CN106832937A - One kind prepares high pressure resistant composite and method using technique for atomic layer deposition is carbon nano-tube modified - Google Patents
One kind prepares high pressure resistant composite and method using technique for atomic layer deposition is carbon nano-tube modified Download PDFInfo
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- CN106832937A CN106832937A CN201710008237.8A CN201710008237A CN106832937A CN 106832937 A CN106832937 A CN 106832937A CN 201710008237 A CN201710008237 A CN 201710008237A CN 106832937 A CN106832937 A CN 106832937A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
High pressure resistant composite and method are prepared using technique for atomic layer deposition is carbon nano-tube modified the invention discloses one kind, is mainly comprised the following steps：1) it is acidified CNT with the mix acid liquor of nitric acid with sulfuric acid；2) CNT after acidifying is placed in the ald chamber that temperature is 295~305 degrees Celsius, using trimethyl silicon source and deionized water as the precursor source of ALD deposition film, the carbon nano tube surface deposition of aluminium oxide after acidifying；3) in post-depositional CNT being evenly spread into polymeric matrix using sonic oscillation and magnetic agitation, by sol evenning machine sample preparation and dry, obtain high pressure resistant composite.The polymer matrix composite and straight polymer matrix phase ratio of the doping conducting particles of composite obtained in the inventive method and document report, breakdown strength is significantly increased, there is high-k to prepare, 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 one kind is repaiied using technique for atomic layer deposition
Decorations CNT prepares high pressure resistant composite and method.
【Background technology】
Polymeric material generally has high insulating property, and resist chemical is good, is at present using most wide the features such as easy processing
One of general material.But, although the dielectric breakdown strength of polymer (E very high always>200kV mm-1), but relative dielectric
Constant but very low (κ<5), this constrains the application of polymer significantly.Therefore, the same of polymer other excellent in performance is being ensured
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
Relative dielectric constant, such as lead titanates, lead titanate-zirconate, titanium are improved to the ferroelectric ceramic grain of the high-k that adulterated in polymer
The particles such as sour barium form 0-3 type composites.However, because the dielectric constant of polymer is very low, it is relative in order to significantly improve
Dielectric constant, the content of ceramic particle generally will be more than 50%, after the ceramic particle of doping high content, the elasticity of composite
Significantly reduce, mechanical performance also substantially weakens.Meanwhile, the dielectric breakdown strength of the composite for obtaining is remarkably decreased.It is another
Method is then the composite by being obtained to the conductive filler (such as metallic) that adulterated in polymer, doping conductive filler
Dielectric constant can be obtained by following equation
κm=κ (p-pc)-s (1)
κ in formulamThe relative dielectric constant of composite is represented, κ represents the relative dielectric constant of polymer substrate, and p is represented
The mass fraction of doping, pcRepresent threshold concentration.Can be obtained by formula, when the close infiltration threshold of the mass fraction of conductive filler
Value, the relative dielectric constant of composite has and significantly increases.But, because the conductor non-conductor near percolation threshold turns
Change, the dielectric loss of composite is usually very high, and dielectric breakdown strength is similarly significantly decreased.
【The content of the invention】
It is an object of the invention to solve problems of the prior art, there is provided a kind of to utilize ald skill
Art is carbon nano-tube modified to prepare high pressure resistant composite and method, and one is deposited in carbon nano tube surface using technique for atomic layer deposition
Layer ultra-thin aluminum oxide, then high pressure resistant composite is prepared by the CNT after doping and modification, ensureing dielectric higher
The relative dielectric constant of composite is improved while breakdown strength.
The present invention is achieved through the following technical solutions：
Comprise the following steps：
(1) it is acidified CNT with acid solution；
(2) by technique for atomic layer deposition, the carbon nano tube surface deposited oxide with silicon source and precursor source after acidifying
Aluminium film；
(3) in the CNT of deposited oxide aluminium film being evenly spread into polymeric matrix, CNT-polymerization is obtained
Thing dispersion liquid；Wherein, the carbon nanotube mass of deposited oxide aluminium film accounts for the 0.2~1% of polymer matrix weight；
(4) by carbon nano tube-polymer dispersion liquid is by sol evenning machine sample preparation and dries, high pressure resistant composite is obtained.
Further, acid solution uses the mix acid liquor of sulfuric acid and nitric acid in step (1)；With acid solution acid in step (1)
The concrete operations of carbon nano tube are：
(101) it is 1 according to the volume ratio of nitric acid and sulfuric acid：(3~5) mix acid liquor is configured, wherein, the mass fraction of nitric acid
It is 70%, the mass fraction of sulfuric acid is 98%；To add matching somebody with somebody for 100~300 milligrams of CNTs in every 20 milliliters of mix acid liquors
Than to CNT is added in mix acid liquor, obtaining carbon nano tube suspension；
(102) by carbon nano tube suspension sonic oscillation 20~60 minutes, then it is placed in magnetic force in 50~100 DEG C of water-bath and stirs
Mix 2~5 hours；
(103) carbon nano tube suspension after stirring is diluted and suction filtration with deionized water, until the pH value of filtrate reaches 5
More than；
(104) filter residue and drying that obtains suction filtration is simultaneously collected, the CNT after being acidified.
Further, silicon source is trimethyl aluminium in step (2), and precursor source is deionized water, oxygen or oxygen plasma.
Further, the concrete operations of deposited oxide aluminium film are in step (2)：
(201) CNT after acidifying is placed in 295~305 DEG C of ald chamber；
(202) with nitrogen or inert gas as carrier gas, silicon source, 0.1~0.4 second used time are blown into vapour form, then pass through
Nitrogen or the unnecessary silicon source of inert gas purging discharge, 10~20 seconds used times；Then pulse enters the forerunner that can be reacted with silicon source
Body source steam, 0.1~1 second used time, the carbon nano tube surface after acidifying equably deposits last layer aluminum oxide film；Pass through again
Nitrogen or inert gas purging discharge residue, 3~16 seconds used times, complete a production cycle；
(203) production cycle of repeat step (202), the carbon nano tube surface depositing several layers aluminum oxide film after acidifying
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 films are added in every 15 milliliters of toluene
Nanotube meter, the CNT of deposited oxide aluminium film is scattered in toluene, sonic oscillation 1~2 hour, obtains suspending liquid A；
Based on the polymeric matrix of 4.4g is added in every 10 milliliters of toluene, polymeric matrix is scattered in toluene, magnetic agitation 20~
60 minutes, obtain suspension B；Suspending liquid A is poured into suspension B, magnetic agitation obtains mixed liquor C in 20~60 minutes；Mixing
Liquid C sonic oscillations under the condition of ice bath remove toluene after 2~5 hours, until the concentration of polymeric matrix reaches 0.8g/mL.
Further, polymeric matrix includes polydimethylsiloxane prepolymer thing and supporting crosslinking agent, type in step (3)
Number be Sylgard 184；Wherein, the mass ratio of polydimethylsiloxane prepolymer thing and supporting crosslinking agent is 10:(1~4).
Further, step (4) is by the concrete operations that sol evenning machine prepares test sample and drying：
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 of dryings 10~30 minutes, then be placed in 8~12 hours in 110~130 DEG C of baking oven, obtain
To high pressure resistant composite.
Further, hydrophobic glass substrate is through the following steps that obtained：
By sheet glass acetone, absolute ethyl alcohol and deionized water, ultrasound is cleaned up for 10~30 minutes respectively first, uses nitrogen
Air-blowing is done；It is 1 that the sheet glass after cleaning is placed in into nitric acid and sulfuric acid volume ratio again：Sonic oscillation 20 in the mix acid liquor of (3~5)
~60 minutes, nitrogen was dried up after being cleaned using deionized water；The sheet glass after acid treatment and drying is finally placed in trimethyl chlorine
10~30 minutes in solution of silane, deionized water cleaning is simultaneously dried up with nitrogen, obtains hydrophobic sheet glass.
It is as described above to be obtained using the carbon nano-tube modified method for preparing high pressure resistant composite of technique for atomic layer deposition
High pressure resistant composite, its thickness be 50~300 microns.
Compared with prior art, the present invention has following beneficial technique effect：
Using technique for atomic layer deposition depositing ultrathin alumina come carbon nano-tube modified in the inventive method, in CNT
Surface is doped in polymer substrate again after forming one layer of ultrathin insulating layer, and composite is improved using the CNT after modification
Dielectric properties and lifted or keep material high resistance to breakdown characteristics；The present invention is received using technique for atomic layer deposition (ALD) in carbon
The aluminum oxide of depositing ultrathin on mitron, the thickness of aluminum oxide can accurately be controlled simply by the period of technique for atomic layer deposition
System is in monoatomic layer magnitude.CNT is promoted to be dispersed in polymeric matrix by magnetic agitation and sonic oscillation, it is multiple
The relative dielectric constant of condensation material is significantly improved, while different from the document report of other doping conductive fillers, composite
Dielectric breakdown strength will not only occur obvious reduction compared to polymer, or even in finite concentration, and composite hits
Intensity is worn more than polymeric matrix breakdown strength in itself.The inventive method is simple to operate, and raw material sources are wide, easily realizes, is system
The standby polymer matrix composite with high-k, high breakdown field strength provides new thinking, preceding with good application
Scape and economic benefit.
The present invention not only effectively improves the relative dielectric constant of composite, and can strengthen two for polymer arrives
Four times；Further significantly improve the dielectric breakdown strength of composite, up to 109kV/mm.This causes prepared being combined
Material suffers from huge application value and potentiality in terms of the research such as dielectric elastomer and energy storage material.
【Brief description of the drawings】
Fig. 1 is the energy spectrum diagram of CNT after present invention acidifying.
Fig. 2 be the present invention acidifying and after the deposition of aluminium oxide of surface CNT energy spectrum diagram.
Fig. 3 is the graph of relation of composite relative dielectric constant of the present invention and mass fraction.
Fig. 4 is the graph of relation of composite dielectric breakdown strength of the present invention and mass fraction.
【Specific embodiment】
The present invention comprises the following steps：
(1) it is acidified CNT with the mix acid liquor of nitric acid with sulfuric acid；
According to volume ratio scope it is 1 by the sulfuric acid of the nitric acid of mass fraction 70% and mass fraction 98%:(3~5) match somebody with somebody
Mix acid liquor is put, to add 100~300 milligrams of proportionings of particle to add CNT in every 20 milliliters of nitration mixture, carbon nanometer is obtained
Pipe suspension；The carbon nano tube suspension for obtaining is placed in 50~100 degrees Celsius of water-bath after 20~60 minutes by sonic oscillation
Middle magnetic agitation 2~5 hours；Diluted in the suspension deionized water for obtaining, and suction filtration is carried out using Suction filtration device, until outstanding
The hydrogen ionexponent of supernatant liquid reaches 5 or more (i.e. pH value is more than 5)；Dry and collect, the carbon nanometer after being acidified
Pipe.
(2) CNT after acidifying is placed in 295~305 degrees Celsius of ald chamber, with trimethyl silicon source
With deionized water as precursor source, nitrogen buffer gas, vapor form is blown into trimethyl silicon source, 0.1~0.4 second used time, then
The unnecessary trimethyl silicon source of discharge, 10~20 seconds used times are purged by nitrogen；Then pulse enters can react with trimethyl silicon source
Deionized water precursor source steam, 0.1~1 second used time, uniformly conformally (covered completely in each place in carbon nano tube surface
Lid) deposition last layer aluminum oxide film, one layer of aluminum oxide film film thickness is 0.1 nanometer；Discharge residue is purged by nitrogen again,
3~16 seconds used times, complete a cycle；Aluminum oxide film film thickness is controlled by repeating the above-mentioned production cycle, such as is repeated up to
Carbon nano tube surface deposit thickness after acidifying is 5 nanometers of aluminum oxide film.Precursor source can also use oxygen or oxygen etc.
Gas ions etc., carrier gas can use inert gas such as helium etc..
(3) CNT after deposition of aluminium oxide evenly spreads to polymeric matrix by sonic oscillation and magnetic agitation
In；
CNT after the modification of 8.8~44mg is scattered in 15 milliliters of toluene, sonic oscillation 1~2 hour is obtained
To suspending liquid A；The polymeric matrix of 4.4g is scattered in 10 milliliters of toluene, magnetic agitation 20~60 minutes obtains suspension
B；A is poured slowly into mixed liquor C is obtained in B, in mixed liquor C, the carbon nanotube mass after modification accounts for the 0.2 of polymer quality
~1%；Magnetic agitation is carried out 20~60 minutes to C, then sonic oscillation 2~5 hours under condition of ice bath；It is natural in fume hood
Volatilization removes toluene, until the concentration of polymer reaches 0.8g/mL, carbon nano tube-polymer dispersion liquid is obtained；What is used is poly-
Compound is polydimethylsiloxane, and dimethyl silicone polymer (PDMS) is made up of two parts, and wherein component A is prepolymer,
Component B is crosslinking agent, and component A and component B is 10 in mass ratio:(1~4) can crosslink reaction after mixing and obtain PDMS.
The model of dimethyl silicone polymer (PDMS) is Sylgard 184.
(4) prepare test sample using sol evenning machine and dry：
By sheet glass acetone, absolute ethyl alcohol, ultrasound is cleaned up deionized water for 10~30 minutes respectively, is blown with nitrogen
It is dry；It is 1 that sheet glass after cleaning is placed in nitric acid than sulfuric acid volume:3 to 1:Sonic oscillation 20 in mix acid liquor in 5 proportions
~60 minutes, nitrogen was dried up after being cleaned using deionized water；Sheet glass after acid treatment is placed in 10 in trim,ethylchlorosilane solution
~30 minutes, deionized water cleaning was simultaneously dried up with nitrogen, obtains hydrophobic sheet glass.
By carbon nano tube-polymer dispersant liquid drop on hydrophobic sheet glass, 1000~2000 rpms rotation 10~
20 seconds, 50~100 degrees Celsius of dryings 10~30 minutes, then be placed in 8~12 hours in 110~130 degrees Celsius of baking ovens and dry, obtain
High pressure resistant composite.
Obtained thickness of composite material of the invention is 50~300 microns.
Presently preferred embodiments of the present invention is described in detail below in conjunction with the accompanying drawings, so that advantages and features of the invention energy
It is easier to be readily appreciated by one skilled in the art, apparent is clearly defined so as to be made to protection scope of the present invention.
Embodiment 1：
(1) it is acidified CNT with the mix acid liquor of nitric acid with sulfuric acid；
Volume ratio according to nitric acid and sulfuric acid is 1:4 configuration mix acid liquors, to add 200 milligrams in every 20 milliliters of nitration mixture
The proportioning of particle adds CNT, obtains carbon nano tube suspension；The carbon nano tube suspension for obtaining is by sonic oscillation 30
Magnetic agitation 3 hours in 70 degrees Celsius of water-bath are placed in after minute；Diluted in the suspension deionized water for obtaining, and using taking out
Filter device carries out suction filtration, until the hydrogen ionexponent of suspension reaches 5；Dry and collect, the carbon nanometer after being acidified
Pipe.
(2) CNT after acidifying is placed in 300 DEG C of ald chamber, nitrogen buffer gas, vapor form
Trimethyl silicon source, 0.1 second used time are blown into, then the unnecessary trimethyl silicon source of discharge, 10 seconds used times are purged by nitrogen；Then pulse
Enter the deionized water precursor source steam that can be reacted with trimethyl silicon source, it is 0.1 second used time, uniformly conformal in carbon nano tube surface
Ground deposition last layer aluminum oxide film；Discharge residue is purged by nitrogen again, 3 seconds used times, a cycle is completed；Repeat above-mentioned
Production cycle is until the carbon nano tube surface deposit thickness after acidifying is 5 nanometers of aluminum oxide film.
(3) CNT after deposition of aluminium oxide evenly spreads to polymeric matrix by sonic oscillation and magnetic agitation
In；
CNT after 13.2 milligrams are modified is scattered in 15 milliliters of toluene solution, and sonic oscillation 1 hour is obtained
Suspending liquid A；The dimethyl silicone polymer of 4 grams of component As and 0.4 gram of B component is scattered in 10 milliliters of toluene solutions, mechanical agitation
20 minutes, obtain suspension B；A is poured slowly into mixed liquor C is obtained in B, in mixed liquor C, the carbon nanotube mass after modification
Account for the 0.3% of polymer matrix weight；Magnetic agitation is carried out 20 minutes to C, then sonic oscillation 2 hours under condition of ice bath；
Magnetic agitation removes toluene in ventilating kitchen under normal temperature, until the concentration of polymer reaches 0.8g/mL, prepared CNT-poly-
Compound dispersion liquid；
(4) prepare test sample using sol evenning machine and dry：
By sheet glass acetone, absolute ethyl alcohol, ultrasound is cleaned up deionized water for 10 minutes respectively, is dried up with nitrogen；Clearly
It is 1 that sheet glass after washing is placed in nitric acid than sulfuric acid volume:Sonic oscillation 20 minutes, use in mix acid liquor in 4 proportions
Nitrogen drying after deionized water cleaning；Sheet glass after acid treatment is placed in 10 minutes, deionized water in trim,ethylchlorosilane solution
Clean and dried up 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 dried 10 minutes, then is placed in drying in 8 hours in 110 degrees Celsius of baking ovens, obtains high pressure resistant composite.
Effect of the invention is by following checking：
Method of testing：
The CNT before and after deposition of aluminium oxide is observed using field emission scanning electron microscope (FSEM), and is done
Power spectrum (EDS) elementary analysis, is taken multiple measurements using high-precision digital-display micrometer to sample, determines test compound material sample
Thickness, use broadband dielectric spectroscopy test system measure the dielectric property of sample and puncturing for DC power system test sample
Intensity.
The deposition of aluminum oxide
Fig. 1 and Biao 1 are the power spectrum elementary analysis results of CNT after acidifying, after Fig. 2 and Biao 2 is deposition of aluminium oxide
Power spectrum elementary analysis result.
The power spectrum elementary analysis result of CNT after the acidifying of table 1
| 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 elementary analysis result after the deposition of aluminium oxide of table 2
| 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 |
Result according to power spectrum elementary analysis it can be found that in the EDS results of CNT after deposition of aluminium oxide, observation
The presence of aluminium is arrived, has illustrated that aluminum oxide has had been deposited into carbon nano tube surface really.
The dielectric breakdown strength for measuring the composite is 109kV/mm.
Embodiment 2
Carbon nanotube mass after modification in step (3) is adjusted to account for respectively 0.2%, 0.5% and of polymer quality
0.7%, other conditions are same as Example 1, and the relative dielectric constant to gained composite carries out compliance test result.
Fig. 3 is the relation curve of the relative dielectric constant with mass fraction of composite.Realize that result shows, for ALD
Composite prepared by the CNT 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, twice is increased；When doping concentration is 0.5wt%, dielectric
Constant is 10 in frequency-215 are brought up to by 3.5 at Hz, has been enhanced more than 4 times, relative dielectric constant has been significantly improved, and with mixing
The raising of miscellaneous concentration, relative dielectric constant is further enhanced.
Embodiment 3
The direct doped carbon nanometer pipe in step (3), and doping is respectively 0~1%, other conditions and the phase of embodiment 1
Together, puncturing for gained composite is verified.
Fig. 4 and Biao 3 are respectively the relationship graphs between the dielectric breakdown of composite and doping concentration.
The dielectric breakdown strength of composite obtained in the embodiment 2 of table 3
| Carbon nano tube-doped amount (%) | 0.3 | 0.5 | 0.7 |
| Dielectric breakdown strength (kV/mm, CNT is unmodified) | 37 | 28.5 | 15.8 |
| Dielectric breakdown strength (kV/mm, carbon nano tube modified rear) | 109 | 78 | 80 |
Test result indicate that, the dielectric breakdown strength that direct doped carbon nanometer pipe obtains composite is significantly reduced；And it is right
The composite prepared after doped aluminium is carbon nano-tube modified, test result indicate that, with the raising of doping concentration, dielectric
Breakdown strength was significantly improved before this, even more than polymeric matrix disruptive field intensity in itself, when concentration more than 0.3wt% it
Afterwards, dielectric breakdown starts to be reduced with the raising of concentration, but breakdown strength is remained on 75kV/mm.
Embodiment 4：
(1) it is acidified CNT with the mix acid liquor of nitric acid with sulfuric acid；
Volume ratio according to nitric acid and sulfuric acid is 1:3 configuration mix acid liquors, to add 100 milligrams in every 20 milliliters of nitration mixture
The proportioning of particle adds CNT, obtains carbon nano tube suspension；The carbon nano tube suspension for obtaining is by sonic oscillation 20
Magnetic agitation 2 hours in 50 degrees Celsius of water-bath are placed in after minute；Diluted in the suspension deionized water for obtaining, and using taking out
Filter device carries out suction filtration, until the hydrogen ionexponent of suspension reaches 6；Dry and collect, the carbon nanometer after being acidified
Pipe.
(2) CNT after acidifying is placed in 295 DEG C of ald chamber, nitrogen buffer gas, vapor form
Trimethyl silicon source, 0.2 second used time are blown into, then the unnecessary trimethyl silicon source of discharge, 15 seconds used times are purged by nitrogen；Then pulse
Enter the deionized water precursor source steam that can be reacted with trimethyl silicon source, it is 0.5 second used time, uniformly conformal in carbon nano tube surface
Ground deposition last layer aluminum oxide film；Discharge residue is purged by nitrogen again, 5 seconds used times, a cycle is completed；Repeat above-mentioned
Production cycle is until the carbon nano tube surface deposit thickness after acidifying is 5 nanometers of aluminum oxide film.
(3) CNT after deposition of aluminium oxide evenly spreads to polymeric matrix by sonic oscillation and magnetic agitation
In；
CNT after 22 milligrams are modified is scattered in 15 milliliters of toluene solution, and sonic oscillation 1.5 hours is obtained
Suspending liquid A；4.4 grams of dimethyl silicone polymer is scattered in 10 milliliters of toluene solutions, mechanical agitation 30 minutes is suspended
Liquid B, component A and the mass ratio of B component are 10 in dimethyl silicone polymer:2；A is poured slowly into mixed liquor C is obtained in B, mixed
Close in liquid C, the carbon nanotube mass after modification accounts for the 0.5% of polymer matrix weight；Magnetic agitation is carried out 30 minutes to C, with
Sonic oscillation 3 hours under condition of ice bath afterwards；Magnetic agitation removes toluene in ventilating kitchen under normal temperature, until the concentration of polymer
0.8g/mL is reached, carbon nano tube-polymer dispersion liquid is obtained；
(4) prepare test sample using sol evenning machine and dry：
By sheet glass acetone, absolute ethyl alcohol, ultrasound is cleaned up deionized water for 15 minutes respectively, is dried up with nitrogen；Clearly
It is 1 that sheet glass after washing is placed in nitric acid than sulfuric acid volume:Sonic oscillation 30 minutes, clear using deionized water in 3 mix acid liquor
Wash rear nitrogen drying；Sheet glass after acid treatment is placed in 15 minutes in trim,ethylchlorosilane solution, and deionized water is cleaned and uses nitrogen
Air-blowing is done, and 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 dried 15 minutes, then is placed in drying in 12 hours in 120 degrees Celsius of baking ovens, obtains high pressure resistant composite.
Embodiment 5：
(1) it is acidified CNT with the mix acid liquor of nitric acid with sulfuric acid；
Volume ratio according to nitric acid and sulfuric acid is 1:4 configuration mix acid liquors, to add 200 milligrams in every 20 milliliters of nitration mixture
The proportioning of particle adds CNT, obtains carbon nano tube suspension；The carbon nano tube suspension for obtaining is by sonic oscillation 60
Magnetic agitation 5 hours in 100 degrees Celsius of water-bath are placed in after minute；Diluted in the suspension deionized water for obtaining, and used
Suction filtration device carries out suction filtration, until the hydrogen ionexponent of suspension reaches 6.5；Dry and collect, the carbon after being acidified
Nanotube.
(2) CNT after acidifying is placed in 305 DEG C of ald chamber, nitrogen buffer gas, vapor form
Trimethyl silicon source, 0.4 second used time are blown into, then the unnecessary trimethyl silicon source of discharge, 20 seconds used times are purged by nitrogen；Then pulse
Enter the deionized water precursor source steam that can be reacted with trimethyl silicon source, it is 0.8 second used time, uniformly conformal in carbon nano tube surface
Ground deposition last layer aluminum oxide film；Discharge residue is purged by nitrogen again, 10 seconds used times, a cycle is completed；In repetition
The production cycle is stated until the carbon nano tube surface deposit thickness after acidifying is 5 nanometers of aluminum oxide film.
(3) CNT after deposition of aluminium oxide evenly spreads to polymeric matrix by sonic oscillation and magnetic agitation
In；
CNT after 22 milligrams are modified is scattered in 15 milliliters of toluene solution, and sonic oscillation 2 hours is hanged
Supernatant liquid A；4.4 grams of dimethyl silicone polymer is scattered in 10 milliliters of toluene solutions, mechanical agitation 40 minutes obtains suspension
B, component A and the mass ratio of B component are 10 in dimethyl silicone polymer:3；A is poured slowly into mixed liquor C is obtained in B, in mixing
In liquid C, the carbon nanotube mass after modification accounts for the 0.5% of polymer matrix weight；Magnetic agitation is carried out 40 minutes to C, then
Sonic oscillation 4 hours under condition of ice bath；Magnetic agitation removes toluene in ventilating kitchen under normal temperature, until the concentration of polymer reaches
To 0.8g/mL, carbon nano tube-polymer dispersion liquid is obtained；
(4) prepare test sample using sol evenning machine and dry：
By sheet glass acetone, absolute ethyl alcohol, ultrasound is cleaned up deionized water for 20 minutes respectively, is dried up with nitrogen；Clearly
It is 1 that sheet glass after washing is placed in nitric acid than sulfuric acid volume:Sonic oscillation 40 minutes, clear using deionized water in 5 mix acid liquor
Wash rear nitrogen drying；Sheet glass after acid treatment is placed in 20 minutes in trim,ethylchlorosilane solution, and deionized water is cleaned and uses nitrogen
Air-blowing is done, and 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 dried 20 minutes, then is placed in drying in 10 hours in 130 degrees Celsius of baking ovens, obtains high pressure resistant composite.
Embodiment 6：
(1) it is acidified CNT with the mix acid liquor of nitric acid with sulfuric acid；
Volume ratio according to nitric acid and sulfuric acid is 1:5 configuration mix acid liquors, to add 300 milligrams in every 20 milliliters of nitration mixture
The proportioning of particle adds CNT, obtains carbon nano tube suspension；The carbon nano tube suspension for obtaining is by sonic oscillation 40
Magnetic agitation 4 hours in 60 degrees Celsius of water-bath are placed in after minute；Diluted in the suspension deionized water for obtaining, and using taking out
Filter device carries out suction filtration, until the hydrogen ionexponent of suspension reaches 6.8；Dry and collect, the carbon after being acidified is received
Mitron.
(2) CNT after acidifying is placed in 298 DEG C of ald chamber, with helium as carrier gas, vapor form
Trimethyl silicon source, 0.3 second used time are blown into, then the unnecessary trimethyl silicon source of discharge, 18 seconds used times are purged by helium；Then pulse
Enter the oxygen plasma precursor source steam that can be reacted with trimethyl silicon source, it is 1 second used time, uniformly conformal in carbon nano tube surface
Ground deposition last layer aluminum oxide film；Discharge residue is purged by helium again, 16 seconds used times, a cycle is completed；In repetition
The production cycle is stated until the carbon nano tube surface deposit thickness after acidifying is 5 nanometers of aluminum oxide film.
(3) CNT after deposition of aluminium oxide evenly spreads to polymeric matrix by sonic oscillation and magnetic agitation
In；
CNT after 22 milligrams are modified is scattered in 15 milliliters of toluene solution, and sonic oscillation 1.2 hours is obtained
Suspending liquid A；4.4 grams of dimethyl silicone polymer is scattered in 10 milliliters of toluene solutions, mechanical agitation 60 minutes is suspended
Liquid B, component A and the mass ratio of B component are 10 in dimethyl silicone polymer:4；A is poured slowly into mixed liquor C is obtained in B, mixed
Close in liquid C, the carbon nanotube mass after modification accounts for the 0.5% of polymer matrix weight；Magnetic agitation is carried out 60 minutes to C, with
Sonic oscillation 5 hours under condition of ice bath afterwards；Magnetic agitation removes toluene in ventilating kitchen under normal temperature, until the concentration of polymer
0.8g/mL is reached, carbon nano tube-polymer dispersion liquid is obtained；
(4) prepare test sample using sol evenning machine and dry：
By sheet glass acetone, absolute ethyl alcohol, ultrasound is cleaned up deionized water for 30 minutes respectively, is dried up with nitrogen；Clearly
It is 1 that sheet glass after washing is placed in nitric acid than sulfuric acid volume:Sonic oscillation 60 minutes, clear using deionized water in 4 mix acid liquor
Wash rear nitrogen drying；Sheet glass after acid treatment is placed in 30 minutes in trim,ethylchlorosilane solution, and deionized water is cleaned and uses nitrogen
Air-blowing is done, and 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 dried 30 minutes, then is placed in drying in 9 hours in 115 degrees Celsius of baking ovens, obtains high pressure resistant composite.
In sum, the inventive method using technique for atomic layer deposition depositing ultrathin alumina layer come carbon nano-tube modified,
And the filler by doping content less than 1wt% is come modified dimethyl polysiloxane, doping process mainly using sonic oscillation with
Magnetic agitation promotes the CNT dispersion in the polymer matrix after modification, then prepares test specimens by sol evenning machine
Product.The method have the advantages that while so that the dielectric constant of composite improves, the dielectric of composite
Breakdown strength will not only occur obvious reduction compared to polymer, or even in finite concentration, the breakdown field of composite
Exceed polymeric matrix intensity in itself by force, whole preparation process is simple and easy to apply.
The polymer matrix composite of the doping conducting particles of composite obtained in the inventive method and document report with
And straight polymer matrix phase ratio, breakdown strength is significantly increased, to prepare with high-k, the polymer of high breakdown field strength
Based composites provide new thinking, have a good application prospect and economic benefit.
Embodiments of the invention are the foregoing is only, the scope of the claims of the invention is not thereby limited, it is every to utilize this hair
Equivalent structure or equivalent flow conversion that bright specification and accompanying drawing content are made, or directly or indirectly it is used in other related skills
Art field, is included within the scope of the present invention.
Claims (10)
1. a kind of carbon nano-tube modified method for preparing high pressure resistant composite of utilization technique for atomic layer deposition, it is characterised in that
Comprise the following steps：
(1) it is acidified CNT with acid solution；
(2) by technique for atomic layer deposition, the carbon nano tube surface deposition of aluminium oxide with silicon source and precursor source after acidifying is thin
Film；
(3) in the CNT of deposited oxide aluminium film being evenly spread into polymeric matrix, carbon nano tube-polymer point is obtained
Dispersion liquid；Wherein, the carbon nanotube mass of deposited oxide aluminium film accounts for the 0.2~1% of polymer matrix weight；
(4) by carbon nano tube-polymer dispersion liquid is by sol evenning machine sample preparation and dries, high pressure resistant composite is obtained.
2. one kind according to claim 1 prepares high pressure resistant composite using technique for atomic layer deposition is carbon nano-tube modified
Method, it is characterised in that acid solution uses the mix acid liquor of sulfuric acid and nitric acid in step (1)；With acid solution acid in step (1)
The concrete operations of carbon nano tube are：
(101) it is 1 according to the volume ratio of nitric acid and sulfuric acid：(3~5) mix acid liquor is configured, wherein, the mass fraction of nitric acid is
70%, the mass fraction of sulfuric acid is 98%；To add 100~300 milligrams of proportionings of CNT in every 20 milliliters of mix acid liquors,
To CNT is added in mix acid liquor, carbon nano tube suspension is obtained；
(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) by the carbon nano tube suspension after stirring with deionized water dilute and suction filtration, until the pH value of filtrate reach 5 with
On；
(104) filter residue and drying that obtains suction filtration is simultaneously collected, the CNT after being acidified.
3. one kind according to claim 1 prepares high pressure resistant composite using technique for atomic layer deposition is carbon nano-tube modified
Method, it is characterised in that in step (2) silicon source be trimethyl aluminium, precursor source be deionized water, oxygen or oxygen plasma
Body.
4. one kind according to claim 1 prepares high pressure resistant composite using technique for atomic layer deposition is carbon nano-tube modified
Method, it is characterised in that the concrete operations of deposited oxide aluminium film are in step (2)：
(201) CNT after acidifying is placed in 295~305 DEG C of ald chamber；
(202) with nitrogen or inert gas as carrier gas, it is blown into silicon source in vapour form, 0.1~0.4 second used time, then by nitrogen
Or the unnecessary silicon source of inert gas purging discharge, 10~20 seconds used times；Then pulse enters the precursor source that can be reacted with silicon source
Steam, 0.1~1 second used time, the carbon nano tube surface after acidifying equably deposits last layer aluminum oxide film；Pass through nitrogen again
Or inert gas purging discharge residue, 3~16 seconds used times, complete a production cycle；
(203) production cycle of repeat step (202), the carbon nano tube surface depositing several layers aluminum oxide film after acidifying.
5. one kind according to claim 4 prepares high pressure resistant composite using technique for atomic layer deposition is carbon nano-tube modified
Method, it is characterised in that every layer of the aluminum oxide film film thickness of deposition is 0.1 nanometer.
6. one kind according to claim 1 prepares high pressure resistant composite using technique for atomic layer deposition is carbon nano-tube modified
Method, it is characterised in that in step (3), by every 15 milliliters of toluene add 8.8~44mg deposited oxide aluminium films carbon
Nanotube meter, the CNT of deposited oxide aluminium film is scattered in toluene, sonic oscillation 1~2 hour, obtains suspending liquid A；
Based on the polymeric matrix of 4.4g is added in every 10 milliliters of toluene, polymeric matrix is scattered in toluene, magnetic agitation 20~
60 minutes, obtain suspension B；Suspending liquid A is poured into suspension B, magnetic agitation obtains mixed liquor C in 20~60 minutes；Mixing
Liquid C sonic oscillations under the condition of ice bath remove toluene after 2~5 hours, until the concentration of polymeric matrix reaches 0.8g/mL.
7. one kind according to claim 1 prepares high pressure resistant composite using technique for atomic layer deposition is carbon nano-tube modified
Method, it is characterised in that in step (3) polymeric matrix include polydimethylsiloxane prepolymer thing and supporting crosslinking agent,
Model Sylgard 184；Wherein, the mass ratio of polydimethylsiloxane prepolymer thing and supporting crosslinking agent is 10:(1~4).
8. one kind according to claim 1 prepares high pressure resistant composite using technique for atomic layer deposition is carbon nano-tube modified
Method, it is characterised in that step (4) by sol evenning machine prepare test sample and drying concrete operations be：
By carbon nano tube-polymer dispersant liquid drop in hydrophobic glass substrate, under 1000~2000 rpms of rotating speed
Rotation 10~20 seconds, 50~100 DEG C of dryings 10~30 minutes, then be placed in 8~12 hours in 110~130 DEG C of baking oven, obtain resistance to
High-pressure composite material.
9. one kind according to claim 8 prepares high pressure resistant composite using technique for atomic layer deposition is carbon nano-tube modified
Method, it is characterised in that hydrophobic glass substrate is through the following steps that obtained：
By sheet glass acetone, absolute ethyl alcohol and deionized water, ultrasound is cleaned up for 10~30 minutes respectively first, is blown with nitrogen
It is dry；It is 1 that the sheet glass after cleaning is placed in into nitric acid and sulfuric acid volume ratio again：Sonic oscillation 20~60 in the mix acid liquor of (3~5)
Minute, nitrogen is dried up after being cleaned using deionized water；The sheet glass after acid treatment and drying is finally placed in trim,ethylchlorosilane
10~30 minutes in solution, deionized water cleaning is simultaneously dried up with nitrogen, obtains hydrophobic sheet glass.
10. as claimed in claim 1 using the carbon nano-tube modified side for preparing high pressure resistant composite of technique for atomic layer deposition
High pressure resistant composite obtained in method, it is characterised in that the thickness of obtained high pressure resistant composite is 50~300 microns.
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| CN112920531A (en) * | 2021-02-18 | 2021-06-08 | 西安交通大学 | High energy storage density polymer and method for preparing same based on field arrangement |
| CN114361412A (en) * | 2021-12-16 | 2022-04-15 | 江苏大学 | Multi-walled carbon nanotube negative electrode material and preparation method and application thereof |
| CN114414107A (en) * | 2022-01-26 | 2022-04-29 | 西安交通大学 | High-strength carbon fiber composite material with self-sensing function and preparation method thereof |
| CN117457806A (en) * | 2023-12-26 | 2024-01-26 | 无锡松煜科技有限公司 | Preparation method for passivation layer on surface of crystalline silicon battery with nano-pillar structure |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112920531A (en) * | 2021-02-18 | 2021-06-08 | 西安交通大学 | High energy storage density polymer and method for preparing same based on field arrangement |
| CN114361412A (en) * | 2021-12-16 | 2022-04-15 | 江苏大学 | Multi-walled carbon nanotube negative electrode material and preparation method and application thereof |
| CN114414107A (en) * | 2022-01-26 | 2022-04-29 | 西安交通大学 | High-strength carbon fiber composite material with self-sensing function and preparation method thereof |
| CN114414107B (en) * | 2022-01-26 | 2022-11-01 | 西安交通大学 | High-strength carbon fiber composite material with self-sensing function and preparation method thereof |
| CN117457806A (en) * | 2023-12-26 | 2024-01-26 | 无锡松煜科技有限公司 | Preparation method for passivation layer on surface of crystalline silicon battery with nano-pillar structure |
| CN117457806B (en) * | 2023-12-26 | 2024-03-19 | 无锡松煜科技有限公司 | Preparation method for passivation layer on surface of crystalline silicon battery with nano-pillar structure |
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