CN105271175B - A kind of process for dispersing of CNT - Google Patents
A kind of process for dispersing of CNT Download PDFInfo
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- CN105271175B CN105271175B CN201510785620.5A CN201510785620A CN105271175B CN 105271175 B CN105271175 B CN 105271175B CN 201510785620 A CN201510785620 A CN 201510785620A CN 105271175 B CN105271175 B CN 105271175B
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Abstract
The invention discloses a kind of process for dispersing of CNT, comprise the steps of：CNT is put into aqueous slkali and is heated to after 200 DEG C~500 DEG C, backflow 0.5h~3.0h, room temperature is cooled to, filters, is washed to pH value to 7.0~8.0, obtain CNT mixed liquor；The mixed liquor is added in nitration mixture, 200 DEG C~500 DEG C are heated to, flow back 0.2h~1h, is cooled to room temperature, filters, is washed to pH value to 6.8~7.5, obtain pure carbon nano tube liquid；By the carbon nano tube liquid and dispersant, after 0.2~7h of ultrasonic disperse, finely dispersed carbon nano tube dispersion liquid is obtained.The carbon nano tube dispersion method of the present invention is carried out in pure liquid phase, without high-temperature calcination oxidation, the structure of CNT will not be destroyed, while processing time is short, so that severe oxidation will not occur in nitration mixture processing procedure for CNT, so as to ensure that CNT output capacity is of a relatively high.
Description
Technical field
The present invention relates to carbon nano-tube material field, more particularly to a kind of process for dispersing of CNT.
Background technology
CNT has excellent Physical and mechanical properties, is the preferable enhancing phase for preparing composite.But, due to
There is very strong Van der Waals force between CNT, make it easier to tangle reunion, be difficult to disperse, seriously limiting it strengthens performance
Performance.Current existing process for dispersing has：Ball milling, ultrasonic vibration, addition dispersant etc..Yu Zuolong etc. passes through grinding and stirring
Method block dispersing Nano carbon tubes；By multi-walled carbon nanotube, the ultrasound in strong acid obtains scattered opening carbon nanometer to Tsang etc.
Pipe；Perhaps Longshan, Chen Chuansheng etc. passes through acid cleaning process and obtains scattered CNT；Xiao Qi etc. uses cetyl trimethyl bromination
Ammonium is that dispersant obtains scattered CNT；Ten thousand vast grades have carried out ball milling using low speed ball mill to CNT, carbon is received
Mitron shorten it is scattered, its transmission electron microscope test result indicates that：Low speed ball milling can make CNT opening shorten, carbon after ball milling 5h
Nanometer tube opening is shortened, and effect is readily apparent that；After ball milling 20h, CNT shortens, and occurs and has obvious agglomeration.
The scattered of CNT is carried out using single method, often stability is poor for gained dispersion liquid, it is impossible to long-term to preserve, and for reuniting
CNT does not have peptizaiton, makes aggregate more closely knit on the contrary.CNT can reunite gained dispersion liquid again after the drying,
So that carbon nanotube powder does not have use value after scattered, defect can be caused on the contrary after adding in material, is had a strong impact on compound
Material property.Chinese patent CN102805103A discloses a kind of method of dispersing Nano carbon tubes：First with alkali process CNT,
Again high-temperature calcination then again nitration mixture processing, finally disperse together with dispersant.Easypro " air oxidation just and is once imitated with reference to Sun Xiao
The paper of the research of method purification CNT " is understood, to the CNT without oxygenation pretreatment, more than 500 DEG C, calcines 1h's
Under heating condition, the burn out rate of CNT can reach 40%, i.e., while oxidation of impurities carbon nano tube surface and end cap at
Also occur to aoxidize and scaling loss；For the CNT after alkali process, its reactivity is bigger, and scaling loss can be more serious, and for
Oxidization burning loss unusual serious CNT, then carry out that nitration mixture is ultrasonically treated, then it can be further exacerbated by the oxygen of CNT
Change, so that CNT output capacity is relatively low.
The content of the invention
The technical problem to be solved in the present invention be overcome the deficiencies in the prior art there is provided a kind of preparation technology flow it is simple,
CNT output capacity is of a relatively high, the CNT of good dispersion and stability is respectively provided with dispersion liquid and drying condition
Process for dispersing.
In order to solve the above technical problems, technical scheme proposed by the present invention is：
A kind of process for dispersing of CNT, is comprised the steps of：
1) CNT is put into aqueous slkali and be heated to after 200 DEG C~500 DEG C, backflow 0.5h~3.0h, be cooled to room
Temperature, filters, is washed to pH value to 7.0~8.0, obtain CNT mixed liquor, wherein the matter of the CNT and aqueous slkali
Amount is than being 1:20~40；
2) by step 1) after obtained CNT mixed liquor be added in nitration mixture, be heated to 200 DEG C~500 DEG C, backflow
0.2h~1h, is cooled to room temperature, filters, is washed to pH value to 6.8~7.5, obtains pure carbon nano tube liquid, wherein carbon is received
The volume ratio of mitron mixed liquor and nitration mixture is 1:25~40；
3) by step 2) after obtain after pure carbon nano tube liquid and dispersant, 0.2~7h of ultrasonic disperse, obtain
Finely dispersed carbon nano tube dispersion liquid, wherein pure carbon nano tube liquid and the volume ratio of dispersant are 1:10~20.
Above-mentioned carbon nano tube dispersion method, it is preferred that the step 3) in, dispersant is APES
The mixed liquor of (hereinafter referred to as OP emulsifying agents) and neopelex, or be lauryl sodium sulfate and detergent alkylate
The mixed liquor of sodium sulfonate.Using mixed dispersant than single dispersant effect more preferably, it is more stable；For detergent alkylate sulphur
Sour sodium and lauryl sodium sulfate, two kinds are all anionic surfactant, have synergy in water, are arranged by electrostatic
Reprimand and steric hindrance effect prevent CNT from reuniting；For neopelex and OP emulsifying agents, wherein dodecyl
Benzene sulfonic acid sodium salt is anionic surfactant, and OP emulsifying agents are nonionic surface active agent, and both meetings form mixed micelle
Absorption, by mutually exclusive between each micella of electrostatic effect, hinders CNT reunion, and OP emulsifying agents in carbon nano tube surface
For jelly, carbon nano tube surface can be wrapped in after the drying so that CNT still keeps good dispersion after the drying.
Above-mentioned carbon nano tube dispersion method, it is preferred that the APES and neopelex
Mixed liquor in, APES mass concentration be 1%~12%, neopelex concentration be 0.1g/L~
2.5g/L。
Above-mentioned carbon nano tube dispersion method, it is preferred that the lauryl sodium sulfate and neopelex
In mixed liquor, lauryl sodium sulfate concentration be 0.1g/L~3.5g/L, neopelex concentration be 0.1g/L~
3.5g/L。
Above-mentioned carbon nano tube dispersion method, it is preferred that the step 1) in, aqueous slkali is NaOH or KOH solution, and its is dense
Spend for 1.0mol/L~4mol/L.First it is heated to reflux using NaOH or KOH solution pre-processing CNT in the present invention,
So that the impurity pre-separation such as CNT in raw material and carbon particle, is separated into smaller particle by CNT, increases carbon and receive
The specific surface area of mitron, chemical reactivity increase.
Above-mentioned carbon nano tube dispersion method, it is preferred that the step 2) in, nitration mixture is the mixing of concentrated nitric acid and the concentrated sulfuric acid
The volume ratio of solution, wherein concentrated nitric acid and the concentrated sulfuric acid is 1：3~3：1.Bar is being heated to reflux using the nitration mixture with strong oxidizing property
Reacted under part with CNT, it is CO further to make the oxidations of impurities such as carbon particle therein2Gas, and CNT is due to be steady
Fixed six-membered ring structure, structure is not destroyed by nitration mixture substantially, realizes the purge process of CNT, and nitration mixture processing can make carbon
Nanotube surface produces hydroxyl and carboxyl, increases carbon nanotube hydrophilicity, is allowed to be more easy to scatter in aqueous dispersant.
Above-mentioned carbon nano tube dispersion method, it is preferred that the step 3) in, ultrasonic oscillation work(during ultrasonic disperse
Rate density is 0.35w/cm2~0.70w/cm2.Ultrasonic oscillation is used while using mixed type dispersant, energy can be passed through
Impact and localized hyperthermia help dispersant to open CNT aggregate, so that disperse evenly, it is stable.
Above-mentioned carbon nano tube dispersion method, it is preferred that the step 1), 2) and 3) in, filtering uses vacuum filter.
Compared with prior art, the advantage of the invention is that：
1) directly in high temperature nitration mixture bar after carbon nano tube dispersion method of the invention, the oxygenation pretreatment that CNT is used
Handled under part, due to being aoxidized without high-temperature calcination, the rock-steady structure of CNT will not be destroyed, while processing time is short,
Ensure that CNT will not occur severe oxidation in nitration mixture processing procedure and lose, the CNT finally obtained
Output capacity is of a relatively high.
2) carbon nano tube dispersion method of the invention, is first heated to reflux pre-processing CNT using aqueous slkali,
So that the impurity pre-separation such as CNT in raw material and carbon particle, is separated into smaller particle by CNT, increases carbon and receive
The specific surface area of mitron, chemical reactivity increase.Then using with strong oxidizing property nitration mixture under heated reflux condition with
CNT reacts, and it is CO further to make the oxidations of impurities such as carbon particle therein2Gas, and CNT is due to six for stabilization
Ring structure, structure is not destroyed by nitration mixture substantially, realizes the purge process of CNT, and nitration mixture processing can make CNT
Surface produces hydroxyl and carboxyl, increases carbon nanotube hydrophilicity, is allowed to be more easy to scatter in aqueous dispersant.
3) carbon nano tube dispersion method of the invention, the mixed dispersant of use is more preferable than single dispersant effect,
More stable, its reason is that the moon/nonionic surfactant compound system can produce a large amount of mixed micelle absorption in CNT
Surface, by mutually exclusive between each micella of electrostatic effect, hinders CNT reunion, and the moon/anion surfactant is multiple
It can be acted synergistically with two kinds of activating agents in system, play electrostatic effect and realize peptizaiton.
4) carbon nano tube dispersion method of the invention, using ultrasound while the mixed dispersant using a certain amount of proportioning
Ripple shakes, and by energy impact and localized hyperthermia dispersant can be helped to open CNT aggregate, so that disperse evenly,
It is stable.
5) dispersion liquid that carbon nano tube dispersion method of the invention is obtained has good dispersion and stability, can keep one
More than year.In addition, gained carbon nanotube powder still has preferably dispersiveness after the dispersion liquid of the present invention is dried, will not occur again
The phenomenons such as reunion, and the convenient transport of easily scattered CNT is made, reservoir volume is reduced.
6) carbon nano tube dispersion method of the invention, its scattered flow is simple, it is easy to operate, required raw material is cheap and easy to get,
The whole process deadline is no more than 12 hours, and industrialized production can be achieved.
7) carbon nano tube dispersion method of the invention is carried out in full liquid phase process, it is not necessary to by repeatedly dry and high
Temperature calcining so that the CNT output capacity of acquisition is of a relatively high, while saving energy consumption again.
8) carbon nano tube dispersion method of the invention realizes uniform mixing using high temperature reflux mode, simplifies operation step
Suddenly.
Brief description of the drawings
Fig. 1 is the process chart of the carbon nano tube dispersion method of the embodiment of the present invention 2.
Fig. 2 is the scanning electron microscope diagram of CNT of the embodiment of the present invention 1 after alkali and nitration mixture processing.
Fig. 3 is the SEM after carbon nano tube dispersion liquid prepared by the embodiment of the present invention 1 is stood 2 months
Figure.
Fig. 4 is the photo after carbon nano tube dispersion liquid prepared by the embodiment of the present invention 1 is stood 1 year.
Fig. 5 is the scanning electron microscope diagram of carbon nanotube powder prepared by the embodiment of the present invention 2.
Fig. 6 is the photo after carbon nano tube dispersion liquid prepared by the embodiment of the present invention 2 is stood 1 year.
Embodiment
For the ease of understanding the present invention, more complete is made to the present invention below in conjunction with Figure of description and preferred embodiment
Face, meticulously describe, but protection scope of the present invention is not limited to embodiment in detail below.
Unless otherwise defined, the implication that all technical terms used hereinafter are generally understood that with those skilled in the art
It is identical.Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to the limitation present invention
Protection domain.
Except there is a special instruction, the various reagents used in the present invention, raw material be can be commercially commodity or
Person can pass through product made from known method.
Embodiment 1：
A kind of process for dispersing of CNT of the invention, comprises the following steps：
1) take 2 grams of CNTs to be put into soda boiling pot, then add the NaOH solution that 40 milliliters of concentration are 2mol/L, install
Reflux condensate device.Then begin heat to after 200 DEG C of backflow 3h, be cooled to room temperature.Then by the mixture vacuum mistake of gained
Filter, obtains the fine-powder of black, and the black powder of gained is washed with deionized until the pH value and deionized water of washings
PH value equal (pH=7) when, obtain 10 milliliters of CNT mixed liquors.
2) by step 1) after obtained CNT mixed liquor be added in acid boiling pan, sequentially add 62.5 milliliters of concentrated nitric acids
With 187.5 milliliters of concentrated sulfuric acids, reflux condensation mode and device for absorbing tail gas are installed.Then begin heat to after 200 DEG C, backflow 0.5h,
It is cooled to room temperature.Then vacuum filter falls acid unnecessary in mixture, and the powdered substance of gained is washed with deionized directly
To pH value=7 of washings, 10 milliliters of pure carbon nano tube liquids are obtained.
3) weigh 3.5g neopelexes solid and measure 40 milliliters of OP emulsion liquids, with 60 milliliters of deionizations
Water is made into mixed dispersion liquid, then add step 2) after obtain pure carbon nano tube liquid, using ultrasonic oscillation (ultrasonic wave
Power density is 0.40w/cm2), 1h is shaken, that is, obtains finely dispersed carbon nano tube dispersion liquid.
Fig. 2 is step 2) obtained pure CNT scanning electron microscope image, after handling as can be seen from Figure 2 in raw material
Only remain pure CNT and without other impurities particle, purification process works well.Fig. 3 is dispersion liquid manufactured in the present embodiment
Stand 2 months after with dropper drop take sample put on smooth copper sample stage dry after gained surface sweeping sem image.Disperse as seen from Figure 3
Work well, its reason is that both neopelex and OP emulsifying agents can form mixed micelle, and absorption is in carbon nanometer
Pipe surface, by mutually exclusive between each micella of electrostatic effect, hinders CNT reunion, and OP emulsifying agents are jelly,
Carbon nano tube surface can be wrapped in after drying so that CNT still keeps good dispersion after the drying.
The photo after carbon nano tube dispersion liquid manufactured in the present embodiment is placed 1 year is illustrated in figure 4, is found out from photo,
Dispersion liquid still stable homogeneous, precipitation is not produced still after placing 1 year.
Embodiment 2：
A kind of process for dispersing of CNT of the invention, technological process is as shown in figure 1, comprise the following steps：
1) take 2g CNT to be put into soda boiling pot, then add the NaOH solution that 80 milliliters of concentration are 2mol/L, dress
Good reflux condensate device.Then begin heat to after 500 DEG C of backflow 3h, be cooled to room temperature.Then by the mixture vacuum of gained
Filtering, obtains the fine-powder of black, and the black powder of gained is washed with deionized until the pH value and deionization of washings
During pH value equal (pH=7) of water, 10 milliliters of CNT mixed liquors are obtained.
2) by step 1) after obtained CNT mixed liquor be added in acid boiling pan, sequentially add 300 milliliters of concentrated nitric acids
With 100 milliliters of concentrated sulfuric acids, reflux condensation mode and device for absorbing tail gas are installed.Then begin heat to after 500 DEG C, backflow 0.5h, it is cold
But to room temperature.Then vacuum filter falls acid unnecessary in mixture, the powdered substance of gained is washed with deionized until
PH value=7 of washings, obtain 10 milliliters of pure carbon nano tube liquids.
3) 15g neopelexes and 15g lauryl sodium sulfate are weighed, is made into 200 ml deionized waters mixed
Close dispersion liquid, then add step 2) after obtain pure carbon nano tube liquid, using ultrasonic oscillation (ultrasonic power density
For 0.40w/cm2), 1h is shaken, that is, obtains finely dispersed carbon nano tube dispersion liquid.
4) by finely dispersed carbon nano tube dispersion liquid vacuum filter, then by the CNT obtained by filtering in 60 DEG C of temperature
Degree is lower to dry, the carbon nanotube powder easily disperseed.
Fig. 5 is that easily scattered carbon nanotube powder scanning electron obtained by smooth copper sample stage that the present embodiment is obtained shows
Micro mirror picture, from figure 5 it can be seen that CNT is single state, dispersion effect is good.
Fig. 6 show the photo after carbon nano tube dispersion liquid manufactured in the present embodiment is placed 1 year, as seen from the figure, dispersion liquid
Still stable homogeneous, no to precipitate generation.
Claims (6)
1. a kind of process for dispersing of CNT, it is characterised in that comprise the steps of：
1) CNT is put into aqueous slkali and be heated to after 200 DEG C~500 DEG C, backflow 0.5h~3.0h, be cooled to room temperature, mistake
Filter, be washed to pH value to 7.0~8.0, obtain CNT mixed liquor, wherein the mass ratio of the CNT and aqueous slkali is
1:20~40；
2) by step 1) after obtained CNT mixed liquor be added in nitration mixture, be heated to 200 DEG C~500 DEG C, flow back 0.2h
~1h, is cooled to room temperature, filters, is washed to pH value to 6.8~7.5, obtains pure carbon nano tube liquid, wherein CNT
The volume ratio of mixed liquor and nitration mixture is 1:25~40；
3) by step 2) after obtain after pure carbon nano tube liquid and dispersant, 0.2~7h of ultrasonic disperse, disperseed
Uniform carbon nano tube dispersion liquid, wherein pure CNT and the volume ratio of dispersant are 1:10~20；Dispersant is alkane
The mixed liquor of base phenol polyethenoxy ether and neopelex, or be lauryl sodium sulfate and DBSA
The mixed liquor of sodium；Ultrasonic oscillation power density is 0.35w/cm during ultrasonic disperse2~0.70w/cm2。
2. carbon nano tube dispersion method as claimed in claim 1, it is characterised in that the APES and 12
In the mixed liquor of sodium alkyl benzene sulfonate, APES mass concentration is 1%~12%, and neopelex is dense
Spend for 0.1g/L~2.5g/L.
3. carbon nano tube dispersion method as claimed in claim 1, it is characterised in that the lauryl sodium sulfate and dodecane
In the mixed liquor of base benzene sulfonic acid sodium salt, lauryl sodium sulfate concentration is 0.1g/L~3.5g/L, neopelex concentration
For 0.1g/L~3.5g/L.
4. the carbon nano tube dispersion method as described in any one of claims 1 to 3, it is characterised in that the step 1) in, alkali soluble
Liquid is NaOH or KOH solution, and its concentration is 1.0mol/L~4mol/L.
5. the carbon nano tube dispersion method as described in any one of claims 1 to 3, it is characterised in that the step 2) in, nitration mixture
For concentrated nitric acid and the mixed solution of the concentrated sulfuric acid, the wherein volume ratio of concentrated nitric acid and the concentrated sulfuric acid is 1：3~3：1.
6. the carbon nano tube dispersion method as described in any one of claims 1 to 3, it is characterised in that the step 1), 2) and 3)
In, filtering uses vacuum filter.
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| CN106128543B (en) * | 2016-07-18 | 2021-02-02 | 贵州大学 | Conductive silver paste with good anti-settling effect and preparation method thereof |
| CN107217287B (en) * | 2017-02-10 | 2021-02-19 | 江苏城乡建设职业学院 | Method for regulating and controlling diameter of titanium dioxide nanometer pipe |
| CN109761223B (en) * | 2017-11-09 | 2020-10-30 | 北京华碳元芯电子科技有限责任公司 | Method for removing organic dispersant on surface of carbon nano tube film |
| CN107803208A (en) * | 2017-11-14 | 2018-03-16 | 湘潭大学 | A kind of microwave catalyst, its preparation method and the method that hydrogen sulfide is catalytically decomposed |
| CN108609611B (en) * | 2018-04-12 | 2020-10-27 | 华南理工大学 | High-stability environment-friendly water dispersion of carbon nano tube and preparation method thereof |
| CN108314011A (en) * | 2018-04-13 | 2018-07-24 | 武汉工程大学 | A kind of stable dispersion method of carbon nanotube |
| CN109455696B (en) * | 2018-10-24 | 2020-05-26 | 苏州世名科技股份有限公司 | Aqueous carbon nanotube slurry and preparation method thereof |
| CN110697688A (en) * | 2019-11-15 | 2020-01-17 | 河北北方学院 | Preparation method of carbon nano tube water dispersion |
| CN111559742A (en) * | 2019-12-25 | 2020-08-21 | 江西悦安新材料股份有限公司 | Method for improving stability of carbon nano tube |
| CN112225486B (en) * | 2020-10-19 | 2022-05-03 | 湖南加美乐素新材料股份有限公司 | Stable alkali-free liquid accelerator and preparation method and application thereof |
| CN116589998B (en) * | 2023-07-18 | 2023-10-03 | 克拉玛依市正诚有限公司 | Composite thickening agent for fracturing and preparation method thereof |
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| CN101372330B (en) * | 2008-10-08 | 2011-03-23 | 长沙理工大学 | Method for coating carbon nano-tube with metal doped zinc oxide nano-particle |
| CN103569994B (en) * | 2012-07-27 | 2016-06-15 | 国家纳米科学中心 | The treatment process of a kind of Single Walled Carbon Nanotube |
| CN102805103A (en) * | 2012-08-13 | 2012-12-05 | 同济大学 | Synthesis method of carbon nanotube based sterilizing material |
| CN103183327B (en) * | 2013-03-18 | 2015-05-27 | 江苏苏美仑智能科技有限公司 | Treating agent for carbon nano tube and preparation method of water-soluble carbon nano tube |
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