CN100560526C - The method for preparing carbon nano-tube coextruded film at glass substrate surface - Google Patents
The method for preparing carbon nano-tube coextruded film at glass substrate surface Download PDFInfo
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- CN100560526C CN100560526C CNB2007100370422A CN200710037042A CN100560526C CN 100560526 C CN100560526 C CN 100560526C CN B2007100370422 A CNB2007100370422 A CN B2007100370422A CN 200710037042 A CN200710037042 A CN 200710037042A CN 100560526 C CN100560526 C CN 100560526C
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Abstract
A kind of method for preparing carbon nano-tube coextruded film at glass substrate surface, prepare the sulfonic silane film at hydroxylated glass substrate surface with self-assembly method, then substrate is put into N, in the dinethylformamide carbon nanotube dispersion liquid, at the rare earth modified carbon nanotube of its surface deposition.At first glass substrate is dipped in Pirahan solution, handled 1 hour down for 90 ℃, immerse hydrosulphonyl silane solution behind the cleaning-drying, leave standstill and took out flushing in 6～8 hours, dry up with nitrogen and to place salpeter solution, obtain the glass substrate of surface with the sulfonic silane film, again substrate is inserted the carbon nano tube suspension after rare earth modified, under 20～80 ℃, left standstill 4～20 hours, take out and use a large amount of deionized water rinsings, the flushing back dries up with nitrogen, obtains the glass substrate that surface deposition has the modified carbon nano-tube laminated film.The present invention can be with frictional coefficient 0.8 during from no film be reduced to 0.1, have fairly obvious antifriction function.
Description
Technical field
The present invention relates to a kind of preparation method of carbon nano-tube coextruded film, relate in particular to a kind of method for preparing sulfonic silane-rare earth modified carbon nano-tube laminated film at glass substrate surface.Belong to the film preparation 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 etc. often is in nanometer scale, owing to be subjected to the influence of dimensional effect in the micromachine, micro friction wear and nano-scale thin film lubrication have become key issue, can prepare the self-assembled nanometer film with self-assembling method at present and solve this problem.Compare with other preparation thin film technique, the self-assembled film technology has operability, adaptability is strong, is with a wide range of applications.
Carbon nanotube is most typical monodimension nanometer material, has numerous excellent properties with its particular structure.Carbon nanotube has superpower mechanical property and high aspect ratio, and its tensile strength is 100 times of steel, and density is 1/6～1/7 of steel only, has 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, provide a kind of and prepare the method for carbon nano-tube coextruded film at glass substrate surface, technology is simple, and the laminated film that is self-assembled into has good antifriction performance, solves the friction problem of micro mechanical system.
The present invention is achieved by the following technical solutions, the present invention adopts the surface hydroxylated glass substrate of process as base material, adopt self-assembling method to prepare the hydrosulphonyl silane film on its surface, mercapto functional group with the hydrosulphonyl silane film surface under appropriate reaction conditions is oxidized to sulfonate functional groups, 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 specifically comprises the steps:
1, the pre-treatment of glass substrate, glass substrate adopt hydroxylation to handle.Treatment process: with Pirahan solution (H
2SO
4: H
2O
2=70: 30, V/V) handled 1 hour down in 90 ℃, use the deionized water ultrasonic cleaning again after, be placed in the inherent baking oven of a dust keeper dryly, drying temperature does not have particular requirement.The glass substrate hydroxylation that deals under such time and the temperature is very complete and substrate of glass is very smooth, is not corroded.It is in the benzole soln of 0.1～2.0mmol/L that glass substrate after will handling then immerses hydrosulphonyl silane concentration, leave standstill taking-up in 6～8 hours, the flushing back dries up with nitrogen, placing mass concentration is 30%～60% nitric acid, reacted 2 hours down at 50～80 ℃, take out and use deionized water rinsing, obtain the glass substrate of surface with the sulfonic silane film.
2, preparation carbon nanotube dispersion liquid: carbon nanotube is at room temperature immersed soak 1～4 hour in the rare-earth modifier earlier, filter the back oven dry.The weight percentages of components of the rare-earth modifier that is adopted is: rare earth compound: 0.1～1.5%, ethanol: 96～99.7%, ethylenediamine tetraacetic acid (EDTA) (EDTA): 0.05～0.5%, ammonium chloride: 0.1～1%, nitric acid: 0.02～0.5%, urea: 0.03～1%.The carbon nanotube that processing obtains is put into N by 0.1～0.2mg/ml, and in dinethylformamide (DMF) dispersion agent, ultrasonic dispersing (40W) 1～4 hour obtains stable carbon nano tube suspension.
3, surface-assembled there is the glass substrate of sulfonic silane film immerse in the carbon nano tube suspension for preparing, under 20～80 ℃, left standstill 4～20 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 surface deposition has the modified carbon nano-tube laminated film.
Rare earth compound of the present invention is a kind of in Lanthanum trichloride, Cerium II Chloride, lanthanum trioxide or the cerium oxide; Described carbon nanotube comprises single wall, double-walled or multi-walled carbon nano-tubes; Described hydrosulphonyl silane is a kind of in 3-sulfydryl propyl group methyl dimethoxysilane, the 3-sulfydryl propyl trimethoxy silicane.
The present invention prepares carbon nano-tube coextruded film at hydroxylated glass substrate upper surface, because having carried out hydroxylation, handles glass substrate surface, contain hydrolyzable active group in the hydrosulphonyl silane molecule, can build Si-O by chemistry combines with the base material with active group Si-OH, form the silane self-assembled film that one deck has mercapto groups at substrate surface, with surface-assembled the hydrosulphonyl silane bottom substrate insert in the salpeter solution and leave standstill for some time, the mercapto groups of film surface is become sulfonic group by in-situ oxidation.After again it being inserted carbon nano tube suspension, substrate surface is with deposition of carbon nanotubes.
Technology of the present invention is simple, and the rare-earth modifier of employing belongs to light rare earths, and preparation is simple, does not have problem of environmental pollution; 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.Carbon nano-tube coextruded film also has good wear resistance in addition, 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 are the supports to the technology of the present invention feature, rather than limit.
Embodiment 1:
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, glass substrate adopts hydroxylation pre-treatment, treatment process: glass substrate is dipped in Pirahan solution (H
2SO
4: H
2O
2=70: 30, V/V) in, handled 1 hour down in 90 ℃, use a large amount of deionized water ultrasonic cleaning 20 minutes again, be placed in the inherent baking oven of a dust keeper dry, to leave standstill 6 hours in the glass substrate immersion hydrosulphonyl silane solution after handling, the component volumetric molar concentration of hydrosulphonyl silane solution is: 3-sulfydryl propyl group methyl dimethoxysilane 0.2mmol/L, solvent is a benzole soln.Use chloroform, acetone, deionized water rinsing after the taking-up respectively, remove the organic molecule of surface physics absorption, dry up with nitrogen again that to place weight concentration be 30% nitric acid, 80 ℃ of reaction taking-ups after 1 hour down, use a large amount of deionized water rinsings, so just end sulfydryl in-situ oxidation is become sulfonic group, obtain the glass substrate of surface with the sulfonic silane film.
At room temperature carbon nanotube is immersed in the rare-earth modifier and soaked 1 hour, filter the back oven dry.The weight percentages of components of the rare-earth modifier that adopts is as follows: rare earth compound Lanthanum trichloride 0.3%, ethanol 99.5%, ethylenediamine tetraacetic acid (EDTA) 0.05%, ammonium chloride 0.1%, nitric acid 0.02%, urea 0.03%.The carbon nanotube that processing obtains is put into N by 0.15mg/ml, and in dinethylformamide (DMF) dispersion agent, ultrasonic dispersing (40W) 2 hours obtains stable carbon nano tube suspension.
There is the glass substrate of sulfonic silane film 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 surface deposition has the modified carbon nano-tube laminated film.
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 collection of illustrative plates shows in the Silan-based Thin Films that glass substrate surface is self-assembled into mercapto groups; Behind the in-situ oxidation, high valence state element sulphur is arranged, illustrate that the in-situ oxidation of the mercapto groups success on the surperficial Silan-based Thin Films has become sulfonic group, in the XPS collection of illustrative plates, observed the existence of lanthanum element simultaneously.Can see clearly then that from the SEM picture 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 carbon nano-tube compound film respectively.The carbon nano-tube compound film of glass substrate surface preparation can be with frictional coefficient 0.8 during from no film be reduced to 0.12, 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, the hydroxylation pre-treatment of glass substrate: glass substrate is dipped in the Pirahan solution, handled 1 hour down in 90 ℃, use a large amount of deionized water ultrasonic cleaning 20 minutes again, be placed on drying in the inherent baking oven of a dust keeper, the glass substrate after handling is immersed in the hydrosulphonyl silane solution for preparing, left standstill 7 hours, the component volumetric molar concentration of hydrosulphonyl silane solution is: 3-sulfydryl propyl group methyl dimethoxysilane 1.0mmol/L, and solvent is a benzole soln; After removing the surface physics adsorbed organic matter with chloroform, acetone, deionized water rinsing respectively after the taking-up, dry up with nitrogen that to place mass concentration be 50% nitric acid, reacted 1 hour down at 65 ℃, take out and use a large amount of deionized water rinsings, so just end sulfydryl in-situ oxidation is become sulfonic group, obtain the glass substrate of surface with the sulfonic silane film.
At room temperature carbon nanotube is immersed in the rare-earth modifier and soaked 3 hours, filter the back oven dry.Each weight percentages of components of rare-earth modifier is as follows: rare earth compound 1%, ethanol 96%, ethylenediamine tetraacetic acid (EDTA) 0.5%, ammonium chloride 1%, nitric acid 0.5%, urea 1%.The carbon nanotube that processing obtains is put into N by 0.1mg/ml, and in dinethylformamide (DMF) dispersion agent, ultrasonic dispersing (40W) 3 hours obtains stable carbon nano tube suspension.
There is the glass substrate of sulfonic silane film to immerse in the carbon nano tube suspension for preparing surface-assembled, under 60 ℃, left standstill 6 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 surface deposition has the modified carbon nano-tube laminated film.
Same characterization method is estimated film quality among the employing embodiment 1.
The XPS collection of illustrative plates shows in the thin film layers different in the laminated film that glass substrate surface is self-assembled into and contains sulfonic group, and do not observe the index of silicon-dioxide after the Silan-based Thin Films assembling.See clearly then that from the SEM picture 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 0.11, 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, the hydroxylation pre-treatment of glass substrate: glass substrate is dipped in the Pirahan solution, handled 1 hour down in 90 ℃, use a large amount of deionized water ultrasonic cleaning 20 minutes again, be placed on drying in the inherent baking oven of a dust keeper, the glass substrate after handling is immersed in the hydrosulphonyl silane for preparing, left standstill 8 hours, the component volumetric molar concentration of hydrosulphonyl silane solution is: 3-sulfydryl propyl trimethoxy silicane 2.0mmol/L, and solvent is a benzole soln; After using chloroform, acetone, deionized water rinsing respectively after the taking-up, dry up that to place mass concentration be 60% nitric acid 50 ℃ of reactions 1 hour down with nitrogen, take out and use a large amount of deionized water rinsings, so just end sulfydryl in-situ oxidation is become sulfonic group, obtain the glass substrate of surface with the sulfonic silane film.
At room temperature carbon nanotube is immersed in the rare-earth modifier and soaked 4 hours, filter the back oven dry.The weight percentages of components of the rare-earth modifier that is adopted is: rare earth compound Lanthanum trichloride 1.5%, ethanol 96.5%, ethylenediamine tetraacetic acid (EDTA) 0.2%, ammonium chloride 1%, nitric acid 0.3%, urea 0.5%.The carbon nanotube that processing obtains is put into N by 0.2mg/ml, and in dinethylformamide (DMF) dispersion agent, ultrasonic dispersing (40W) 4 hours obtains stable carbon nano tube suspension.
There is the glass substrate of sulfonic silane film to immerse in the carbon nano tube suspension for preparing surface-assembled, under 80 ℃, left standstill 20 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 surface deposition has the modified carbon nano-tube laminated film.
Same characterization method is estimated film quality among the employing embodiment 1.The XPS collection of illustrative plates shows is successfully assembling the hydrosulphonyl silane film on the substrate surface, and mercapto groups is become sulfonic group by in-situ oxidation; And observe and contain lanthanum element in the film, chemical shift has taken place in its bound energy, and the Rare Earth Lanthanum element that shows substrate surface is to assemble up in the mode of chemical bonding, just looks at the characteristic index less than silane; See clearly then that from the SEM picture 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 (2)
1, a kind ofly prepares the method for carbon nano-tube coextruded film, it is characterized in that comprising the steps: at glass substrate surface
It is H that glass substrate is dipped in volume ratio
2SO
4: H
2O
2In=70: 30 the solution, handled 1 hour down in 90 ℃, dry with being placed on after the deionized water ultrasonic cleaning in the inherent baking oven of dust keeper, it is in the benzole soln of 0.1～2.0mmol/L that glass substrate after will handling then immerses hydrosulphonyl silane concentration, leaves standstill taking-up in 6～8 hours, and the flushing back dries up with nitrogen, placing mass concentration is 30%～60% nitric acid, reacted 1 hour down at 50～80 ℃, take out and use deionized water rinsing, obtain the glass substrate of surface with the sulfonic silane film; Described hydrosulphonyl silane is a kind of in 3-sulfydryl propyl group methyl dimethoxysilane, the 3-sulfydryl propyl trimethoxy silicane;
Carbon nanotube immersed soak 1～4 hour in the rare-earth modifier, filter the back oven dry, the weight percentages of components of the rare-earth modifier that is adopted is: rare earth compound: 0.1～1.5%, ethanol: 96～99.7%, ethylenediamine tetraacetic acid (EDTA): 0.05～0.5%, ammonium chloride: 0.1～1%, nitric acid: 0.02～0.5%, urea: 0.03～1%; The carbon nanotube that processing obtains is put into N by 0.1～0.2mg/ml, the dinethylformamide dispersion agent, 40W ultrasonic dispersing 1～4 hour obtains stable carbon nano tube suspension; Described rare earth compound is a kind of in Lanthanum trichloride, Cerium II Chloride, lanthanum trioxide, the cerium oxide;
There is the glass substrate of sulfonic silane film to immerse in the carbon nano tube suspension for preparing surface-assembled, under 20～80 ℃, left standstill 4～20 hours, take out and use a large amount of deionized water rinsings, the flushing back dries up with nitrogen, obtains the glass substrate that surface deposition has the modified carbon nano-tube laminated film.
2, the method for preparing carbon nano-tube coextruded film according to the glass substrate surface of claim 1 is characterized in that described carbon nanotube is single wall or multi-walled carbon nano-tubes.
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| CN103739621A (en) * | 2010-09-08 | 2014-04-23 | 上海生物医学工程研究中心 | Application of surface treating agent with phosphorylcholine-like structure in material surface modification |
| CN102627409B (en) * | 2011-12-14 | 2015-09-09 | 京东方科技集团股份有限公司 | A kind of method preparing carbon nano-tube film |
| 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 |
| CN103007285B (en) * | 2012-12-10 | 2014-06-25 | 上海交通大学 | Preparation method for folic acid-decorated and rare earth-modified carbon nano tube |
| CN103043648A (en) * | 2012-12-27 | 2013-04-17 | 青岛艾德森能源科技有限公司 | Preparation method for carbon nanotube |
| CN103021763A (en) * | 2012-12-27 | 2013-04-03 | 青岛艾德森能源科技有限公司 | Method for preparing field-emission cathode material |
| CN104051059A (en) * | 2014-05-27 | 2014-09-17 | 东莞市纳利光学材料有限公司 | Carbon nano-tube conductive thin film and preparation method thereof |
| CN104857861B (en) * | 2015-04-24 | 2017-06-06 | 南京工业大学 | A kind of preparation method of the ceramic composite membrane for anionic dye desalination |
| CN106323918A (en) * | 2016-05-31 | 2017-01-11 | 中国科学院苏州纳米技术与纳米仿生研究所 | Local plasma optical imaging ellipsometry biosensor and preparation method thereof |
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