CN1654393A - Method for preparing sulfhydryl silicane-rare earth nano composite film on the surface of glass substrate - Google Patents
Method for preparing sulfhydryl silicane-rare earth nano composite film on the surface of glass substrate Download PDFInfo
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- CN1654393A CN1654393A CN 200510023463 CN200510023463A CN1654393A CN 1654393 A CN1654393 A CN 1654393A CN 200510023463 CN200510023463 CN 200510023463 CN 200510023463 A CN200510023463 A CN 200510023463A CN 1654393 A CN1654393 A CN 1654393A
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Abstract
The self-assembling process of preparing nanometer level composite mercapto silane-RE film on the hydroxylated surface of glass substrate includes first soaking glass substrate inside Pirahan solution for processing at room temperature for 1 hr, cleaning, drying, soaking inside mercapto silane solution for 6-8 hr, flushing, blowing to dry with nitrogen, and self assembling via setting the substrate inside self-assembling solution comprising RE compound, ethanol, EDTA, ammonium chloride, urea and nitric acid to form the self-assembled nanometer level mercapto silane-RE film. The present invention has simple process, and the prepared self-assembled film on the surface of glass substrate has obvious friction reducing and anti-wear effects.
Description
Technical field
The present invention relates to a kind of preparation method of rare earth nanometer composite film, relate in particular to the method that a kind of glass substrate surface prepares the sulfhydryl silane-rare earth nano compound film.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.But the process of some self-assembly laminated film preparation is more loaded down with trivial details comparatively speaking, and bigger to the pollution of environment, and friction reducing effect neither be fine.
Find by literature search, publication number is the preparation method that the Chinese invention patent of CN1403494A discloses a kind of self-assembling ultrathin polymkeric substance, 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, provide a kind of glass substrate surface to prepare the method for sulfhydryl silane-rare earth nano compound film, solve the friction problem of micro mechanical system, preparation technology is simple, and the film that is self-assembled into has good antifriction performance.
The present invention is achieved by the following technical solutions, and the present invention adopts the surface hydroxylated glass substrate of process as base material, adopts self-assembling method to prepare the sulfhydryl silane-rare earth nanometer film on its surface, and method is as follows:
At first, the pre-treatment of glass substrate, glass substrate adopts hydroxylation to handle.Treatment process: with Pirahan solution (H
2SO
4: H
2O
2=70: 30, V/V) under room temperature, handled 1 hour, 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.Glass substrate after handling is immersed in the hydrosulphonyl silane solution for preparing, left standstill 6～8 hours, after using chloroform, acetone, deionized water rinsing respectively after the taking-up, dry up with nitrogen and to be placed in the rare earth self-assembly solution for preparing, under 80～100 ℃, assembled 10～12 hours, and promptly obtained sulfhydryl silane-rare earth self-assembled nanometer film.
The component volumetric molar concentration of the hydrosulphonyl silane solution that the present invention adopts is: hydrosulphonyl silane 0.1～1.5mmol/L, solvent are benzole soln.
The weight percentages of components of the rare earth self-assembly solution that the present invention adopts is: ethanol content: 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, the cerium oxide; Hydrosulphonyl silane is a kind of in 3-sulfydryl propyl group methyl dimethoxysilane, the 3-sulfydryl propyl trimethoxy silicane.
The present invention adopts rare earth self-assembly solution self-assembly sulfhydryl silane-rare earth nano compound film on hydroxylated glass substrate, 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 one deck self-assembled film at substrate surface, and in the hydrosulphonyl silane molecule-the SH group has reactive behavior, and the number of chemical reaction can take place.With surface-assembled after the hydrosulphonyl silane bottom substrate inserts earth solution ,-SH group and rare earth element generation complex reaction, thus form one deck rare earth nanometer film again on the silane surface.And rare earth is self-assembled into that membrane process is simple, and cost is low, environmentally safe, and the film that is self-assembled into reaches Nano grade, good film-forming property.Adopt the rare earth nanometer film branch of method self-assembly of the present invention even, the film forming densification has good antifriction function.
Embodiment
Below technical scheme of the present invention is further described but component that technical characterictic of the present invention is not limited to provide in following examples and processing parameter by specific embodiment.
Embodiment 1:
At first, the pre-treatment of glass substrate, glass substrate adopts hydroxylation to handle.Treatment process: with Pirahan solution (H
2SO
4: H
2O
2=70: 30, V/V) under room temperature, handled 1 hour, use a large amount of deionized water ultrasonic cleaning 15 minutes again, be placed in the inherent baking oven of a dust keeper dry, glass substrate after handling is immersed in the hydrosulphonyl silane solution for preparing, left standstill 8 hours, the component volumetric molar concentration of hydrosulphonyl silane solution is: 3-sulfydryl propyl group methyl dimethoxysilane 0.2mmol/L, and solvent is a benzole soln; After using chloroform, acetone, deionized water rinsing respectively after the taking-up, dry up with nitrogen and to be placed in the rare earth self-assembly solution for preparing, under 80 ℃, assembled 12 hours, promptly obtain sulfhydryl silane-rare earth self-assembled nanometer film.
The weight percentages of components of rare earth self-assembly solution is: ethanol content: 60%, and Cerium II Chloride: 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: between 5～7nm, the thickness of laminated film is between 15～45nm at the organic film thickness that is self-assembled on the glass substrate.XPS spectrum figure shows at glass substrate surface and has successfully assembled sulfydryl organosilane film; Contain rare earth element in the film that will obtain after will in earth solution, assembling with the substrate of organosilane film, 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 sulfydryl, 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 0.1, have fairly obvious antifriction function.
Embodiment 2:
At first, the pre-treatment of glass substrate, glass substrate adopts hydroxylation to handle.Treatment process: under room temperature, handled 1 hour with Pirahan solution, use a large amount of deionized water ultrasonic cleaning 20 minutes again, be placed in the inherent baking oven of a dust keeper dry, glass substrate after handling is immersed in the hydrosulphonyl silane solution for preparing, left standstill 6 hours, the component volumetric molar concentration of hydrosulphonyl silane solution is: 3-sulfydryl propyl group methyl dimethoxysilane 0.8mmol/L, and solvent is a benzole soln; After using chloroform, acetone, deionized water rinsing respectively after the taking-up, dry up with nitrogen and to be placed in the rare earth self-assembly solution for preparing, under 90 ℃, assembled 11 hours, promptly obtain sulfhydryl silane-rare earth self-assembled nanometer film.
The weight percentages of components of rare earth self-assembly solution is: ethanol content: 80%, and Lanthanum trichloride: 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: between 5～10nm, the thickness of laminated film is between 15～40nm at the organic film thickness that is self-assembled on the glass substrate.XPS spectrum figure shows at glass substrate surface and has successfully assembled sulfydryl organosilane film; Contain rare earth element in the film that will obtain after will in earth solution, assembling with the substrate of organosilane film, 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 sulfydryl, so the surface of glass substrate has all covered rare earth nanometer composite film.
Embodiment 3:
At first, the pre-treatment of glass substrate, glass substrate adopts hydroxylation to handle.Treatment process: under room temperature, handled 1 hour with Pirahan solution, use a large amount of deionized water ultrasonic cleaning again, be placed in the inherent baking oven of a dust keeper dry, glass substrate after handling is immersed in the hydrosulphonyl silane solution for preparing, left standstill 8 hours, the component volumetric molar concentration of hydrosulphonyl silane solution is: 3-sulfydryl propyl trimethoxy silicane 1.5mmol/L, and solvent is a benzole soln; After using chloroform, acetone, deionized water rinsing respectively after the taking-up, dry up with nitrogen and to be placed in the rare earth self-assembly solution for preparing, under 100 ℃, assembled 10 hours, promptly obtain sulfhydryl silane-rare earth self-assembled nanometer film.
The weight percentages of components of rare earth self-assembly solution is: ethanol content: 70%, and Cerium II Chloride: 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: between 5～10nm, the thickness of laminated film is between 15～50nm at the organic film thickness that is self-assembled on the glass substrate.XPS spectrum figure shows at glass substrate surface and has successfully assembled sulfydryl organosilane film; Contain rare earth element in the film that will obtain after will in earth solution, assembling with the substrate of organosilane film, complex reaction has taken place in the group on itself and organosilane surface, and its surface observation is less than the index of silicon-dioxide and sulfydryl, thus the surface coverage of glass substrate rare earth nanometer composite film.
Claims (2)
1, a kind of glass substrate surface prepares the method for sulfhydryl silane-rare earth nano compound film, it is characterized in that, it is H that glass substrate is dipped in volume ratio
2SO
4: H
2O
2In=70: 30 the solution, under room temperature, handled 1 hour, dry with being placed on after the deionized water ultrasonic cleaning in the inherent baking oven of a dust keeper, glass substrate after will handling then immerses in the hydrosulphonyl silane solution for preparing, leave standstill taking-up in 6～8 hours, the flushing back dries up with nitrogen, this substrate is inserted in the rare earth self-assembly solution for preparing again, under 80～100 ℃, assembled 10～12 hours, and promptly obtained sulfhydryl silane-rare earth self-assembled nanometer film; Wherein, the component volumetric molar concentration of described hydrosulphonyl silane solution is: hydrosulphonyl silane 0.1～1.5mmol/L, solvent are benzole soln; The weight percentages of components of rare earth self-assembly solution is: ethanol content: 60%～80%, and 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 method for preparing the sulfhydryl silane-rare earth nano compound film according to the glass substrate surface of 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; Hydrosulphonyl silane is a kind of in 3-sulfydryl propyl group methyl dimethoxysilane, the 3-sulfydryl propyl trimethoxy silicane.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100366562C (en) * | 2005-12-29 | 2008-02-06 | 上海交通大学 | Production method of glass substrate surface self-assembly polyelectrolyte-rare earth nanometer film |
| CN102633441A (en) * | 2012-04-12 | 2012-08-15 | 东华大学 | Method for preparing rare earth doped ceramic composite film on glass substrate |
| CN106277815A (en) * | 2016-07-22 | 2017-01-04 | 上海交通大学 | A kind of NaYF4: the preparation method of the upper switching film of Yb/Er |
-
2005
- 2005-01-20 CN CN 200510023463 patent/CN1654393A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100366562C (en) * | 2005-12-29 | 2008-02-06 | 上海交通大学 | Production method of glass substrate surface self-assembly polyelectrolyte-rare earth nanometer film |
| CN102633441A (en) * | 2012-04-12 | 2012-08-15 | 东华大学 | Method for preparing rare earth doped ceramic composite film on glass substrate |
| CN106277815A (en) * | 2016-07-22 | 2017-01-04 | 上海交通大学 | A kind of NaYF4: the preparation method of the upper switching film of Yb/Er |
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