CN106832937B - It is a kind of to prepare high pressure resistant composite material and method using technique for atomic layer deposition is carbon nano-tube modified - Google Patents
It is a kind of to prepare high pressure resistant composite material and method using technique for atomic layer deposition is carbon nano-tube modified Download PDFInfo
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- CN106832937B CN106832937B CN201710008237.8A CN201710008237A CN106832937B CN 106832937 B CN106832937 B CN 106832937B CN 201710008237 A CN201710008237 A CN 201710008237A CN 106832937 B CN106832937 B CN 106832937B
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Abstract
High pressure resistant composite material and method, key step are prepared using technique for atomic layer deposition is carbon nano-tube modified the invention discloses a kind of are as follows: 1) are acidified carbon nanotube with the mix acid liquor of sulfuric acid and nitric acid；2) carbon nanotube after acidification is placed in the carbon nano tube surface deposition of aluminium oxide that the atomic layer deposition that temperature is 295~305 degrees Celsius is intracavitary, using trimethyl silicon source and deionized water as the precursor source of ALD deposition film, after acidification；3) post-depositional carbon nanotube is evenly spread in polymeric matrix using sonic oscillation and magnetic agitation, by sol evenning machine sample preparation and dries, obtains high pressure resistant composite material.Composite material made from the method for the present invention is compared with the polymer matrix composite and straight polymer matrix of doping conducting particles reported in the literature, breakdown strength is significantly increased, there is high dielectric constant for preparation, the polymer matrix composite of high breakdown field strength provides new thinking.
Description
[technical field]
The invention belongs to high pressure resistant technical field of composite preparation, and in particular to a kind of to be repaired using technique for atomic layer deposition
Decorations carbon nanotube prepares high pressure resistant composite material and method.
[background technique]
Polymer material usually has the features such as high insulating property, resist chemical is good, easy processing, is that current use is most wide
One of general material.Although however, the dielectric breakdown strength of polymer very high (E > 200kV mm always-1), but opposite dielectric
Constant is very low (κ < 5), this constrains the application of polymer significantly.Therefore, guaranteeing the same of other excellent in performance of polymer
When to greatly improve its relative dielectric constant be the important goal that scientific research and engineering practice are pursued.A kind of relatively common method is
The ferroelectric ceramic grain of high dielectric constant is adulterated into polymer to improve relative dielectric constant, such as lead titanates, lead titanate-zirconate, titanium
The particles such as sour barium form 0-3 type composite material.However, the dielectric constant due to polymer is very low, it is opposite in order to significantly improve
Dielectric constant, the content of ceramic particle usually will be more than 50%, after the ceramic particle of doping high-content, the elasticity of composite material
It significantly reduces, mechanical performance also obviously weakens.Meanwhile the dielectric breakdown strength of obtained composite material is remarkably decreased.It is another
Method is then to adulterate the composite material that conductive filler obtains by adulterating conductive filler (such as metallic) into polymer
Dielectric constant can be obtained by following equation
κm=κ (p-pc)-s (1)
κ in formulamIndicate that the relative dielectric constant of composite material, κ indicate that the relative dielectric constant of polymer substrate, p indicate
The mass fraction of doping, pcIndicate threshold concentration.It is available by formula, when the close infiltration threshold of the mass fraction of conductive filler
Value, the relative dielectric constant of composite material has to be increased significantly.But since the conductor non-conductor near percolation threshold turns
It changes, the dielectric loss of composite material is usually very high, and dielectric breakdown strength similarly reduces significantly.
[summary of the invention]
It is an object of the invention to solve problems of the prior art, a kind of utilization atomic layer deposition skill is provided
Art is carbon nano-tube modified to prepare high pressure resistant composite material and method, deposits one in carbon nano tube surface using technique for atomic layer deposition
The ultra-thin aluminium oxide of layer, then high pressure resistant composite material is prepared by the carbon nanotube after doping and modification, guaranteeing higher dielectric
The relative dielectric constant of composite material is improved while breakdown strength.
The present invention is achieved through the following technical solutions:
The following steps are included:
(1) carbon nanotube is acidified with acid solution；
(2) by technique for atomic layer deposition, with the carbon nano tube surface deposited oxide of silicon source and precursor source after acidification
Aluminium film；
(3) carbon nanotube of deposited oxide aluminium film is evenly spread in polymeric matrix, obtains carbon nanotube-polymerization
Object dispersion liquid；Wherein, the carbon nanotube mass of deposited oxide aluminium film accounts for the 0.2~1% of polymer matrix weight；
(4) carbon nano tube-polymer dispersion liquid is passed through into sol evenning machine sample preparation and dried, obtain high pressure resistant composite material.
Further, in step (1) acid solution using sulfuric acid and nitric acid mix acid liquor；With acid solution acid in step (1)
The concrete operations of carbon nano tube are as follows:
(101) it is 1:(3~5 according to the volume ratio of nitric acid and sulfuric acid) configuration mix acid liquor, wherein the mass fraction of nitric acid
It is 70%, the mass fraction of sulfuric acid is 98%；Matching for 100~300 milligrams of carbon nanotubes to be added in every 20 milliliters of mix acid liquors
Than carbon nanotube is added into mix acid liquor, obtains carbon nano tube suspension；
(102) it by carbon nano tube suspension sonic oscillation 20~60 minutes, then is placed in magnetic force in 50~100 DEG C of water-bath and stirs
It mixes 2~5 hours；
(103) the carbon nano tube suspension deionized water after stirring is diluted and is filtered, until the pH value of filtrate reaches 5
More than；
(104) obtained filter residue and drying and collection will be filtered, the carbon nanotube after being acidified.
Further, silicon source is trimethyl aluminium in step (2), and precursor source is deionized water, oxygen or oxygen plasma.
Further, in step (2) deposited oxide aluminium film concrete operations are as follows:
(201) atomic layer deposition for the carbon nanotube after acidification being placed in 295~305 DEG C is intracavitary；
(202) using nitrogen or inert gas as carrier gas, it is blown into silicon source in vapour form, the used time 0.1~0.4 second, then pass through
Nitrogen or inert gas, which purge, is discharged extra silicon source, and the used time 10~20 seconds；Then pulse enters the forerunner that can be reacted with silicon source
Body source steam, the used time 0.1~1 second, the carbon nano tube surface after acidification equably deposited upper one layer of aluminum oxide film；Pass through again
Nitrogen or inert gas purging discharge residue, the used time 3~16 seconds, complete a production cycle；
(203) production cycle of step (202), the carbon nano tube surface depositing several layers aluminum oxide film after acidification are repeated
Film.
Further, every layer of the aluminum oxide film film thickness of deposition is 0.1 nanometer.
Further, in step (3), by the carbon that 8.8~44mg deposited oxide aluminium film is added in every 15 milliliters of toluene
Nanotube meter disperses the carbon nanotube of deposited oxide aluminium film in toluene, sonic oscillation 1~2 hour, obtains suspending liquid A；
By being added in every 10 milliliters of toluene based on the polymeric matrix of 4.4g, disperse polymeric matrix in toluene, magnetic agitation 20~
60 minutes, obtain suspension B；Suspending liquid A is poured into suspension B, obtains mixed liquor C within magnetic agitation 20~60 minutes；Mixing
Liquid C sonic oscillation under condition of ice bath removed toluene after 2~5 hours, until the concentration of polymeric matrix reaches 0.8g/mL.
Further, polymeric matrix includes polydimethylsiloxane prepolymer object and matched crosslinking agent, type in step (3)
Number be Sylgard 184；Wherein, the mass ratio of polydimethylsiloxane prepolymer object and matched crosslinking agent is 10:(1~4).
Further, the concrete operations that step (4) prepares test sample by sol evenning machine and dries are as follows:
By carbon nano tube-polymer dispersant liquid drop in hydrophobic glass substrate, in 1000~2000 rpms turn
The lower rotation of speed 10~20 seconds, 50~100 DEG C drying 10~30 minutes, then be placed in 110~130 DEG C of baking oven 8~12 hours, obtain
To high pressure resistant composite material.
Further, hydrophobic glass substrate is through the following steps that obtained:
By sheet glass acetone, dehydrated alcohol and deionized water, ultrasound cleans up for 10~30 minutes respectively first, uses nitrogen
Air-blowing is dry；It is 1:(3~5 that the sheet glass after cleaning, which is placed in nitric acid and sulfuric acid volume ratio, again) mix acid liquor in sonic oscillation 20
It~60 minutes, is dried with nitrogen after being cleaned using deionized water；Sheet glass after finally acid is handled and dried up is placed in trimethyl chlorine
10~30 minutes in solution of silane, deionized water is cleaned and is used and is dried with nitrogen, and obtains hydrophobic sheet glass.
It is made as described above using the carbon nano-tube modified method for preparing high pressure resistant composite material of technique for atomic layer deposition
High pressure resistant composite material, with a thickness of 50~300 microns.
Compared with prior art, the invention has the following beneficial technical effects:
Using technique for atomic layer deposition depositing ultrathin alumina come carbon nano-tube modified in the method for the present invention, in carbon nanotube
Surface is doped in polymer substrate again after forming one layer of ultrathin insulating layer, improves composite material using the carbon nanotube after modification
Dielectric properties and promote or keep the resistance to breakdown characteristics of height of material；The present invention is received using technique for atomic layer deposition (ALD) in carbon
The thickness of the aluminium oxide of depositing ultrathin on mitron, aluminium oxide can accurately be controlled simply by the recurring number of technique for atomic layer deposition
System is in monoatomic layer magnitude.Promote carbon nanotube evenly dispersed in a polymer matrix by magnetic agitation and sonic oscillation, it is multiple
The relative dielectric constant of condensation material significantly improves, while being different from the document report of other doping conductive fillers, composite material
Dielectric breakdown strength will not only occur significantly to reduce compared to polymer, or even in a certain concentration, and composite material is hit
Wear the breakdown strength that intensity is more than polymeric matrix itself.The method of the present invention is easy to operate, and raw material sources are wide, Yi Shixian, for system
Standby to have high dielectric constant, the polymer matrix composite of high breakdown field strength provides new thinking, before having good application
Scape and economic benefit.
The present invention not only effectively improves the relative dielectric constant of composite material, can enhance two for polymer and arrive
Four times；Further significantly improve the dielectric breakdown strength of composite material, up to 109kV/mm.This makes prepared compound
Material suffers from huge application value and potentiality in terms of the research such as dielectric elastomer and energy storage material.
[Detailed description of the invention]
Fig. 1 is the energy spectrum diagram of carbon nanotube after present invention acidification.
Fig. 2 be the present invention acidification and after the deposition of aluminium oxide of surface carbon nanotube energy spectrum diagram.
Fig. 3 is the graph of relation of composite material relative dielectric constant and mass fraction of the present invention.
Fig. 4 is the graph of relation of composite material dielectric breakdown strength and mass fraction of the present invention.
[specific embodiment]
The present invention includes the following steps:
(1) carbon nanotube is acidified with the mix acid liquor of sulfuric acid and nitric acid；
According to volume ratio range it is 1:(3~5 by the sulfuric acid of the nitric acid of mass fraction 70% and mass fraction 98%) match
Mix acid liquor is set, carbon nanotube is added so that the proportion of 100~300 milligrams of particles to be added in every 20 milliliters of nitration mixture, obtains carbon nanometer
Pipe suspension；Obtained carbon nano tube suspension is by 50~100 degrees Celsius of sonic oscillation 20~be placed in after sixty minutes of water-bath
Middle magnetic agitation 2~5 hours；Obtained suspension is diluted in deionized water, and is filtered using Suction filtration device, until outstanding
The hydrogen ionexponent of supernatant liquid reaches 5 or more (i.e. pH value is 5 or more)；It dries and collects, the carbon nanometer after being acidified
Pipe.
(2) atomic layer deposition for the carbon nanotube after acidification being placed in 295~305 degrees Celsius is intracavitary, with trimethyl silicon source
With deionized water as precursor source, nitrogen buffer gas, vapor form is blown into trimethyl silicon source, and the used time 0.1~0.4 second, then
It is purged by nitrogen and extra trimethyl silicon source is discharged, the used time 10~20 seconds；Then pulse, which enters, to react with trimethyl silicon source
Deionized water precursor source steam, the used time 0.1~1 second, uniformly conformally (covered completely in each place in carbon nano tube surface
Lid) the upper one layer of aluminum oxide film of deposition, one layer of aluminum oxide film film thickness is 0.1 nanometer；Discharge residue is purged by nitrogen again,
Used time 3~16 seconds, complete a cycle；Aluminum oxide film film thickness is controlled by repeating the above-mentioned production cycle, for example is repeated up to
The aluminum oxide film that carbon nano tube surface deposition thickness after acidification is 5 nanometers.Precursor source can also use oxygen or oxygen etc.
Gas ions etc., carrier gas can use inert gas such as helium etc..
(3) carbon nanotube after deposition of aluminium oxide evenly spreads to polymeric matrix by sonic oscillation and magnetic agitation
In；
It disperses the carbon nanotube after the modification of 8.8~44mg in 15 milliliters of toluene, sonic oscillation 1~2 hour, obtains
To suspending liquid A；It disperses the polymeric matrix of 4.4g in 10 milliliters of toluene, magnetic agitation 20~60 minutes, obtains suspension
B；A is poured slowly into B and obtains mixed liquor C, in mixed liquor C, the carbon nanotube mass after modification accounts for the 0.2 of polymer quality
~1%；C is carried out magnetic agitation 20~60 minutes, subsequent sonic oscillation 2~5 hours under condition of ice bath；It is natural in draught cupboard
Volatilization removes toluene, until the concentration of polymer reaches 0.8g/mL, carbon nano tube-polymer dispersion liquid is made；It is used poly-
Conjunction object is polydimethylsiloxane, and dimethyl silicone polymer (PDMS) consists of two parts, and wherein component A is prepolymer,
Component B is crosslinking agent, and component A is 10:(1~4 with component B in mass ratio) it can crosslink and react to obtain PDMS after mixing.
The model of dimethyl silicone polymer (PDMS) is Sylgard 184.
(4) test sample is prepared using sol evenning machine and dry:
By sheet glass acetone, dehydrated alcohol, ultrasound cleans up deionized water for 10~30 minutes respectively, is blown with nitrogen
It is dry；It is sonic oscillation 20 in the mix acid liquor in 1:3 to 1:5 proportional region that sheet glass after cleaning, which is placed in nitric acid than sulfuric acid volume,
It~60 minutes, is dried with nitrogen after being cleaned using deionized water；Treated that sheet glass is placed in 10 in trim,ethylchlorosilane solution for acid
~30 minutes, deionized water was cleaned and is used and is dried with nitrogen, and obtained hydrophobic sheet glass.
By carbon nano tube-polymer dispersant liquid drop on hydrophobic sheet glass, 1000~2000 rpms of rotations 10~
20 seconds, 50~100 degrees Celsius drying 10~30 minutes, then be placed in 110~130 degrees Celsius of baking ovens 8~12 hours and dry, obtain
High pressure resistant composite material.
Thickness of composite material produced by the present invention is 50~300 microns.
The preferred embodiments of the present invention will be described in detail with reference to the accompanying drawing, so that advantages and features of the invention energy
It is easier to be readily appreciated by one skilled in the art, so as to make a clearer definition of the protection scope of the present invention.
Embodiment 1:
(1) carbon nanotube is acidified with the mix acid liquor of sulfuric acid and nitric acid；
It is that 1:4 configures mix acid liquor according to the volume ratio of nitric acid and sulfuric acid, 200 milligrams to be added in every 20 milliliters of nitration mixture
Carbon nanotube is added in the proportion of particle, obtains carbon nano tube suspension；Obtained carbon nano tube suspension passes through sonic oscillation 30
Minute is placed in 70 degrees Celsius of water-bath magnetic agitation 3 hours；Obtained suspension is diluted in deionized water, and uses pumping
Filter device is filtered, until the hydrogen ionexponent of suspension reaches 5；It dries and collects, the carbon nanometer after being acidified
Pipe.
(2) atomic layer deposition for the carbon nanotube after acidification being placed in 300 DEG C is intracavitary, nitrogen buffer gas, vapor form
It is blown into trimethyl silicon source, the used time 0.1 second, then extra trimethyl silicon source is discharged by nitrogen purging, the used time 10 seconds；Then pulse
Enter the deionized water precursor source steam that can be reacted with trimethyl silicon source, it is the used time 0.1 second, uniformly conformal in carbon nano tube surface
Ground deposits upper one layer of aluminum oxide film；Discharge residue is purged by nitrogen again, the used time 3 seconds, completes a cycle；It repeats above-mentioned
Production cycle is until the aluminum oxide film that the carbon nano tube surface deposition thickness after acidification is 5 nanometers.
(3) carbon nanotube after deposition of aluminium oxide evenly spreads to polymeric matrix by sonic oscillation and magnetic agitation
In；
It disperses the carbon nanotube after 13.2 milligrams of modifications in 15 milliliters of toluene solution, sonic oscillation 1 hour, obtains
Suspending liquid A；It disperses the dimethyl silicone polymer of 4 grams of component As and 0.4 gram of B component in 10 milliliters of toluene solutions, mechanical stirring
20 minutes, obtain suspension B；A is poured slowly into B and obtains mixed liquor C, the carbon nanotube mass in mixed liquor C, after modification
Account for the 0.3% of polymer matrix weight；C is carried out magnetic agitation 20 minutes, subsequent sonic oscillation 2 hours under condition of ice bath；
Magnetic agitation removes toluene in ventilating kitchen under room temperature, until the concentration of polymer reaches 0.8g/mL, it is poly- that carbon nanotube-is made
Close object dispersion liquid；
(4) test sample is prepared using sol evenning machine and dry:
By sheet glass acetone, dehydrated alcohol, ultrasound cleans up deionized water for 10 minutes respectively, with being dried with nitrogen；Clearly
It is sonic oscillation 20 minutes in the mix acid liquor in 1:4 proportional region that sheet glass after washing, which is placed in nitric acid than sulfuric acid volume, is used
It is dried with nitrogen after deionized water cleaning；Treated that sheet glass is placed in trim,ethylchlorosilane solution 10 minutes for acid, deionized water
It cleans and uses and be dried with nitrogen, obtain hydrophobic sheet glass.
By carbon nano tube-polymer dispersant liquid drop on hydrophobic sheet glass, 1000 rpms rotate 10 seconds, and 50 is Celsius
Degree is 10 minutes dry, then is placed in 8 hours in 110 degrees Celsius of baking ovens and dries, and obtains high pressure resistant composite material.
Effect of the invention by verifying as follows:
Test method:
The carbon nanotube before and after deposition of aluminium oxide is observed using field emission scanning electron microscope (FSEM), and is done
Power spectrum (EDS) elemental analysis, takes multiple measurements sample using high-precision digital-display micrometer, determines test composite sample
Thickness, use broadband dielectric spectroscopy test macro measurement sample dielectric property and DC power system test sample breakdown
Intensity.
The deposition of aluminium oxide
After Fig. 1 and table 1 are the power spectrum elemental analyses of carbon nanotube after acidification as a result, Fig. 2 and table 2 be deposition of aluminium oxide
Power spectrum elemental analysis result.
The power spectrum elemental analysis result of carbon nanotube after table 1 is acidified
| Element | Mass fraction (%) | Atomicity (%) | Net content | Error (%) |
| Carbon | 44.62 | 64.46 | 55.5 | 12.54 |
| Oxygen | 4.87 | 5.28 | 16.87 | 16.42 |
| Silicon | 48.71 | 30.1 | 1793.67 | 1,93 |
| Gold | 1.8 | 0.16 | 2.06 | 63.12 |
Power spectrum elemental analysis result after 2 deposition of aluminium oxide of table
| Element | Mass fraction (%) | Atomic quantity (%) | Net content | Error (%) |
| Carbon | 84.91 | 89.17 | 366.5 | 4.87 |
| Oxygen | 12.7 | 10.01 | 21.7 | 14.62 |
| Aluminium | 0.35 | 0.16 | 6.72 | 21.62 |
| Silicon | 1.9 | 0.54 | 25.49 | 8.61 |
According to the result of power spectrum elemental analysis it can be found that in the EDS result of the carbon nanotube after deposition of aluminium oxide, observation
The presence for having arrived aluminium illustrates that aluminium oxide has had been deposited into carbon nano tube surface really.
The dielectric breakdown strength for measuring the composite material is 109kV/mm.
Embodiment 2
It is adjusted to the carbon nanotube mass after modification in step (3) to account for 0.2%, 0.5% and of polymer quality respectively
0.7%, other conditions are same as Example 1, carry out compliance test result to the relative dielectric constant of gained composite material.
Fig. 3 is the relative dielectric constant of composite material and the relation curve of mass fraction.Realize the result shows that, for ALD
The composite material of carbon nanotube preparation after deposition of aluminium oxide modification, when doped carbon nanometer pipe mass fraction is 0.7wt%, dielectric
Constant is 10 in frequency74 are increased by the 2 of polymer at Hz, is increased twice；When doping concentration is 0.5wt%, dielectric
Constant is 10 in frequency-215 have been increased to by 3.5 at Hz, has been enhanced more than 4 times, relative dielectric constant significantly improves, and with mixing
The raising of miscellaneous concentration, relative dielectric constant further enhance.
Embodiment 3
The direct doped carbon nanometer pipe in step (3), and doping is respectively 0~1%, other conditions and 1 phase of embodiment
Together, the breakdown of gained composite material is verified.
Fig. 4 and table 3 are the relationship graph between the dielectric breakdown of composite material and doping concentration respectively.
The dielectric breakdown strength of composite material made from 3 embodiment 2 of table
| Carbon nano tube-doped amount (%) | 0.3 | 0.5 | 0.7 |
| Dielectric breakdown strength (kV/mm, carbon nanotube are unmodified) | 37 | 28.5 | 15.8 |
| Dielectric breakdown strength (kV/mm, after carbon nano tube modified) | 109 | 78 | 80 |
The experimental results showed that the dielectric breakdown strength that direct doped carbon nanometer pipe obtains composite material significantly reduces；And it is right
The composite material prepared after doped aluminium is carbon nano-tube modified, the experimental results showed that, with the raising of doping concentration, dielectric
Breakdown strength was significantly improved before this, even more than the disruptive field intensity of polymeric matrix itself, when concentration be more than 0.3wt% it
Afterwards, dielectric breakdown starts the raising with concentration and reduces, but breakdown strength remains on 75kV/mm.
Embodiment 4:
(1) carbon nanotube is acidified with the mix acid liquor of sulfuric acid and nitric acid；
It is that 1:3 configures mix acid liquor according to the volume ratio of nitric acid and sulfuric acid, 100 milligrams to be added in every 20 milliliters of nitration mixture
Carbon nanotube is added in the proportion of particle, obtains carbon nano tube suspension；Obtained carbon nano tube suspension passes through sonic oscillation 20
Minute is placed in 50 degrees Celsius of water-bath magnetic agitation 2 hours；Obtained suspension is diluted in deionized water, and uses pumping
Filter device is filtered, until the hydrogen ionexponent of suspension reaches 6；It dries and collects, the carbon nanometer after being acidified
Pipe.
(2) atomic layer deposition for the carbon nanotube after acidification being placed in 295 DEG C is intracavitary, nitrogen buffer gas, vapor form
It is blown into trimethyl silicon source, the used time 0.2 second, then extra trimethyl silicon source is discharged by nitrogen purging, the used time 15 seconds；Then pulse
Enter the deionized water precursor source steam that can be reacted with trimethyl silicon source, it is the used time 0.5 second, uniformly conformal in carbon nano tube surface
Ground deposits upper one layer of aluminum oxide film；Discharge residue is purged by nitrogen again, the used time 5 seconds, completes a cycle；It repeats above-mentioned
Production cycle is until the aluminum oxide film that the carbon nano tube surface deposition thickness after acidification is 5 nanometers.
(3) carbon nanotube after deposition of aluminium oxide evenly spreads to polymeric matrix by sonic oscillation and magnetic agitation
In；
It disperses the carbon nanotube after 22 milligrams of modifications in 15 milliliters of toluene solution, sonic oscillation 1.5 hours, obtains
Suspending liquid A；It disperses 4.4 grams of dimethyl silicone polymer in 10 milliliters of toluene solutions, mechanical stirring 30 minutes, is suspended
Liquid B, the mass ratio of component A and B component is 10:2 in dimethyl silicone polymer；A is poured slowly into B and obtains mixed liquor C, mixed
It closes in liquid C, the carbon nanotube mass after modification accounts for the 0.5% of polymer matrix weight；C is carried out magnetic agitation 30 minutes, with
Sonic oscillation 3 hours under condition of ice bath afterwards；Magnetic agitation removes toluene in ventilating kitchen under room temperature, until the concentration of polymer
Reach 0.8g/mL, carbon nano tube-polymer dispersion liquid is made；
(4) test sample is prepared using sol evenning machine and dry:
By sheet glass acetone, dehydrated alcohol, ultrasound cleans up deionized water for 15 minutes respectively, with being dried with nitrogen；Clearly
It is sonic oscillation 30 minutes in the mix acid liquor of 1:3 that sheet glass after washing, which is placed in nitric acid than sulfuric acid volume, clear using deionized water
It is dried with nitrogen after washing；Treated that sheet glass is placed in trim,ethylchlorosilane solution 15 minutes for acid, and deionized water cleans and uses nitrogen
Air-blowing is dry, obtains hydrophobic sheet glass.
By carbon nano tube-polymer dispersant liquid drop on hydrophobic sheet glass, 1500 rpms rotate 20 seconds, and 60 is Celsius
Degree is 15 minutes dry, then is placed in 12 hours in 120 degrees Celsius of baking ovens and dries, and obtains high pressure resistant composite material.
Embodiment 5:
(1) carbon nanotube is acidified with the mix acid liquor of sulfuric acid and nitric acid；
It is that 1:4 configures mix acid liquor according to the volume ratio of nitric acid and sulfuric acid, 200 milligrams to be added in every 20 milliliters of nitration mixture
Carbon nanotube is added in the proportion of particle, obtains carbon nano tube suspension；Obtained carbon nano tube suspension passes through sonic oscillation 60
Minute is placed in 100 degrees Celsius of water-bath magnetic agitation 5 hours；Obtained suspension is diluted in deionized water, and is used
Suction filtration device is filtered, until the hydrogen ionexponent of suspension reaches 6.5；It dries and collects, the carbon after being acidified
Nanotube.
(2) atomic layer deposition for the carbon nanotube after acidification being placed in 305 DEG C is intracavitary, nitrogen buffer gas, vapor form
It is blown into trimethyl silicon source, the used time 0.4 second, then extra trimethyl silicon source is discharged by nitrogen purging, the used time 20 seconds；Then pulse
Enter the deionized water precursor source steam that can be reacted with trimethyl silicon source, it is the used time 0.8 second, uniformly conformal in carbon nano tube surface
Ground deposits upper one layer of aluminum oxide film；Discharge residue is purged by nitrogen again, the used time 10 seconds, completes a cycle；In repetition
The production cycle is stated until the aluminum oxide film that the carbon nano tube surface deposition thickness after acidification is 5 nanometers.
(3) carbon nanotube after deposition of aluminium oxide evenly spreads to polymeric matrix by sonic oscillation and magnetic agitation
In；
It disperses the carbon nanotube after 22 milligrams of modifications in 15 milliliters of toluene solution, sonic oscillation 2 hours, is hanged
Supernatant liquid A；It disperses 4.4 grams of dimethyl silicone polymer in 10 milliliters of toluene solutions, mechanical stirring 40 minutes, obtains suspension
B, the mass ratio of component A and B component is 10:3 in dimethyl silicone polymer；A is poured slowly into B and obtains mixed liquor C, is being mixed
In liquid C, the carbon nanotube mass after modification accounts for the 0.5% of polymer matrix weight；To C progress magnetic agitation 40 minutes, then
Sonic oscillation 4 hours under condition of ice bath；Magnetic agitation removes toluene in ventilating kitchen under room temperature, until the concentration of polymer reaches
To 0.8g/mL, carbon nano tube-polymer dispersion liquid is made；
(4) test sample is prepared using sol evenning machine and dry:
By sheet glass acetone, dehydrated alcohol, ultrasound cleans up deionized water for 20 minutes respectively, with being dried with nitrogen；Clearly
It is sonic oscillation 40 minutes in the mix acid liquor of 1:5 that sheet glass after washing, which is placed in nitric acid than sulfuric acid volume, clear using deionized water
It is dried with nitrogen after washing；Treated that sheet glass is placed in trim,ethylchlorosilane solution 20 minutes for acid, and deionized water cleans and uses nitrogen
Air-blowing is dry, obtains hydrophobic sheet glass.
By carbon nano tube-polymer dispersant liquid drop on hydrophobic sheet glass, 1800 rpms rotate 15 seconds, and 100 take the photograph
Family name's degree is 20 minutes dry, then is placed in 10 hours in 130 degrees Celsius of baking ovens and dries, and obtains high pressure resistant composite material.
Embodiment 6:
(1) carbon nanotube is acidified with the mix acid liquor of sulfuric acid and nitric acid；
It is that 1:5 configures mix acid liquor according to the volume ratio of nitric acid and sulfuric acid, 300 milligrams to be added in every 20 milliliters of nitration mixture
Carbon nanotube is added in the proportion of particle, obtains carbon nano tube suspension；Obtained carbon nano tube suspension passes through sonic oscillation 40
Minute is placed in 60 degrees Celsius of water-bath magnetic agitation 4 hours；Obtained suspension is diluted in deionized water, and uses pumping
Filter device is filtered, until the hydrogen ionexponent of suspension reaches 6.8；It dries and collects, the carbon after being acidified is received
Mitron.
(2) atomic layer deposition for the carbon nanotube after acidification being placed in 298 DEG C is intracavitary, using helium as carrier gas, vapor form
It is blown into trimethyl silicon source, the used time 0.3 second, then extra trimethyl silicon source is discharged by helium purging, the used time 18 seconds；Then pulse
Enter the oxygen plasma precursor source steam that can be reacted with trimethyl silicon source, it is the used time 1 second, uniformly conformal in carbon nano tube surface
Ground deposits upper one layer of aluminum oxide film；Discharge residue is purged by helium again, the used time 16 seconds, completes a cycle；In repetition
The production cycle is stated until the aluminum oxide film that the carbon nano tube surface deposition thickness after acidification is 5 nanometers.
(3) carbon nanotube after deposition of aluminium oxide evenly spreads to polymeric matrix by sonic oscillation and magnetic agitation
In；
It disperses the carbon nanotube after 22 milligrams of modifications in 15 milliliters of toluene solution, sonic oscillation 1.2 hours, obtains
Suspending liquid A；It disperses 4.4 grams of dimethyl silicone polymer in 10 milliliters of toluene solutions, mechanical stirring 60 minutes, is suspended
Liquid B, the mass ratio of component A and B component is 10:4 in dimethyl silicone polymer；A is poured slowly into B and obtains mixed liquor C, mixed
It closes in liquid C, the carbon nanotube mass after modification accounts for the 0.5% of polymer matrix weight；C is carried out magnetic agitation 60 minutes, with
Sonic oscillation 5 hours under condition of ice bath afterwards；Magnetic agitation removes toluene in ventilating kitchen under room temperature, until the concentration of polymer
Reach 0.8g/mL, carbon nano tube-polymer dispersion liquid is made；
(4) test sample is prepared using sol evenning machine and dry:
By sheet glass acetone, dehydrated alcohol, ultrasound cleans up deionized water for 30 minutes respectively, with being dried with nitrogen；Clearly
It is sonic oscillation 60 minutes in the mix acid liquor of 1:4 that sheet glass after washing, which is placed in nitric acid than sulfuric acid volume, clear using deionized water
It is dried with nitrogen after washing；Treated that sheet glass is placed in trim,ethylchlorosilane solution 30 minutes for acid, and deionized water cleans and uses nitrogen
Air-blowing is dry, obtains hydrophobic sheet glass.
By carbon nano tube-polymer dispersant liquid drop on hydrophobic sheet glass, 2000 rpms rotate 12 seconds, and 80 is Celsius
Degree is 30 minutes dry, then is placed in 9 hours in 115 degrees Celsius of baking ovens and dries, and obtains high pressure resistant composite material.
In conclusion the method for the present invention using technique for atomic layer deposition depositing ultrathin alumina layer come carbon nano-tube modified,
And by doping content lower than 1wt% filler come modified dimethyl polysiloxane, doping process mainly use sonic oscillation with
Magnetic agitation promotes the carbon nanotube dispersion in the polymer matrix after modification, then prepares test specimens by sol evenning machine
Product.The method have the advantages that while the dielectric constant of composite material is improved, the dielectric of composite material
Breakdown strength will not only occur significantly to reduce compared to polymer, or even in a certain concentration, the breakdown field of composite material
Strong is more than the intensity of polymeric matrix itself, and whole preparation process is simple and easy.
Composite material made from the method for the present invention and it is reported in the literature doping conducting particles polymer matrix composite with
And straight polymer matrix is compared, breakdown strength is significantly increased, and has high dielectric constant, the polymer of high breakdown field strength for preparation
Based composites provide new thinking, have a good application prospect and economic benefit.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalent structure or equivalent flow shift made by bright specification and accompanying drawing content is applied directly or indirectly in other relevant skills
Art field, is included within the scope of the present invention.
Claims (10)
1. a kind of utilize the carbon nano-tube modified method for preparing high pressure resistant composite material of technique for atomic layer deposition, which is characterized in that
The following steps are included:
(1) carbon nanotube is acidified with acid solution；
(2) thin with the carbon nano tube surface deposition of aluminium oxide of silicon source and precursor source after acidification by technique for atomic layer deposition
Film；
(3) carbon nanotube of deposited oxide aluminium film is evenly spread in polymeric matrix, obtains carbon nano tube-polymer point
Dispersion liquid；Wherein, the carbon nanotube mass of deposited oxide aluminium film accounts for the 0.2~1% of polymer matrix weight；
(4) carbon nano tube-polymer dispersion liquid is passed through into sol evenning machine sample preparation and dried, obtain high pressure resistant composite material.
2. according to claim 1 a kind of high pressure resistant composite material is prepared using technique for atomic layer deposition is carbon nano-tube modified
Method, which is characterized in that in step (1) acid solution using sulfuric acid and nitric acid mix acid liquor；With acid solution acid in step (1)
The concrete operations of carbon nano tube are as follows:
(101) it is 1:(3~5 according to the volume ratio of nitric acid and sulfuric acid) configuration mix acid liquor, wherein the mass fraction of nitric acid is
70%, the mass fraction of sulfuric acid is 98%；The proportion of 100~300 milligrams of carbon nanotubes to be added in every 20 milliliters of mix acid liquors,
Carbon nanotube is added into mix acid liquor, obtains carbon nano tube suspension；
(102) by carbon nano tube suspension sonic oscillation 20~60 minutes, then it is placed in magnetic agitation 2 in 50~100 DEG C of water-bath
~5 hours；
(103) the carbon nano tube suspension deionized water after stirring is diluted and is filtered, until the pH value of filtrate reach 5 with
On；
(104) obtained filter residue and drying and collection will be filtered, the carbon nanotube after being acidified.
3. according to claim 1 a kind of high pressure resistant composite material is prepared using technique for atomic layer deposition is carbon nano-tube modified
Method, which is characterized in that in step (2) silicon source be trimethyl aluminium, precursor source be deionized water, oxygen or oxygen plasma
Body.
4. according to claim 1 a kind of high pressure resistant composite material is prepared using technique for atomic layer deposition is carbon nano-tube modified
Method, which is characterized in that the concrete operations of deposited oxide aluminium film in step (2) are as follows:
(201) atomic layer deposition for the carbon nanotube after acidification being placed in 295~305 DEG C is intracavitary；
(202) using nitrogen or inert gas as carrier gas, it is blown into silicon source in vapour form, the used time 0.1~0.4 second, then pass through nitrogen
Or the silicon source that inert gas purging discharge is extra, the used time 10~20 seconds；Then pulse enters the precursor source that can be reacted with silicon source
Steam, the used time 0.1~1 second, the carbon nano tube surface after acidification equably deposited upper one layer of aluminum oxide film；Pass through nitrogen again
Or inert gas purging discharge residue, the used time 3~16 seconds, complete a production cycle；
(203) production cycle of step (202), the carbon nano tube surface depositing several layers aluminum oxide film after acidification are repeated.
5. according to claim 4 a kind of high pressure resistant composite material is prepared using technique for atomic layer deposition is carbon nano-tube modified
Method, which is characterized in that every layer of the aluminum oxide film film thickness of deposition is 0.1 nanometer.
6. according to claim 1 a kind of high pressure resistant composite material is prepared using technique for atomic layer deposition is carbon nano-tube modified
Method, which is characterized in that in step (3), by every 15 milliliters of toluene be added 8.8~44mg deposited oxide aluminium film carbon
Nanotube meter disperses the carbon nanotube of deposited oxide aluminium film in toluene, sonic oscillation 1~2 hour, obtains suspending liquid A；
By being added in every 10 milliliters of toluene based on the polymeric matrix of 4.4g, disperse polymeric matrix in toluene, magnetic agitation 20~
60 minutes, obtain suspension B；Suspending liquid A is poured into suspension B, obtains mixed liquor C within magnetic agitation 20~60 minutes；Mixing
Liquid C sonic oscillation under condition of ice bath removed toluene after 2~5 hours, until the concentration of polymeric matrix reaches 0.8g/mL.
7. according to claim 1 a kind of high pressure resistant composite material is prepared using technique for atomic layer deposition is carbon nano-tube modified
Method, which is characterized in that polymeric matrix includes polydimethylsiloxane prepolymer object and matched crosslinking agent in step (3),
Model Sylgard 184；Wherein, the mass ratio of polydimethylsiloxane prepolymer object and matched crosslinking agent is 10:(1~4).
8. according to claim 1 a kind of high pressure resistant composite material is prepared using technique for atomic layer deposition is carbon nano-tube modified
Method, which is characterized in that step (4) pass through sol evenning machine prepare test sample and dry concrete operations are as follows:
By carbon nano tube-polymer dispersant liquid drop in hydrophobic glass substrate, under 1000~2000 rpms of revolving speed
Rotation 10~20 seconds, 50~100 DEG C drying 10~30 minutes, then be placed in 110~130 DEG C of baking oven 8~12 hours, obtain resistance to
High-pressure composite material.
9. according to claim 8 a kind of high pressure resistant composite material is prepared using technique for atomic layer deposition is carbon nano-tube modified
Method, which is characterized in that hydrophobic glass substrate is through the following steps that obtained:
By sheet glass acetone, dehydrated alcohol and deionized water, ultrasound cleans up for 10~30 minutes respectively first, is blown with nitrogen
It is dry；It is 1:(3~5 that the sheet glass after cleaning, which is placed in nitric acid and sulfuric acid volume ratio, again) mix acid liquor in sonic oscillation 20~60
Minute, it is dried with nitrogen after being cleaned using deionized water；Sheet glass after finally acid is handled and dried up is placed in trim,ethylchlorosilane
10~30 minutes in solution, deionized water is cleaned and is used and is dried with nitrogen, and obtains hydrophobic sheet glass.
10. utilizing the carbon nano-tube modified side for preparing high pressure resistant composite material of technique for atomic layer deposition as described in claim 1
High pressure resistant composite material made from method, which is characterized in that high pressure resistant composite material obtained with a thickness of 50~300 microns.
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| CN103214850A (en) * | 2013-05-13 | 2013-07-24 | 哈尔滨理工大学 | Mixed silicon rubber-based conductive nonlinear insulating material |
| CN105420689A (en) * | 2015-11-06 | 2016-03-23 | 中国人民解放军国防科学技术大学 | Oriented carbon nano tube and aluminum oxide hybrid fiber and preparation method thereof |
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| CN103214850A (en) * | 2013-05-13 | 2013-07-24 | 哈尔滨理工大学 | Mixed silicon rubber-based conductive nonlinear insulating material |
| CN105420689A (en) * | 2015-11-06 | 2016-03-23 | 中国人民解放军国防科学技术大学 | Oriented carbon nano tube and aluminum oxide hybrid fiber and preparation method thereof |
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