CN100556838C - The preparation method of phosphate group silicane-carbon nano tube composite film on glass substrate surface - Google Patents
The preparation method of phosphate group silicane-carbon nano tube composite film on glass substrate surface Download PDFInfo
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- CN100556838C CN100556838C CNB2007100370441A CN200710037044A CN100556838C CN 100556838 C CN100556838 C CN 100556838C CN B2007100370441 A CNB2007100370441 A CN B2007100370441A CN 200710037044 A CN200710037044 A CN 200710037044A CN 100556838 C CN100556838 C CN 100556838C
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Abstract
The present invention relates to a kind of preparation method of phosphate group silicane-carbon nano tube composite film on glass substrate surface, 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, after leaving standstill for some time, film surface will be assembled phosphate group, again substrate is inserted the carbon nano tube suspension after rare earth modified, left standstill 4～16 hours at 20～60 ℃, take out and use a large amount of deionized water rinsings, the flushing back dries up with nitrogen, so just obtains the glass substrate that surface deposition has the modified carbon nano-tube laminated film.Processing method of the present invention is simple, and the carbon nano-tube coextruded film for preparing at glass substrate surface has obvious antifriction, wear-resisting effect.
Description
Technical field
The present invention relates to a kind of preparation method of carbon nano-tube coextruded film, relate in particular to the preparation method of a kind of glass substrate surface self-assembly phosphate group silicone hydride-rare earth modified carbon nanotube pipe laminated film.Belong to the film preparing technology field.
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 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 improve the antifriction antiwear on monocrystalline silicon substrate surface by self-assembling method at monocrystalline silicon substrate surface preparation self-assembled film at present.Compare with other preparation thin film technique, the self-assembled film technology has operability, adaptability is strong, is with a wide range of applications, and the Study of Friction Properties of self-assembled film has become one of advanced subject of tribological field.
Carbon nanotube is a kind of of nano material, and carbon nanotube is the seamless hollow tube that is rolled into by the graphite flake that carbon atom forms, and has peculiar electric property, superpower mechanical property, good adsorption property, thereby has caused very big attention in the material field.But carbon nanotube radial nano-grade size and high surface energy cause its easy reunion, and be dispersed relatively poor, reduced the effective L D ratio of carbon nanotube.In addition, the carbon nano tube surface feature is similar to graphite, and insoluble in most solvents, wet performance is poor, is difficult to be formed with effective adhesive with substrate.In order to improve the dispersed of carbon nanotube and to increase it and the bonding force of substrate interface, must assemble methods such as active group by surface modification and substrate surface to carbon nanotube, improve the interface combination degree between carbon nanotube and the substrate surface, obtain 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 improvement and the research of carbon nanotube to film performance.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of preparation method of phosphate group silicane-carbon nano tube composite film on glass substrate surface is provided, be used to solve the friction problem of micro mechanical system, preparation technology is simple, and the laminated film that is self-assembled into has good antifriction performance.
For realizing this purpose, in the technical scheme of the present invention, adopt the surface hydroxylated glass substrate of process as base material, adopt self-assembling method to prepare the aminosilane film on its surface, under appropriate reaction conditions, the amido functional group of aminosilane film surface is oxidized to phosphate functional group then, use N again, dinethylformamide (DMF) carbon nanotube dispersion liquid contains the laminated film of rare earth modified carbon nanotube pipe in the silane surface preparation.
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: it is 98% vitriol oil: 30%H that glass substrate is placed volume ratio
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, obtains the film substrate that surface-assembled has phosphate group.
Again carbon nanotube is at room temperature immersed and soak 2～6 hours in the rare-earth modifier, filter the back oven dry.The carbon nanotube that processing obtains is put into N by 0.05～0.15mg/ml, and in dinethylformamide (DMF) dispersion agent, ultrasonic dispersing (40W) 2～6 hours obtains stable carbon nano tube suspension.Then surface-assembled there is the film substrate of phosphate group to immerse in the carbon nano tube suspension for preparing, left standstill 4～16 hours at 20～60 ℃, take out and use a large amount of deionized water rinsings, the flushing back dries up with nitrogen, so just obtains the glass substrate that there is phosphate group silicone hydride-carbon nano-tube coextruded film on the surface.
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 modifier that the present invention adopts is: rare earth compound 0.1～2%, alcohol 95～99.7%, ethylenediamine tetraacetic acid (EDTA) 0.05～0.5%, ammonium chloride 0.1～1%, nitric acid 0.02～0.5%, urea 0.03～1%.
Rare earth compound of the present invention is a kind of in Lanthanum trichloride, Cerium II Chloride, lanthanum trioxide or the cerium oxide.
Carbon nanotube of the present invention comprises single wall, double-walled or multi-walled carbon nano-tubes.
The present invention is self-assembly phosphate group silicone hydride-carbon nano-tube coextruded 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.After again it being inserted carbon nano tube suspension, substrate surface is with deposition of carbon nanotubes.
Rare-earth modifier configuration among the present invention is simple, and the carbon nano-tube coextruded film for preparing at glass substrate surface 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:
Carbon nanotube: the multi-walled carbon nano-tubes that Nanometer Port Co., Ltd., Shenzhen produces.
At first carry out the pre-treatment of glass substrate, glass substrate adopts hydroxylation to handle.Treatment process: it is 98% vitriol oil: 30%H that glass substrate is placed volume ratio
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.
At room temperature carbon nanotube is immersed in the rare-earth modifier and soaked 2 hours, filter the back oven dry.The carbon nanotube that processing is obtained is put into N by 0.05mg/ml then, and in dinethylformamide (DMF) dispersion agent, ultrasonic dispersing (40W) 2 hours obtains stable carbon nano tube suspension.
There is the glass substrate of phosphate group Silan-based Thin Films to immerse in the carbon nano tube suspension for preparing surface-assembled, under 20 ℃, left standstill 4 hours, take out and use a large amount of deionized water rinsings, the flushing back dries up with nitrogen, so just obtains the glass substrate that there is phosphate group silicone hydride-carbon nano-tube coextruded film on the surface.
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 the rare-earth modifier that adopts is: rare earth compound Lanthanum trichloride 0.1%, ethanol 99.7%, ethylenediamine tetraacetic acid (EDTA) 0.05%, ammonium chloride 0.1%, nitric acid 0.02%, urea 0.03%.
Adopt SPM-9500 atomic force microscope (AFM), JEM-2010 scanning electronic microscope (SEM) and PHI-5702 type x-photoelectron spectroscopy (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 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 reacting for some time in the acetonitrile solution of 5-trimethylpyridine, observe film surface by XPS phosphoric is arranged, the assembled phosphate group of having gone up of film surface is described, in the XPS collection of illustrative plates, has observed the existence of lanthanum element simultaneously.The SEM picture sees clearly that then carbon nanotube is deposited on the surface of glass substrate, has formed carbon nano-tube coextruded 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 carbon nano-tube compound film respectively.The carbon nano-tube coextruded film of glass substrate surface preparation can be with frictional coefficient 0.8 during from no film be reduced to about 0.15, have fairly obvious antifriction function.
Embodiment 2:
Carbon nanotube: Single Walled Carbon Nanotube, double-walled carbon nano-tube and multi-walled carbon nano-tubes that Nanometer Port Co., Ltd., Shenzhen produces.
At first carry out the pre-treatment of glass substrate, glass substrate adopts hydroxylation to handle.Treatment process: it is 98% vitriol oil: 30%H that glass substrate is placed volume ratio
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.
At room temperature carbon nanotube is immersed in the rare-earth modifier and soaked 3 hours, filter the back oven dry.The carbon nanotube that processing is obtained is put into N by 0.1mg/ml then, and in dinethylformamide (DMF) dispersion agent, ultrasonic dispersing (40W) 4 hours obtains steady suspension.
There is the glass substrate of phosphate group Silan-based Thin Films to immerse in the carbon nano tube suspension for preparing surface-assembled, under 40 ℃, left standstill 8 hours, take out and use a large amount of deionized water rinsings, the flushing back dries up with nitrogen, so just obtains the glass substrate that there is phosphate group silicone hydride-carbon nano-tube coextruded film on the surface.
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 modifier is: rare earth compound 1.5%, ethanol 96%, ethylenediamine tetraacetic acid (EDTA) 0.2%, ammonium chloride 0.8%, nitric acid 0.5%, urea 1%.
Adopt the characterization method among the embodiment 1 that film quality is estimated.
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; The SEM picture sees clearly that then carbon nanotube is deposited on the surface of glass substrate, has formed carbon nano-tube coextruded film; The carbon nano-tube coextruded film of glass substrate surface preparation can be with frictional coefficient 0.8 during from no film be reduced to about 0.12, have fairly obvious antifriction function.
Embodiment 3:
Carbon nanotube: Single Walled Carbon Nanotube, double-walled carbon nano-tube and multi-walled carbon nano-tubes that Nanometer Port Co., Ltd., Shenzhen produces.
At first carry out the pre-treatment of glass substrate, glass substrate adopts hydroxylation to handle.Treatment process: it is 98% vitriol oil: 30%H that glass substrate is placed volume ratio
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.
At room temperature carbon nanotube is immersed in the rare-earth modifier and soaked 6 hours, filter the back oven dry.The carbon nanotube that processing obtains is put into N by 0.15mg/ml then, and in dinethylformamide (DMF) dispersion agent, ultrasonic dispersing (40W) 6 hours obtains steady suspension.
There is the glass substrate of phosphate group Silan-based Thin Films to immerse in the carbon nano tube suspension for preparing surface-assembled, under 60 ℃, left standstill 16 hours, take out and use a large amount of deionized water rinsings, the flushing back dries up with nitrogen, so just obtains the glass substrate that there is phosphate group silicone hydride-carbon nano-tube coextruded film on the surface.
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 modifier is: rare earth compound 2%, alcohol 95 %, ethylenediamine tetraacetic acid (EDTA) 0.5%, ammonium chloride 1%, nitric acid 0.5%, urea 1%.
Adopt the laboratory apparatus among the embodiment 1 that film is estimated, 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; The SEM picture sees clearly that then carbon nanotube is deposited on the surface of glass substrate, has formed carbon nano-tube coextruded film.The carbon nano-tube coextruded film of glass substrate surface preparation 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 of preparation method of phosphate group silicane-carbon nano tube composite film on glass substrate surface is characterized in that it is 98% vitriol oil: 30%H that glass substrate is placed volume ratio
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, obtains the film substrate that surface-assembled has phosphate group;
Again carbon nanotube is at room temperature immersed and soak 2～6 hours in the rare-earth modifier, filter the back oven dry; The carbon nanotube that processing obtains is put into N by 0.05～0.15mg/ml, in the dinethylformamide dispersion agent, 40W ultrasonic dispersing 2～6 hours, obtain stable carbon nano tube suspension, then surface-assembled there is the film substrate of phosphate group to immerse in the carbon nano tube suspension for preparing, left standstill 4～16 hours, take out and use a large amount of deionized water rinsings at 20～60 ℃, the flushing back dries up with nitrogen, obtains the glass substrate that there is phosphate group silicone hydride-carbon nano-tube coextruded film on the surface;
Wherein, the volume percent of aminosilane is 0.5～2% in the described aminosilane solution, and 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 modifier is: rare earth compound 0.1～2%, alcohol 95～99.7%, ethylenediamine tetraacetic acid (EDTA) 0.05～0.5%, ammonium chloride 0.1～1%, nitric acid 0.02～0.5%, urea 0.03～1%; Described rare earth compound is a kind of in Lanthanum trichloride, Cerium II Chloride, lanthanum trioxide, the cerium oxide.
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Cited By (1)
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| CN102582148A (en) * | 2012-02-15 | 2012-07-18 | 上海交通大学 | Method for preparing phosphoryl silane-carbon nano tube composite thin film on surface of titanium alloy |
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| CN102936139A (en) * | 2012-11-12 | 2013-02-20 | 东华大学 | Method for preparing rare earth modification carbon nano tube ceramic composite film on glass substrate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102582148A (en) * | 2012-02-15 | 2012-07-18 | 上海交通大学 | Method for preparing phosphoryl silane-carbon nano tube composite thin film on surface of titanium alloy |
| CN102582148B (en) * | 2012-02-15 | 2014-11-12 | 上海交通大学 | Method for preparing phosphoryl silane-carbon nano tube composite thin film on surface of titanium alloy |
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