CN1635064A - Process for preparing ZrO#-[2]/perfluoropolyether composite lubrication thin film - Google Patents
Process for preparing ZrO#-[2]/perfluoropolyether composite lubrication thin film Download PDFInfo
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- CN1635064A CN1635064A CN 200310117750 CN200310117750A CN1635064A CN 1635064 A CN1635064 A CN 1635064A CN 200310117750 CN200310117750 CN 200310117750 CN 200310117750 A CN200310117750 A CN 200310117750A CN 1635064 A CN1635064 A CN 1635064A
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- zro
- film
- ceramic membrane
- pfpe
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Abstract
The invention discloses a process for preparing ZrO#-[2]/perfluoropolyether composite lubrication thin film on the surface of solid materials, wherein the Sol-Gel process is employed to prepare ZrO2 ceramic film on slide glasses, monocrystalline silicon sheet, aluminum sheet or stainless steel substrate, then a Dip-coating method is employed for preparing single-layer all-fluorine polyether ultra-thin lubricant film on the ZrO2 ceramic film. The prepared lubricant film has good tribology performance, thus can be used as antifriction and antiwear protective coatings.
Description
Technical field:
The present invention relates to a kind ofly prepare ZrO at solid material surface
2The method of/PFPE composite lubricating film is so that provide effective means for protection and the lubrication problem that solves material in micromachine and the magnetic recording system.
Background technology:
The micro electronic mechanical system (brief note is MEMS) that the middle and later periods eighties rises or claim that micromachine (Micro machine) has that volume is little, a series of characteristics such as light weight, energy consumption are low, integrated level and intelligent degree height, have huge application potential in information technology and bioengineering field.It should be noted that, microminiaturization along with the scantlings of the structure of micromachine, the ratio of its surface-area and volume enlarges markedly, for internal force and gravity, electrostatic force and frictional force become needs top-priority object, " contact " and " separation " often alternately generation in this system, at this moment adhesion problems may become the important factor of control mechanical property quality.Therefore the lubricated of micromachine proposed challenge to traditional lubrication theory and technology.The polymer ultra-thin film lubrication technology that development in recent years is got up is expected to become the effective means that solves MEMS system lubrication problem.Micro Lub at micromachine is learned the theoretical investigation that fundamental research at first is conceived to boundary lubrication, then is based on the lubricated of magnetic head-disk system in application facet.In recent years, in the research of wear-resistant coating and computer disk application, find ZrO
2Ceramic membrane has good heat, chemistry and mechanical stability, and low frictional coefficient and good abrasion resistance are expected in severe rugged environment as wear-resisting or protective coating, therefore to ZrO
2The research of film has caused that the various countries scholar payes attention to widely.Have found that on the other hand; PFPE (Perfluoropolyethers; be abbreviated as PFPE) series lubricant agent has good chemistry and thermostability, low surface tension and volatility and at the film forming ability of solid surface excellence, is the first-selected lubricant of making the disk protect lubricant film.
Summary of the invention:
The purpose of this invention is to provide and a kind ofly prepare ZrO at solid material surface
2The method of/PFPE composite lubricating film.
The present invention combines the preparation of inorganic hard coat and the preparation of organic polymer ultrathin lubrication membrane, for protection and the lubrication problem that solves material in micromachine and the magnetic recording system provides effective means.The present invention at first adopts sol-gel method (Sol-Gel Process is called for short the S-G method) to prepare ZrO on substrates such as slide glass, monocrystalline silicon piece, aluminium flake or stainless steel
2Ceramic membrane utilizes dip-coating (Dip-coating) technology at ZrO then
2Prepared individual layer PFPE ultrathin lubrication membrane on the ceramic membrane.
Preparation method of the present invention comprises following two steps successively:
(1) ZrO
2The preparation of ceramic membrane:
(1) heating for dissolving in dehydrated alcohol with zirconium inorganic salt and stable complexation agent, wherein the stable complexation agent is methyl ethyl diketone or citric acid, with acid for adjusting pH=1～3, add organic film coalescence aid polyvinyl alcohol or polyoxyethylene glycol then, the solution that makes is placed the water-bath ageing 24～96 hours, obtain the zirconia base precursor sol of clear;
(2) do substrate with slide glass, monocrystalline silicon piece, aluminium flake or the stainless steel substrates of cleaning, the precursor sol that makes is prepared sol pellicle with dipping-pulling method on ground, 15～25 ℃ of system film temperatures, relative humidity 40%～50%, control pull rate are in 10～90cm/min scope to obtain the uniform sol film;
(3) with sol pellicle in air in 20～70 ℃ down dry, be heated to 500～550 ℃ and be incubated 20～30 minutes then, naturally cool to room temperature at last, promptly obtain required ZrO
2Ceramic membrane.
(2) ZrO
2The preparation of ceramic membrane monolayer surface PFPE ultrathin lubrication membrane:
(1) with Freon-113 (C
2Cl
3F
3) or Vertrel XF (C
5H
2F
10) be the PFPE solution of 0.1～0.2% (volume ratio) for the solvent compound concentration; With the ZrO that makes
2Ceramic membrane immerses in the PFPE solution for preparing and soaked 0.5-2 minute under room temperature;
(2) take out after corresponding solvent is thoroughly cleaned and dried up, the gained film was handled 20～30 minutes at 150 ℃ of following constant temperature, naturally cool to room temperature then, can be at ZrO
2Obtain the PFPE ultrathin lubrication membrane of individual layer on the ceramic membrane surface.
At preparation ZrO
2The addition of used stable complexation agent is 0.1～2 times of zirconium inorganic salt molar weight in the process of ceramic membrane.
At preparation ZrO
2The addition of used organic film coalescence aid is 0.1～1% of a precursor sol volume in the process of ceramic membrane.
Said PFPE is that FOMBLIN PFPE[trade name is Z-Dol among the present invention, and molecular formula is HOCH
2-CF
2-O-(CF
2-CF
2-O)
p-(CF
2O)
q-CF
2-CH
2OH, molecular weight are about 2000 and 4000 respectively, note by abridging to be Z-Dol2000 and Z-Dol4000] and FOMBLIN AM[molecular formula be R-CF
2-O-(CF
2-CF
2-O)
n-(CF
2O)
m-CF
2-R, R=Ar-CH
2-O CH
2-, molecular weight is about 2000 and 3000 respectively, notes by abridging to be AM2001 and AM3001].
The effect that the present invention adds organic film coalescence aid is in order to prevent the volatilization of the solvent in the colloidal sol.
The present invention has compared following advantage with prior art:
(1) material toxicity is little, and price is low;
(2) ZrO
2Film densification, even, thickness can freely be controlled, and surfaceness is low;
(3) ZrO
2The film antiwear and friction reduction property is good;
(4) when at ZrO
2The ceramic membrane surface preparation behind the PFPE composite lubricating film, the antiwear and friction reduction property of film further improves, and the antistick performance is good;
(5) preparation technology is simple, feasibility is strong.
Embodiment:
Embodiment 1:
ZrO on slide glass and the monocrystalline silicon piece
2The preparation process of/PFPE composite lubricating film is as follows:
(1) under violent stirring, with 0.02mol crystallization zirconyl chloride heating for dissolving in the dehydrated alcohol of 100ml, add citric acid and regulate PH=2.5, add the 0.6ml Macrogol 2000, the solution ageing in water-bath that makes was promptly obtained the zirconium white precursor sol of clear in 72 hours;
(2) do substrate with monocrystalline silicon piece and sheet glass;
(3) with the ZrO that makes
2Colloidal sol prepares sol pellicle with dipping-pulling method on slide glass or silicon single crystal ground, 15～25 ℃ of system film temperatures, relative humidity 40～50%, control pull rate are that 42.4cm/min is to obtain sol pellicle;
(4) with sol pellicle in air in room temperature～50 ℃ dry 15min down, then at 50min internal heating to 550 ℃ and be incubated 30min, in stove, naturally cool to room temperature at last, promptly obtain ZrO
2Film.
(5) with Freon-113 be solvent, the Z-Dol2000 or the Z-Dol4000 solution of preparation 0.2%;
(6) with the ZrO that makes
2Film immerses in the PFPE solution for preparing rapidly and soak 1min under room temperature, takes out after Freon-113 washes N
2Air-blowing is done, and promptly obtains the PFPE lubricant film of individual layer, and the gained film is handled 30min in 150 ℃ of following constant temperature in baking oven, naturally cools to room temperature then.
ZrO involved in the present invention
2Ceramic membrane has good tribological property, can be used as antifriction, wear-resistant protective coating.Individual layer PFPE lubricant film involved in the present invention has good antifriction, wear-resistant and antistick performance.The test method that adopts is as follows:
Friction-wear test is carried out on the static and dynamic friction coefficient determinator that Nippon Union K. K produces.Sliding velocity 90mmmin
-1, unidirectional sliding stroke is 9mm, the normal direction load is 0.5N.The idol part is selected GCr15 steel ball and the Si of φ 3mm for use
3N
4Ceramic Balls.Under room temperature and relative humidity RH=40%～45% condition, measure.Measured clean silicon substrate (SiO respectively
2/ Si), ZrO
2/ SiO
2And Z-Dol4000/ZrO
2Respectively with GCr15 steel ball and Si
3N
4Ceramic Balls is the friction and wear behavior when rubbing under 0.5N load, found that: clean silicon substrate with steel ball and Ceramic Balls when rubbing, the i.e. increase (0.7～0.8) rapidly of back frictional coefficient of sliding through several times, serious wear.Monocrystalline silicon surface dip-coating ZrO
2Behind the film, with GCr15 steel ball and Si
3N
4The frictional coefficient of Ceramic Balls when rubbing significantly reduces (0.12～0.16), and still keeps low frictional coefficient after the slip number of times surpasses 5000 times, is suitable under underload, low sliding velocity as antifriction, wear-resistant protective coating.But, with scanning electron microscope its surperficial grinding defect morphology is observed, find to exist tangible polishing scratch, this shows and is necessary to apply lubricant film to alleviate its wearing and tearing at this film surface.And at ZrO
2After having prepared the Z-Dol4000 lubricant film of individual layer on the film surface, no matter be and the soft GCr15 steel ball or the Si of high rigidity
3N
4Ceramic Balls all shows good anti-friction anti-attrition performance (frictional coefficient is lower than 0.1) to rubbing.And after the slip number of times surpassed 5000 times, frictional coefficient did not change, and the film surface smoother does not have tangible polishing scratch to occur.
Above frictional experiment data show, ZrO involved in the present invention
2Ceramic membrane has good tribological property, can be used as antifriction, wear-resistant protective coating, ZrO
2The individual layer PFPE composite lubricating film of film surface preparation can further reduce frictional coefficient, improve friction durability, has antistick effect preferably simultaneously, and being expected provides effective means for the protection and the lubrication problem of material in micromachine and the magnetic recording system.
Embodiment 2:
ZrO on aluminium and the stainless steel substrates
2The preparation process of ceramic membrane and the ultra-thin composite lubricating film of PFPE is as follows:
(1) the crystallization zirconyl chloride changes the crystallization zirconium chloride among the embodiment 1, regulates PH=2.5 and changes PH=1.5 into:
(2) do substrate with aluminium and stainless steel substrates:
(3) change used PFPE Z-Dol2000 or Z-Dol4000 into AM2001 or AM3001, solvent for use changes Vertrel XF into:
(4) other steps are with embodiment 1.
Claims (3)
1. one kind prepares ZrO
2The method of/PFPE composite lubricating film, preparation method comprise following two steps successively:
(1) ZrO
2The preparation of ceramic membrane:
(1) heating for dissolving in dehydrated alcohol with zirconium inorganic salt and stable complexation agent, wherein the stable complexation agent is methyl ethyl diketone or citric acid, with acid for adjusting pH=1～3, add organic film coalescence aid polyvinyl alcohol or polyoxyethylene glycol then, the solution that makes is placed the water-bath ageing 24～96 hours, obtain the zirconia base precursor sol of clear;
(2) do substrate with slide glass, monocrystalline silicon piece, aluminium flake or the stainless steel substrates of cleaning, the precursor sol that makes is prepared sol pellicle with dipping-pulling method on ground, 15～25 ℃ of system film temperatures, relative humidity 40%～50%, control pull rate are in 10～90cm/min scope to obtain the uniform sol film;
(3) with sol pellicle in air in 20～70 ℃ down dry, be heated to 500～550 ℃ and be incubated 20～30 minutes then, naturally cool to room temperature at last, promptly obtain required ZrO
2Ceramic membrane;
(2) ZrO
2The preparation of ceramic membrane monolayer surface PFPE ultrathin lubrication membrane:
(1) with Freon-113 (C
2Cl
3F
3) or Vertrel XF (C
5H
2F
10) be the PFPE solution of 0.1～0.2% (volume ratio) for the solvent compound concentration; With the ZrO that makes
2Ceramic membrane immerses in the PFPE solution for preparing and soaked under room temperature 0.5～2 minute;
(2) take out after corresponding solvent is thoroughly cleaned and dried up, the gained film was handled 20～30 minutes at 150 ℃ of following constant temperature, naturally cool to room temperature then, can be at ZrO
2Obtain the PFPE ultrathin lubrication membrane of individual layer on the ceramic membrane surface.
2,, it is characterized in that at preparation ZrO as the said method of claim 1
2The addition of used stable complexation agent is 0.1～2 times of zirconium inorganic salt molar weight in the process of ceramic membrane.
3,, it is characterized in that at preparation ZrO as the said method of claim 1
2The addition of used organic film coalescence aid is 0.1～1% of a precursor sol volume in the process of ceramic membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310117750 CN1635064A (en) | 2003-12-30 | 2003-12-30 | Process for preparing ZrO#-[2]/perfluoropolyether composite lubrication thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310117750 CN1635064A (en) | 2003-12-30 | 2003-12-30 | Process for preparing ZrO#-[2]/perfluoropolyether composite lubrication thin film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1635064A true CN1635064A (en) | 2005-07-06 |
Family
ID=34843716
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200310117750 Pending CN1635064A (en) | 2003-12-30 | 2003-12-30 | Process for preparing ZrO#-[2]/perfluoropolyether composite lubrication thin film |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100447305C (en) * | 2006-07-14 | 2008-12-31 | 西南大学 | Method for preparing magnesium oxide anti-corrosion protective film by sol-gel technology |
| CN101117525B (en) * | 2007-07-17 | 2011-02-23 | 陈志君 | Intelligent film coating material and method for making same |
| CN101734610B (en) * | 2009-12-15 | 2012-05-23 | 江苏大学 | Multilayer film for low load working condition of micro electro mechanical system and preparation method thereof |
| CN102618362A (en) * | 2012-02-27 | 2012-08-01 | 深圳市优宝惠新材料科技有限公司 | Friction-reducing lubricating coating composition |
| CN110658301A (en) * | 2019-10-29 | 2020-01-07 | 山东东岳高分子材料有限公司 | Method for measuring peroxide content in perfluoropolyether |
| CN111635804A (en) * | 2019-11-22 | 2020-09-08 | 中国科学院兰州化学物理研究所 | Perfluoropolyether supermolecule gel composite nanoparticle lubricant and preparation method and application thereof |
| CN114381200A (en) * | 2020-10-21 | 2022-04-22 | 惠州市海兰新材料有限公司 | Composite antibacterial mildew-proof coating and use method thereof |
-
2003
- 2003-12-30 CN CN 200310117750 patent/CN1635064A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100447305C (en) * | 2006-07-14 | 2008-12-31 | 西南大学 | Method for preparing magnesium oxide anti-corrosion protective film by sol-gel technology |
| CN101117525B (en) * | 2007-07-17 | 2011-02-23 | 陈志君 | Intelligent film coating material and method for making same |
| CN101734610B (en) * | 2009-12-15 | 2012-05-23 | 江苏大学 | Multilayer film for low load working condition of micro electro mechanical system and preparation method thereof |
| CN102618362A (en) * | 2012-02-27 | 2012-08-01 | 深圳市优宝惠新材料科技有限公司 | Friction-reducing lubricating coating composition |
| CN110658301A (en) * | 2019-10-29 | 2020-01-07 | 山东东岳高分子材料有限公司 | Method for measuring peroxide content in perfluoropolyether |
| CN111635804A (en) * | 2019-11-22 | 2020-09-08 | 中国科学院兰州化学物理研究所 | Perfluoropolyether supermolecule gel composite nanoparticle lubricant and preparation method and application thereof |
| CN114381200A (en) * | 2020-10-21 | 2022-04-22 | 惠州市海兰新材料有限公司 | Composite antibacterial mildew-proof coating and use method thereof |
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