CN100361916C - Preparation method of glass substrate surface phosphate silicane-rare earth nanometer film - Google Patents
Preparation method of glass substrate surface phosphate silicane-rare earth nanometer film Download PDFInfo
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- CN100361916C CN100361916C CNB2006100249787A CN200610024978A CN100361916C CN 100361916 C CN100361916 C CN 100361916C CN B2006100249787 A CNB2006100249787 A CN B2006100249787A CN 200610024978 A CN200610024978 A CN 200610024978A CN 100361916 C CN100361916 C CN 100361916C
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Abstract
The present invention relates to a preparation method of a phosphate silicane-RE nanometer film on the hydroxylated surface of a glass substrate as base material, which comprises: the substrate is soaked in an aminosilane solution to assemble an aminosilane film on the surface; then, the substrate assembled with aminosilane on the surface is put in a methyl cyanide solution containing phosphoryl chloride and 2, 3, 5-collidine, and stood for a period of time to assemble phosphate groups on the film surface; finally, the substrate attached with the phosphate silicane film is put in an RE self-assembly solution prepared from etanol, RE compounds, edta, ammonium chloride, urea and nitric acid to obtain the phosphate silicane-RE nanometer film. The RE self-assembled film prepared on the glass substrate surface with the simple process method of the present invention has obvious antifriction, anti-wear and antisticking effect.
Description
Technical field
The present invention relates to a kind of preparation method of nano compound film, relate in particular to a kind of preparation method of glass substrate surface self-assembly phosphate group silicone hydride-rare earth nanometer film.Belong to the film preparing technology field.
Background technology
Electromechanics-bodyization, ultrapreciseization and microminiaturized trend appear in the modern mechanical the reach of science, the friction pair gap of many new and high technology devices often is in nanometer scale, because micromachine is subjected to the influence of dimensional effect, so micro friction wear and nano-scale thin film lubrication have become key issue, can prepare self-assembled film at glass surface by self-assembling method at present, study the antifriction antiwear that rare earth improves substrate surface.The self-assembly organic, inorganic composite film is to contain in the organic solution by suitable substrate is immersed, mainly generate a kind of organic two-dimentional molecular film by chemisorption, to insert in the assembling solution that contains rare earth for preparing with the substrate of organic film then, assemble under certain conditions, obtain organic, inorganic composite film.The self-assembled film compact structure that obtains, stability height, and have high-sequential and orientation.The Study of Friction Properties of Organized Molecular Films has become one of advanced subject of tribological field.
Find by literature search, publication number is the preparation method that the Chinese invention patent application of CN1403494 discloses a kind of self-assembling ultrathin polymeric film, at first by the synthetic mould material of radical copolymerization, the thin polymer film that utilizes self-assembling technique to prepare to have various surface propertieies.The polymer ultra-thin film of preparation has antifriction, anti-wear effect, can be used for the lubricated and protection of Micro Electro Mechanical System.This method be with mol ratio be 0.1～10% silane coupling agent and monomer with Diisopropyl azodicarboxylate with the initiator copolymerization, purifying obtains self-assembling polymers; Self-assembly film forming in clean substrate, and in rare gas element, heat-treated 10～24 hours in 100 ℃～200 ℃.The processing condition of the self-assembled film of this method preparation are relatively loaded down with trivial details, and heat treatment period is also longer, and the film of this method preparation is organic film, are not the inorganic rare earth laminated films.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of preparation method of glass substrate surface phosphate silicane-rare earth nanometer film is provided, be used to solve the friction problem of micro mechanical system, preparation technology is simple, and the film that is self-assembled into has good antifriction performance.
For realizing this purpose, in the technical scheme of the present invention, the glass substrate that adopts surface process hydroxylation processing is as base material, substrate is immersed in the aminosilane solution, at substrate surface assembling aminosilane film, then with surface-assembled the substrate of aminosilane insert and contain phosphoryl chloride and 2,3, in the acetonitrile solution of 5-trimethylpyridine, phosphate group in the film surface assembling, at last the surface is inserted by ethanol with the substrate of phosphate group silicone hydride film, rare earth compound, ethylenediamine tetraacetic acid (EDTA), ammonium chloride, urea, in the rare earth self-assembly solution of nitric acid preparation, obtain phosphate group silicone hydride-rare earth nanometer film.
Method of the present invention is specific as follows:
At first carry out the pre-treatment of glass substrate, glass substrate adopts hydroxylation to handle.Treatment process: glass substrate is placed volume ratio 98% vitriol oil: 30%H
2O
2Handled 1 hour under room temperature in=1: 1 the solution, used the deionized water ultrasonic cleaning again 20 minutes, be placed on drying in the inherent baking oven of a dust keeper, drying temperature does not have particular requirement.The glass substrate surface that deals under such time and the temperature is electronegative and substrate of glass is very smooth, is not corroded.Glass substrate after handling is immersed in the aminosilane solution for preparing, left standstill 12 hours, use anhydrous methanol, deionized water rinsing after the taking-up respectively, dry up to place with nitrogen then and contain phosphoryl chloride and 2,3, reaction is 20 minutes in the acetonitrile solution of 5-trimethylpyridine, takes out the back and uses a large amount of deionized water rinsings, has obtained on the surface-assembled film substrate of phosphate group.Again the surface is inserted in the rare earth self-assembly solution for preparing with the film substrate of phosphate group, under 80 ℃, assembled 12 hours, promptly obtain phosphate group silicone hydride-rare earth nanometer film.
The volume percent of aminosilane is 0.5～2% in the aminosilane solution that the present invention adopts, and solvent is an anhydrous methanol.The component volume percent of the acetonitrile solution that the present invention adopts is: phosphoryl chloride 15～25%, 2,3,5-trimethylpyridine 15～25%, acetonitrile 50～70%.
The weight percentages of components of the rare earth self-assembly solution that the present invention adopts is: ethanol 60～80%, rare earth compound 4.5～7%, ethylenediamine tetraacetic acid (EDTA) (EDTA) 1～4%, ammonium chloride 2～5%, urea 12～25%, nitric acid 0.5～1.5%.
Rare earth compound of the present invention is a kind of in Lanthanum trichloride, Cerium II Chloride, lanthanum trioxide or the cerium oxide.
The present invention adopts in rare-earth modifier self-assembly phosphate group silicone hydride-rare earth nanometer composite film on hydroxylated glass substrate, because having carried out hydroxylation, handles glass substrate surface, contain hydrolyzable active group in the amino silane molecules, can build Si-O by chemistry and combine, form the silane self-assembled film that one deck has amino group at substrate surface with base material with active group Si-OH; With surface-assembled the substrate of aminosilane insert and contain phosphoryl chloride and 2,3, in the acetonitrile solution of 5-trimethylpyridine, leave standstill for some time after, film surface will be assembled phosphate group.Again it is inserted in the earth solution at last and since phosphate group not only have can with the proton of rare earth metal cationic exchange, and in addition can with rare earth metal coordinate P=O base, thereby form one deck rare earth nanometer film again on the silane surface.
Rare earth self-assembly solution allocation among the present invention is simple, and the phosphate group silicone hydride-rare earth nanometer film that is self-assembled into has and is evenly distributed advantages such as film forming densification.Rare earth self-assembled film in the glass substrate surface preparation has fairly obvious antifriction function, and has good wear resistance, is expected to become micromachine ideal boundary lubricant film.
Embodiment
Below by specific embodiment technical scheme of the present invention is further described.Following examples do not constitute limitation of the invention.
Embodiment 1:
At first carry out the pre-treatment of glass substrate, glass substrate adopts hydroxylation to handle.Treatment process: glass substrate is placed volume ratio 98% vitriol oil: 30%H
2O
2Handled 1 hour under room temperature in=1: 1 the solution, used the deionized water ultrasonic cleaning again 20 minutes, be placed on drying in the inherent baking oven of a dust keeper, drying temperature does not have particular requirement.Glass substrate after handling is immersed in the aminosilane solution for preparing, left standstill 12 hours, after using anhydrous methanol, deionized water rinsing respectively after the taking-up, dry up to be placed on nitrogen and contain phosphoryl chloride and 2,3, reaction is 20 minutes in the acetonitrile solution of 5-trimethylpyridine, takes out a large amount of deionized water rinsings in back, has just assembled phosphate group at film surface like this.Again the surface is inserted in the rare earth self-assembly solution for preparing with the film substrate of phosphate group, under 80 ℃, assembled 12 hours, promptly obtain phosphate group silicone hydride-rare earth self-assembled nanometer film.
Wherein the volume percent of aminosilane is 0.5% in the aminosilane solution of Cai Yonging, and solvent is an anhydrous methanol; The component volume percent of acetonitrile solution is: phosphoryl chloride 15%, 2,3,5-trimethylpyridine 15%, acetonitrile 70%.The weight percentages of components of rare earth self-assembly solution is: ethanol content: 60%, and rare earth compound: 5%, ethylenediamine tetraacetic acid (EDTA) (EDTA): 4%, ammonium chloride: 5%, urea: 25%, nitric acid: 1%.
Adopt SPM-9500 atomic force microscope, L116E type measurement of elliptically polarized li instrument and PHI-5702 type x-photoelectron spectroscopy (XPS) to characterize surface topography, thickness and the chemical ingredients of film.Adopt the little frictional behaviour survey meter of the point pure slip of contact MEASUREMENTS OF THIN frictional coefficient.
The result shows thickness at the organic film that is self-assembled on the glass substrate between 5～7nm, and the laminated film thickness is between 15～40nm.The XPS test pattern shows at glass substrate surface has successfully assembled the aminosilane film; The aminosilane film is presented to contains phosphoryl chloride and 2,3, after reaction for some time, observing film surface by XPS has phosphoric, and the assembled phosphate group of having gone up of film surface is described in the acetonitrile solution of 5-trimethylpyridine; Contain rare earth element in the film that will obtain after will in earth solution, assembling with the substrate of the organosilane film of phosphate group, and complex reaction has taken place in the group on itself and organosilane surface.Surface observation is less than the index of silicon-dioxide and phosphate, so the surface of glass substrate has all covered rare earth nanometer composite film.On a little frictional behaviour survey meter of the pure slip of contact, measure the frictional coefficient of clean glass substrate and glass substrate surface self-assembly rare earth film respectively.The rare earth self-assembled film of glass substrate surface preparation can be with frictional coefficient 0.8 during from no film be reduced to about 0.08, have fairly obvious antifriction function.
Embodiment 2:
At first carry out the pre-treatment of glass substrate, glass substrate adopts hydroxylation to handle.Treatment process: glass substrate is placed volume ratio 98% vitriol oil: 30%H
2O
2Handled 1 hour under room temperature in=1: 1 the solution, used the deionized water ultrasonic cleaning again 20 minutes, be placed on drying in the inherent baking oven of a dust keeper, drying temperature does not have particular requirement.Glass substrate after handling is immersed in the aminosilane solution for preparing, left standstill 12 hours, after using anhydrous methanol, deionized water rinsing respectively after the taking-up, dry up to be placed on nitrogen and contain phosphoryl chloride and 2,3, reaction is 20 minutes in the acetonitrile solution of 5-trimethylpyridine, takes out a large amount of deionized water rinsings in back, has just assembled phosphate group at film surface like this.Again the surface is inserted in the rare earth self-assembly solution for preparing with the film substrate of phosphate group, under 80 ℃, assembled 12 hours, promptly obtain phosphate group silicone hydride-rare earth self-assembled nanometer film.
Wherein the volume percent of aminosilane is 1.5% in the aminosilane solution of Cai Yonging, and solvent is an anhydrous methanol; The component volume percent of acetonitrile solution is: phosphoryl chloride 20%, 2,3,5-trimethylpyridine 20%, acetonitrile 60%.The weight percentages of components of rare earth self-assembly solution is: ethanol content: 80%, and rare earth compound: 4.5%, ethylenediamine tetraacetic acid (EDTA) (EDTA): 1%, ammonium chloride: 2%, urea: 12%, nitric acid: 0.5%.
Adopt the characterization method among the embodiment 1 that film quality is estimated.
The result shows thickness at the organic film that is self-assembled on the glass substrate between 5～10nm, and the laminated film thickness is between 15～45nm.The XPS test pattern shows at glass substrate surface has successfully assembled the aminosilane film; The aminosilane film is presented to contains phosphoryl chloride and 2,3, after reaction for some time, observing film surface by XPS has phosphoric, and the assembled phosphate group of having gone up of film surface is described in the acetonitrile solution of 5-trimethylpyridine; Contain rare earth element in the film that will obtain after will in earth solution, assembling with the substrate of the organosilane film of phosphate group, and complex reaction has taken place in the group on itself and organosilane surface.Surface observation is less than the index of silicon-dioxide and phosphate, so the surface of glass substrate has all covered rare earth nanometer composite film.
Embodiment 3:
At first carry out the pre-treatment of glass substrate, glass substrate adopts hydroxylation to handle.Treatment process: glass substrate is placed volume ratio 98% vitriol oil: 30%H
2O
2Handled 1 hour under room temperature in=1: 1 the solution, used the deionized water ultrasonic cleaning again 20 minutes, be placed on drying in the inherent baking oven of a dust keeper, drying temperature does not have particular requirement.Glass substrate after handling is immersed in the aminosilane solution for preparing, left standstill 12 hours, after using anhydrous methanol, deionized water rinsing respectively after the taking-up, dry up to be placed on nitrogen and contain phosphoryl chloride and 2,3, reaction is 20 minutes in the acetonitrile solution of 5-trimethylpyridine, takes out a large amount of deionized water rinsings in back, has just assembled phosphate group at film surface like this.Again the surface is inserted in the rare earth self-assembly solution for preparing with the film substrate of phosphate group, under 80 ℃, assembled 12 hours, promptly obtain phosphate group silicone hydride-rare earth self-assembled nanometer film.
Wherein the volume percent of aminosilane is 2% in the aminosilane solution of Cai Yonging, and solvent is an anhydrous methanol; The component volume percent of acetonitrile solution is: phosphoryl chloride 25%, 2,3,5-trimethylpyridine 25%, acetonitrile 50%.The weight percentages of components of rare earth self-assembly solution is: ethanol content: 70%, and rare earth compound: 5%, ethylenediamine tetraacetic acid (EDTA) (EDTA): 4%, ammonium chloride: 5%, urea: 15%, nitric acid: 1%.
Adopt the laboratory apparatus among the embodiment 1 that film is estimated, the result shows thickness at the organic film that is self-assembled on the glass substrate between 5～10nm, and the laminated film thickness is between 15～50nm.The XPS test pattern shows at glass substrate surface has successfully assembled the aminosilane film; The aminosilane film is presented to contains phosphoryl chloride and 2,3, after reaction for some time, observing film surface by XPS has phosphoric, and the assembled phosphate group of having gone up of film surface is described in the acetonitrile solution of 5-trimethylpyridine; Contain rare earth element in the film that will obtain after will in earth solution, assembling with the substrate of the organosilane film of phosphate group, and complex reaction has taken place in the group on itself and organosilane surface.Surface observation is less than the index of silicon-dioxide and phosphate, so the surface of glass substrate has all covered rare earth nanometer composite film.
Claims (2)
1. the preparation method of a glass substrate surface phosphate silicane-rare earth nanometer film is characterized in that glass substrate is placed volume ratio 98% vitriol oil: 30%H
2O
2Under room temperature, handled 1 hour in=1: 1 the solution, used the deionized water ultrasonic cleaning again 20 minutes, be placed in the inherent baking oven of a dust keeper dry; Glass substrate after handling is immersed in the aminosilane solution for preparing, left standstill 12 hours, use anhydrous methanol, deionized water rinsing after the taking-up respectively, dry up to place with nitrogen then and contain phosphoryl chloride and 2,3, reaction is 20 minutes in the acetonitrile solution of 5-trimethylpyridine, takes out the back and uses deionized water rinsing, has obtained on the surface-assembled film substrate of phosphate group; Again the surface is inserted in the rare earth self-assembly solution for preparing with the film substrate of phosphate group, under 80 ℃, assembled 12 hours, promptly obtain phosphate group silicone hydride-rare earth nanometer film; Wherein, in the described aminosilane solution aminosilane volume percent be 0.5～2%, solvent is an anhydrous methanol; The component volume percent of described acetonitrile solution is: phosphoryl chloride 15～25%, 2,3,5-trimethylpyridine 15～25%, acetonitrile 50～70%; The weight percentages of components of described rare earth self-assembly solution is: ethanol 60～80%, rare earth compound 4.5～7%, ethylenediamine tetraacetic acid (EDTA) 1～4%, ammonium chloride 2～5%, urea 12～25%, nitric acid 0.5～1.5%.
2. the preparation method of glass substrate surface phosphate silicane-rare earth nanometer film as claimed in claim 1 is characterized in that described rare earth compound is a kind of in Lanthanum trichloride, Cerium II Chloride, lanthanum trioxide, the cerium oxide.
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| CNB2006100249787A CN100361916C (en) | 2006-03-23 | 2006-03-23 | Preparation method of glass substrate surface phosphate silicane-rare earth nanometer film |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6531814B1 (en) * | 2000-02-17 | 2003-03-11 | General Electric Company | Fluorescent lamp coating and coating recycling method |
| CN1403494A (en) * | 2002-09-15 | 2003-03-19 | 中国科学院兰州化学物理研究所 | Prepn of self-assembled superthin polymer film |
| CN1654392A (en) * | 2005-01-20 | 2005-08-17 | 上海交通大学 | Method for preparing sulfonic silicane-rare earth nano composite film on the surface of glass substrate |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6531814B1 (en) * | 2000-02-17 | 2003-03-11 | General Electric Company | Fluorescent lamp coating and coating recycling method |
| CN1403494A (en) * | 2002-09-15 | 2003-03-19 | 中国科学院兰州化学物理研究所 | Prepn of self-assembled superthin polymer film |
| CN1654392A (en) * | 2005-01-20 | 2005-08-17 | 上海交通大学 | Method for preparing sulfonic silicane-rare earth nano composite film on the surface of glass substrate |
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