CN106276850B - High concentration, finely dispersed carbon nano tube suspension preparation method - Google Patents
High concentration, finely dispersed carbon nano tube suspension preparation method Download PDFInfo
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- CN106276850B CN106276850B CN201610647275.3A CN201610647275A CN106276850B CN 106276850 B CN106276850 B CN 106276850B CN 201610647275 A CN201610647275 A CN 201610647275A CN 106276850 B CN106276850 B CN 106276850B
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Abstract
The invention belongs to surface modification of carbon nanotube technical fields, more particularly to a kind of high concentration, finely dispersed carbon nano tube suspension preparation method, this method is first by carbon nanotube to be modified according to the ratio and the concentrated sulfuric acid of 1g:20-50mL, concentrated nitric acid mixed acid solution is mixed, it is modified to be heated to 6-8 hours progress surfaces of 80-100 DEG C of condensing reflux, dilution is washed with deionized after its natural cooling, it is centrifugated out modified carbon nanotube again, finally plus water is configured to suspension and adjusts the carbon nano tube suspension that pH to 7-12 is 10% or so up to mass fraction.It using the suspension concentration height of the method for the present invention preparation, is uniformly dispersed, without excessive organic surface modifying agent, standing 3 months will not be settled.
Description
Technical field
The invention belongs to surface modification of carbon nanotube technical fields, and in particular to a kind of high concentration, finely dispersed carbon are received
Mitron suspension manufacturing methods.
Background technique
Carbon nanotube (CNTs) found that it was a kind of quasi one-dimensional material in 1991 by Japanese Electronic Speculum expert lijima, tool
There is hollow rod structure made of single-layer or multi-layer graphene film winding.Since carbon nanotube caliber is small, large specific surface area, major diameter
Than big, physical and chemical performance is excellent, it is allowed to be widely applied to each field.But the large specific surface area of CNTs, between Guan Yuguan
There is strong model ylid bloom action, therefore easily reunites in solvent and ceramic matrix.This feature of CNTs difficulty dispersion, it is serious
Limit its application.
Currently, its dispersion in the base can be improved by carrying out effective surface modification and modification to carbon nanotube
Performance improves the interaction of compatibility enhancing between the two between carbon nanotube and basis material, to improve carbon nanometer
The performance of pipe composite material.Gao Lian et al. promotes gold nanoparticle using citric acid modification and is deposited in carbon nano tube surface
(CHEN D L, GAO Lian.Synthesis and Sintering Behavior of (Ce, Cu)-SnO2Nanopowders
by Polymeric Precursor Methods[J].Journal of Inorganic Materials,2004,19(1):
58-62), Lu Zhihua et al. effectively raises stability (Lu Zhihua, Sun Kangning, the Ren Shuai of carbon nano tube suspension using SDS
The surface modification and Study on dispersity [J] Rare Metals Materials and engineering of equal multi-walled carbon nanotube, 2007,36 (S3): 100-
103), Lixia ZHANG et al. is carried out surface to it using polyvinyl alcohol enveloped carbon nanometer tube modified (Lixia ZHANG, Shandong multi wall carbon is received
Mitron Study on dispersity [J] synthetic fibers, 2008,37 (06): 32-35), Chen Chuansheng et al. utilizes citric acid modification carbon nanometer
Pipe improves its dispersibility (such as Chen Chuansheng, Liu Tiangui, Chen little Hua Modified Carbon Nanotubes with Citric Acid and its dispersibility in water
Energy [J] Sichuan University's journal (engineering science version), 2008,40 (03): 108-111), Chen little Hua et al. dodecyl bromination
Its dispersibility in water is set to be improved (the table of the carbon nanotube such as Chen little Hua, Chen Chuansheng, Sun Lei after ammonium is carbon nano-tube modified
Face is modified and its dispersion performance in water studies [J] Hunan University journal (natural science edition), 2004,31 (05): 18-
21).It to sum up, is highly effective method using the modified dispersibility to solve CNTs in surface.But the use of surfactant makes
In carbon nano tube suspension there are more macromolecule organic, the presence of carbon nanotube organic matter in application process influences
It plays itself excellent physical and chemical performance.
The present invention carries out surface using a certain proportion of mixed acid oxide/carbon nanometer tube and is modified, and is washed by deionized water dilution
It washs for several times and is centrifuged, be then diluted and adjust pH, be finally configured to the carbon nano tube suspension that concentration is greater than 10wt%, the carbon
It does not settle within nanotube suspension standing 3 months or more.
Summary of the invention
It is an object of the invention to solve, existing organic impurities during existing surface modification of carbon nanotube are more, carbon is received
The deficiencies of mitron suspension is not sufficiently stable, concentration is lower provides a kind of high concentration, the preparation of finely dispersed carbon nano tube suspension
Method, this method are modified the surface CNTs by the concentrated sulfuric acid, concentrated nitric acid mixed acid, can be made after centrifugation, dilution, tune pH
Standing 3 months or more the high-concentration carbon nano tube suspension not settled.Technical scheme is as follows:
A kind of high concentration, finely dispersed carbon nano tube suspension preparation method, comprising the following steps: (a) is by carbon nanometer
Pipe is added to the concentrated sulfuric acid according to a certain percentage, in concentrated nitric acid mixed acid solution and stirs evenly, and obtains carbon nanotube mixed acid solution；
(b) heating of carbon nanotube mixed acid solution obtained by step (a) is condensed back；(c) carbon nanotube for obtaining step (b)
Suspension is cooling, for several times with deionized water dilution washing；(d) carbon nano tube suspension for obtaining step (c) is centrifugated, and is obtained
To the modified carbon nanotube in surface；(e) the modified carbon nanotube in surface and deionized water are hybridly prepared into suspension, adjusted
Save pH to alkalinity to obtain the final product.
According to above scheme, the concentrated sulfuric acid in step (a) mixed acid solution, concentrated nitric acid volume ratio be 3:2, carbon nanometer
The amount ratio of pipe and mixed acid solution is 1g:20-50mL.
According to above scheme, carbon nanotube mixed acid solution is heated to 80-100 DEG C of condensing reflux 6-8h in step (b).
According to above scheme, when carbon nano tube suspension is centrifugated in step (d), centrifuge speed 10000rpm,
Being centrifuged number is 4-6 times, and each centrifugation time is 10min.
According to above scheme, the carbon nano tube suspension pH that step (e) is prepared is in 7-12, and concentration is in 10wt% or more.
According to above scheme, the mass concentration of the concentrated sulfuric acid is 95-98%, and the mass concentration of the concentrated nitric acid is 65-
68%.
Carbon nanotube described in above scheme is multi-walled carbon nanotube.
Compared with common carbon nano tube surface modification process, the method for the present invention has the advantages that (1) preparation
Carbon nano tube suspension is more pure, without extra surfactant, will not influence its excellent physical and chemical performance；(2) carbon is received
Mitron and mixed acid are mixed according to the ratio of 1g:20-50ml, and preferably the volume ratio of the concentrated sulfuric acid and concentrated nitric acid is 3 in mixed acid:
2, guarantee that carbon nanotube obtains effectively aoxidizing and surface is modified；(3) small in 80~100 DEG C of temperature selected condensing refluxes 6~8
When, the structure that not only can guarantee that carbon nanotube was fully oxidized but also do not destroyed itself；(4) acid of diluted strong is washed with deionized
Property；(5) sufficiently centrifugation, obtains pure modified carbon nano-tube；(6) the carbon nano tube suspension concentration one that conventional method is prepared
As in 1-5wt%, carbon nano tube suspension concentration prepared by the present invention 10wt% or more and dispersibility it is excellent, stand 3 months
It does not also settle above.
Specific embodiment
To make those of ordinary skill in the art fully understand technical solution of the present invention and beneficial effect, below in conjunction with specific
Embodiment is further described.
Carbon nanotube used in the present invention is general commercial multi-walled carbon nanotube, prepares the concentrated sulfuric acid used in mixed acid
Mass concentration is 95-98%, and the mass concentration of concentrated nitric acid is 65-68%.
Embodiment 1
The mixed acid of 250ml (concentrated sulfuric acid and concentrated nitric acid volume ratio be 3:2) is poured into the more of 5g according to the proportion of 1g:50mL
It is uniformly mixed to obtain carbon nanotube mixed acid solution in wall carbon nano tube, carbon nanotube mixed acid solution is heated to 80 DEG C and is condensed back to
Stream stops heating after 6 hours, after its natural cooling for several times with deionized water dilution washing.By the carbon nanotube after dilution washing
Suspension is placed in a centrifuge, and is centrifuged 4 times under the revolving speed of 10000rpm, every time centrifugation 10 minutes, is obtained the modified carbon in surface and is received
Mitron.40ml deionized water is added in the carbon nanotube being precipitated to centrifugation and is configured to multi-walled carbon nanotube suspension, followed by
Its PH is adjusted to 7 by a small amount of concentrated ammonia liquor, finally obtains the multi-walled carbon nanotube suspension that evenly dispersed concentration is 10wt% or more.
Embodiment 2
The mixed acid of 100ml (concentrated sulfuric acid and concentrated nitric acid volume ratio be 3:2) is poured into the more of 5g according to the proportion of 1g:20mL
It is uniformly mixed to obtain carbon nanotube mixed acid solution in wall carbon nano tube, carbon nanotube mixed acid solution is heated to 100 DEG C of condensations
Stop heating after reflux 8 hours, after its natural cooling for several times with deionized water dilution washing.By the carbon nanometer after dilution washing
Pipe suspension is placed in a centrifuge, and is centrifuged 6 times under the revolving speed of 10000rpm, is obtained the modified carbon in surface within centrifugation 10 minutes every time and is received
Mitron.40ml deionized water is added in the carbon nanotube being precipitated to centrifugation and is configured to multi-walled carbon nanotube suspension, followed by
Its PH is adjusted to 12 by a small amount of concentrated ammonia liquor, is finally obtained the multi-walled carbon nanotube that evenly dispersed concentration is 10wt% or more and is suspended
Liquid.
Embodiment 3
The mixed acid of 150ml (concentrated sulfuric acid and concentrated nitric acid volume ratio be 3:2) is poured into the more of 5g according to the proportion of 1g:30mL
It is uniformly mixed to obtain carbon nanotube mixed acid solution in wall carbon nano tube, carbon nanotube mixed acid solution is heated to 90 DEG C and is condensed back to
Stream stops heating after 7 hours, after its natural cooling for several times with deionized water dilution washing.By the carbon nanotube after dilution washing
Suspension is placed in a centrifuge, and is centrifuged 5 times under the revolving speed of 10000rpm, obtains the modified carbon nanometer in surface within centrifugation 10 minutes every time
Pipe.40ml deionized water is added in the carbon nanotube being precipitated to centrifugation and is configured to multi-walled carbon nanotube suspension, followed by few
It measures concentrated ammonia liquor and its PH is adjusted to 10, finally obtain the multi-walled carbon nanotube suspension that evenly dispersed concentration is 10wt% or more.
In order to analyze influence of the mixed acid of different proportion to carbon nano tube suspension stability, We conducted corresponding
Comparative experiments.Experiment condition are as follows: the mixed acid (concentrated sulfuric acid and concentrated nitric acid) of 150ml is poured into 5g's according to the proportion of 1g:30mL
It is uniformly mixed to obtain carbon nanotube mixed acid solution in multi-walled carbon nanotube, carbon nanotube mixed acid solution is heated to 80 DEG C of condensations
Stop heating after reflux 6 hours, after its natural cooling for several times with deionized water dilution washing.By the carbon nanometer after dilution washing
Pipe suspension is placed in a centrifuge, and is centrifuged 5 times under the revolving speed of 10000rpm, is obtained the modified carbon in surface within centrifugation 10 minutes every time and is received
Mitron.40ml deionized water is added in the carbon nanotube being precipitated to centrifugation and is configured to multi-walled carbon nanotube suspension, followed by
Its PH is adjusted to 7 by a small amount of concentrated ammonia liquor, finally obtains the multi-walled carbon nanotube suspension that evenly dispersed concentration is 10wt% or more.
The volume ratio of the concentrated sulfuric acid and concentrated nitric acid is 3:3 in A group, and the volume ratio of the concentrated sulfuric acid and concentrated nitric acid is 3:1, the concentrated sulfuric acid in C group in B group
Volume ratio with concentrated nitric acid is 3:2.
Carbon nano tube suspension made from 5mLA, B, C group and embodiment 1-3 is taken to be fitted into test tube respectively, in room temperature condition
Lower standing, observes and records the variation of suspension daily.As a result, it has been found that after the carbon nano tube suspension of A group and B group stands 7 days
It is settled, all sedimentation finishes soon；And the carbon nano tube suspension of C group and embodiment 1-3, it stands so far (more than 3
Month) all do not settle.
Claims (4)
1. a kind of high concentration, finely dispersed carbon nano tube suspension preparation method, which comprises the following steps:
(a) carbon nanotube is added to the concentrated sulfuric acid according to a certain percentage, in concentrated nitric acid mixed acid solution and is stirred evenly, carbon is obtained and receives
Mitron mixed acid solution；
(b) heating of carbon nanotube mixed acid solution obtained by step (a) is condensed back；
(c) carbon nano tube suspension for obtaining step (b) is cooling, for several times with deionized water dilution washing；
(d) carbon nano tube suspension for obtaining step (c) is centrifugated, and obtains the modified carbon nanotube in surface；
(e) the modified carbon nanotube in surface and deionized water are hybridly prepared into suspension, adjusting pH to alkalinity to obtain the final product；
Wherein, the concentrated sulfuric acid in step (a) mixed acid solution, concentrated nitric acid volume ratio be 3:2, carbon nanotube and mixed acid solution
Amount ratio is 1g:20-50mL；Carbon nanotube mixed acid solution is heated to 80-100 DEG C of condensing reflux 6-8h in step (b)；Step
Suddenly the carbon nano tube suspension pH that (e) is prepared is in 7-12, and concentration is in 10wt% or more.
2. a kind of high concentration as described in claim 1, finely dispersed carbon nano tube suspension preparation method, feature exist
In: when carbon nano tube suspension is centrifugated in step (d), centrifuge speed 10000rpm, centrifugation number is 4-6 times, often
Secondary centrifugation time is 10min.
3. a kind of high concentration as described in claim 1, finely dispersed carbon nano tube suspension preparation method, feature exist
In: the mass concentration of the concentrated sulfuric acid is 95-98%, and the mass concentration of the concentrated nitric acid is 65-68%.
4. a kind of high concentration as described in claim 1, finely dispersed carbon nano tube suspension preparation method, feature exist
In: the carbon nanotube is multi-walled carbon nanotube.
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| CN110589807A (en) * | 2019-09-19 | 2019-12-20 | 天津大学 | Acidification treatment method for improving dispersibility of carbon nano tube in neutral solution |
| CN112250338A (en) * | 2020-10-19 | 2021-01-22 | 湖南加美乐素新材料股份有限公司 | Polycarboxylate superplasticizer for concrete prefabricated part and preparation method thereof |
| CN115873424A (en) * | 2022-11-29 | 2023-03-31 | 江西悦安新材料股份有限公司 | Carbon nano tube modified particle and preparation method and application thereof |
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