconium oxide porcelain coating on self assembled functional organosilane single layer film Download PDFInfo
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- CN1184016C CN1184016C CN 02159872 CN02159872A CN1184016C CN 1184016 C CN1184016 C CN 1184016C CN 02159872 CN02159872 CN 02159872 CN 02159872 A CN02159872 A CN 02159872A CN 1184016 C CN1184016 C CN 1184016C
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Abstract
The present invention discloses a method for preparing zirconia ceramics thin film on the surface of a self-assembly single-layer thin film of functional the organosilane. Organosilane containing sulfur is used as raw materials, and can be easily absorbed on a single crystal silicon chip or the surface of a glass slide. The method of the present invention comprises the steps that an organosilane containing sulfur self-assembly single-layer thin film is prepared on monocrystalline silicon or the surface of the glass slide; base groups containing sulfur on the surface of the thin film are oxygenized to sulfonic groups; a zirconia ceramics thin film is prepared on the surface of the self-assembly single-layer thin film by using the chemical adsorption of the sulfonic acid group to zirconium sulphate nano particles. The present invention is characterized in that the raw material is cheap and low toxic, and the cost is low; the thin film is dense and uniform, and the surface of the thin film is in low roughness. The film forming operation can be carried out in a large area without limited by technologies and shapes; the antifriction property, the resistance to abrasion, and the block resistance of the thin film are good, and the manufacturing process is simple. The results of friction and abrasion test shows that the zirconia ceramics film and a substrate piece of the present invention have the advantages of good binding ability, favorable antifriction property and resistance to abrasion; the present invention can be become to an effective means for solving the protection and the lubrication problems of materials in micro machines.
Description
Technical field:
The present invention relates to a kind of preparation method at functionalization organosilan self-assembled monolayer surface preparation zirconia ceramics film.
Background technology:
That the zirconia ceramics film has is high temperature resistant, corrosion-resistant, chemical stability is good, mechanical strength is high, coefficient of friction is low and good performance such as long service life, can be used as protective coating and be used as antifriction or anti-friction material in severe rugged environment in micro electronic mechanical system (brief note is MEMS) or micromachine (Micromachine) and magnetic recording system.Thereby become one of the ceramic material the most widely of functional material, tribological field research in recent years.At present, the technology of preparing of zirconia ceramics film mainly contains vapour deposition, sputtering sedimentation, plasma spraying and sol-gel process etc.
Recent two decades comes, and self assembly becomes the focus of research as the new technique of the orderly ultrathin membrane of preparation.This is that (Self-Assembed Monolayers SAMs) has certain chemical stability and thermodynamic stability thereby make self-assembled film because self-assembling technique is adsorbed on bioactive molecule on the out-phase interface by chemical bond.Discover, (＜100 ℃) can immerse the substrate that has prepared self-assembled monolayer in the aqueous solution of some inorganic salts at low temperatures, make the functional group generation chemical reaction on inorganic salt nanometer particle and self-assembled monolayer surface, prepare oxide nano-film with this.This method is to be subjected to the inspiration that pottery forms in the organism at low temperatures and to be gradually adopted by people, thereby is called as " biomimetic method ".Utilize the sull surface ratio of this self-assembling method preparation more even, fine and close, have potential application prospect in fields such as optics, electricity, biology and materialogies.
Summary of the invention:
The purpose of this invention is to provide a kind of method, to solve the protection and the lubrication problem of material in the micromachine at functionalization organosilan self-assembled monolayer surface preparation zirconia ceramics film.
Preparation method of the present invention comprises A and two steps of B successively:
A. the preparation of functionalization organosilan self-assembled monolayer:
(1) does substrate with monocrystalline silicon piece or the slide handled, choose the organosilan that easily is adsorbed in monocrystalline silicon piece or slide surface and be mixed with solution, substrate immersed in the organosilan solution react, obtain having the organosilan self-assembled monolayer of certain ordered;
(2) will prepare in the substrate immersion oxidizing agent solution of organosilan self-assembled monolayer, the terminal functionality in the organic molecule carried out oxidation, promptly obtain having the functionalization organosilan self-assembled monolayer of certain ordered.
B. the preparation of zirconia composite lubricating film on the organic film of self-assembled monolayer:
(1) aqueous hydrochloric acid solution of preparation zirconium inorganic salts makes its pH value between 1-2;
(2) substrate that will prepare functionalization organosilan self-assembled monolayer immerses in the aqueous hydrochloric acid solution of zirconium inorganic salts, at 70 ℃ of reaction certain hours down; After the substrate taking-up, use deionized water rinsing, ultrasonic cleaning then, nitrogen dries up;
(3) substrate is heated to 500 ℃ and be incubated 2h, naturally cools to room temperature, obtain the zirconia ceramics film.
Organosilan involved in the present invention is sulfydryl propyl trimethoxy silicane ((CH
3O)
3Si (CH
2)
3SH) (be abbreviated as MPTS) or hexadecyl trichlorosilane thiacetate (Cl
3Si (CH
2)
16SC (O) CH
3) (being abbreviated as TSHT), they have good chemisorbed characteristic at monocrystalline silicon piece or slide surface, with the adhesion of substrate strong (covalent bond);
Solvent involved in the present invention is respectively: the solvent of MPTS is dry toluene or anhydrous benzene, and the solvent of TSHT is a dicyclohexyl alkane;
The used oxidant of the present invention is respectively: the oxidant of MPTS is the mixed solution of hydrogen peroxide (volumn concentration is 30%) and Peracetic Acid, and the oxidant of TSHT is (2KHSO
5KHSO
4K
2SO
4) the aqueous solution.
Zirconium inorganic salts involved in the present invention are zirconium sulfate;
The present invention has compared following advantage with prior art:
(1) raw material cheapness, low toxicity, cost is low;
(2) film densification, even, surface roughness is low;
(3) can the large tracts of land film forming, not limited by the technology shape;
(4) film antiwear and antifriction and antisticking performance are good;
(5) preparation technology is simple.
In severe rugged environment, under conditions such as high vacuum, elemental oxygen, intense radiation, deep-etching, the surfacecti proteon problem of material is an important subject of tribology.Under this environment, requiring material both to have good tribological property has and has environment tolerance preferably, and material is proposed very high requirement.Generally solved by technology such as ion injection, solid lubrication, but cost and research expenditure are higher, effect is unsatisfactory sometimes.The prepared zirconia ceramics film of the present invention had both had good tribological property, had good environment tolerance simultaneously, was expected to solve this type of problem.In order to understand the present invention better, describe by example:
The specific embodiment:
Embodiment 1: the preparation of sulfonated MPTS self-assembled monolayer zirconia surface ceramic membrane comprises two steps of A and B successively:
The preparation of A. sulfonated MPTS self-assembled monolayer:
(1) doing substrate with monocrystalline silicon piece, is that 70%: 30% the concentrated sulfuric acid and the mixed solution of hydrogen peroxide (Piranha solution) clean distilled water rinsing, N with volume ratio down at 90 ℃
2Air-blowing is done;
(2) preparation 1 * 10
-3The anhydrous toluene solution of M MPTS;
(3) monocrystalline silicon piece that will clean immerses in the MPTS weak solution for preparing rapidly and react 12h under room temperature; Thoroughly clean and dry up with chloroform, deionized water respectively after the taking-up, promptly obtain having the MPTS single thin film of certain ordered with nitrogen;
(4) substrate that will prepare the MPTS self-assembled monolayer immerses in the mixed solution of 30ml hydrogen peroxide (volumn concentration is 30%) and Peracetic Acid (volume ratio is 1: 5) again, at 48 ℃ of reaction 1h; Thoroughly clean with acetone, deionized water, chloroform respectively after the taking-up, dry up with nitrogen at last, can obtain to have the Sulfonated MPTS self-assembled monolayer of certain ordered.
B. the preparation of zirconia composite lubricating film on sulfonated MPTS self-assembled monolayer:
(1) with the zirconium sulfate (Zr (SO4) of 35.5g
24H
2O) powder is dissolved in the 100ml deionized water, stirs it is dissolved fully, obtains the zirconium sulfate aqueous solution of 0.1M; Measure the 92.7ml deionized water and add in the 4ml zirconium sulfate solution, and then add in the concentrated hydrochloric acid of 3.3ml, make the HCl solution of 4mM zirconium sulfate/0.4M, make its solution pH value between 1-2;
(2) substrate that will prepare sulfonated MPTS self-assembled monolayer immerses in the zirconium sulfate aqueous hydrochloric acid solution make, at 70 ° of reaction 6h; After substrate taken out, deionized water rinsing 3 times, ultrasonic cleaning 30min then, nitrogen dries up;
(3) substrate is heated to 500 ℃ and be incubated 2h, naturally cools to room temperature, obtain the zirconia ceramics film.
The prepared zirconia ceramics film of the present invention has good tribological property, can be used as antifriction, wear-resistant protective coating.The test method that adopts is as follows:
The tribological property of table 1 zirconia ceramics film
The wear-out life coefficient of friction
Load (N)
The worn out value of (number of times) stationary value
0.5＞5000 0.12-0.14 are not worn out
1.0 4450 0.13-0.15 0.70
2.0 2190 0.0.13-0.14 0.70
3.0 650 0.14-0.16 0.70
Friction-wear test is carried out on Nippon Union K. K's static and dynamic friction coefficient analyzer.Experiment condition is normal load 0.5,1.0,2.0,3.0N, and unidirectional sliding stroke is 9mm, sliding speed 90mmmin
-1, coefficient of friction is by the automatic record of recorder.Slip cycle-index when be worn through with film the friction durability of zirconia ceramics film is represented.When coefficient of friction raises gradually and reach a stationary value, think that film is worn out.Mating plate is selected φ 3mmGCr15 steel ball for use.Time measure at room temperature and relative humidity RH=40%～45%.The results are shown in Table 1.Friction, wear test result show that zirconia ceramics film involved in the present invention (0.5N) under low load has good tribological property, can be used as antifriction, wear-resistant protective coating, is expected the lubriation material as micromachine (MEMs).
Embodiment 2: the preparation of sulfonated TSHT self-assembled monolayer zirconia surface ceramic membrane comprises two steps of A and B successively:
The preparation of A. sulfonated TSHT self-assembled monolayer:
(1) do substrate with slide, cleaning method is with embodiment 1;
(5) the dicyclohexyl solution of preparation 1% (volume ratio) TSHT;
(6) slide that will clean immerses in the TSHT weak solution for preparing rapidly and react 5h under room temperature, takes out the back and thoroughly cleans and dry up with nitrogen with chloroform, promptly obtains having the TSHT single thin film of certain ordered;
(7) substrate that will prepare the TSHT self-assembled monolayer immerses 30ml oxidant (2KHSO
5KHSO
4K
2SO
4) in the aqueous solution, at room temperature react 6h; Thoroughly clean with acetone, deionized water, chloroform respectively after the taking-up, dry up with nitrogen at last, can obtain to have the sulfonated TSHT self-assembled monolayer of certain ordered.
B. the preparation of zirconia ceramics film on sulfonated TSHT self-assembled monolayer:
(4) compound method of zirconium sulfate aqueous hydrochloric acid solution is with embodiment 1;
(5) substrate that will prepare sulfonated TSHT single thin film immerses in the zirconium sulfate aqueous hydrochloric acid solution make, at 70 ° of reaction 24h; Substrate is taken out, deionized water rinsing 3 times, ultrasonic cleaning 1h then, nitrogen dries up;
(6) heat treatment process of substrate is with embodiment 1.
Claims (3)
1. method at functionalization organosilan self-assembled monolayer surface preparation zirconia ceramics film is characterized in that this method comprises A and two steps of B successively:
The preparation of A. sulfonated organosilan self-assembled monolayer:
(1) does substrate with monocrystalline silicon piece or the slide handled, choose the organosilan that easily is adsorbed in monocrystalline silicon piece or slide surface and be mixed with solution, substrate immersed in the organosilan solution react, obtain having the organosilan self-assembled monolayer of certain ordered;
(2) will prepare in the substrate immersion oxidizing agent solution of organosilan self-assembled monolayer, the terminal functionality in the organic molecule carried out oxidation, promptly obtain having the sulfonated organosilan self-assembled monolayer of certain ordered.
B. the preparation of zirconia composite lubricating film on sulfonated organosilan self-assembled monolayer:
(1) aqueous hydrochloric acid solution of preparation zirconium sulfate makes its pH value between 1-2;
(2) substrate that will prepare sulfonated organosilan self-assembled monolayer immerses in the zirconium sulfate aqueous hydrochloric acid solution make, 70 ° of reactions;
(3) substrate is heated to 500 ℃ and insulation, naturally cools to room temperature, obtain the zirconia ceramics film.
2. the method for claim 1 is characterized in that organosilan solution is 1 * 10
-3The dicyclohexyl alkane solution of the anhydrous toluene solution of M sulfydryl propyl trimethoxy silicane or 1% volume ratio hexadecyl trichlorosilane thiacetate.
3. the method for claim 1, the oxidant that it is characterized in that sulfydryl propyl trimethoxy silicane end group is carried out oxidation is that volumn concentration is the mixed solution of 30% hydrogen peroxide and Peracetic Acid, and volume ratio is 1: 5, and the reaction time can not be less than 1h; And the oxidant that the end group oxidation of hexadecyl trichlorosilane thiacetate is used is KHSO
5KHSO
4K
2SO
4The aqueous solution at room temperature reacts 6h.
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|---|---|---|---|
| CN 02159872 CN1184016C (en) | 2002-12-24 | 2002-12-24 | Method for preparing zirconium oxide porcelain coating on self assembled functional organosilane single layer film |
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|---|---|---|---|
| CN 02159872 CN1184016C (en) | 2002-12-24 | 2002-12-24 | Method for preparing zirconium oxide porcelain coating on self assembled functional organosilane single layer film |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102342271A (en) * | 2010-07-23 | 2012-02-08 | 路思谦 | Falling and touching proof microscopic plastic glass slide specimen |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1308059C (en) * | 2004-10-21 | 2007-04-04 | 山西保太和膜科技有限公司 | Preparation method of stainless ceramic compound membrane and product produced thereby |
| CN100383280C (en) * | 2005-01-20 | 2008-04-23 | 上海交通大学 | Method for preparing sulfonic silane-rare earth nanometer compound membrane on single crystal silicon sheet surface |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102342271A (en) * | 2010-07-23 | 2012-02-08 | 路思谦 | Falling and touching proof microscopic plastic glass slide specimen |
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