CN106276850A - 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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- CN106276850A CN106276850A CN201610647275.3A CN201610647275A CN106276850A CN 106276850 A CN106276850 A CN 106276850A CN 201610647275 A CN201610647275 A CN 201610647275A CN 106276850 A CN106276850 A CN 106276850A
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Abstract
The invention belongs to surface modification of carbon nanotube technical field, it is specifically related to a kind of high concentration, finely dispersed carbon nano tube suspension preparation method, the method first by CNT to be modified according to the ratio of 1g:20 50mL and concentrated sulphuric acid, concentrated nitric acid mixed acid solution mixes, it is heated to 80 100 DEG C of condensing refluxes and carries out surface modification in 68 hours, it is washed with deionized dilution after its natural cooling, centrifugation goes out modified CNT again, finally add water and be configured to suspension and regulate pH to 7 12 i.e. to obtain the carbon nano tube suspension that mass fraction is about 10%.Using that the suspension concentration prepared of the inventive method is high, be uniformly dispersed, without excess organic surface modifying agent, standing 3 months will not settle.
Description
Technical field
The invention belongs to surface modification of carbon nanotube technical field, be specifically related to a kind of high concentration, finely dispersed carbon is received
Mitron suspension manufacturing methods.
Background technology
CNT (CNTs) is found in 1991 by Japan Electronic Speculum expert lijima, and it is a kind of quasi one-dimensional material, tool
There is the hollow rod structure that single or multiple lift graphene film winds.Owing to CNT caliber is little, specific surface area big, major diameter
Than big, physical and chemical performance excellence, it is allowed to be widely applied to each field.But, the specific surface area of CNTs is big, between tube and tube
There is strong model ylid bloom action, the most easily reunite in solvent and ceramic matrix.Difficult this feature scattered of CNTs is serious
Limit its application.
At present, by CNT is carried out effective surface modification and modification, its dispersion in the base can be improved
Performance, improves the compatibility between CNT and matrix material and strengthens interaction between the two, thus improve carbon nanometer
The performance of pipe composite.Gao Lian et al. utilizes citric acid modification to promote golden nanometer particle 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. utilizes SDS to effectively raise stability (Lu Zhihua, Sun Kangning, the Ren Shuai of carbon nano tube suspension
Deng. the surface of multi-walled carbon nano-tubes is modified and Study on dispersity [J]. Rare Metals Materials and engineering, 2007,36 (S3): 100-
103), Lixia ZHANG et al. utilize polyvinyl alcohol enveloped carbon nanometer tube to its carry out surface modification (Lixia ZHANG, Shandong. many walls 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 improve its dispersibility in water (Chen Chuansheng, Liu Tiangui, Chen little Hua etc. Modified Carbon Nanotubes with Citric Acid and dispersibility thereof
Energy [J]. Sichuan University's journal (engineering science version), 2008,40 (03): 108-111), Chen little Hua et al. dodecyl bromination
Make after ammonium is carbon nano-tube modified its dispersibility in water be improved (Chen little Hua, Chen Chuansheng, Sun Lei etc. the table of CNT
Face modification and the research of the dispersive property in water [J] thereof. Hunan University's journal (natural science edition), 2004,31 (05): 18-
21).To sum up, utilizing surface modification is highly effective method to solve the dispersibility of CNTs.But the use of surfactant makes
Obtaining in carbon nano tube suspension and there is more macromolecule organic, CNT is organic in application process exists impact
It plays self excellent physical and chemical performance.
The present invention utilizes a certain proportion of mixed acid oxide/carbon nanometer tube to carry out surface modification, is washed by deionized water dilution
Wash for several times and be centrifuged, be then diluted and adjust pH, being finally configured to the concentration carbon nano tube suspension more than 10wt%, this carbon
Nanotube suspension stands and does not settles for more than 3 months.
Summary of the invention
It is an object of the invention to solve that organic impurities present in existing surface modification of carbon nanotube process is many, carbon is received
The deficiencies such as mitron suspension is not sufficiently stable, concentration is relatively low, it is provided that prepared by a kind of high concentration, finely dispersed carbon nano tube suspension
Method, the method by concentrated sulphuric acid, concentrated nitric acid mixed acid to CNTs modifying surface, by centrifugation, dilute, adjust pH after can prepare
Stand the high-concentration carbon nano tube suspension that sedimentation does not occur for more than 3 months.Technical scheme is as follows:
A kind of high concentration, finely dispersed carbon nano tube suspension preparation method, comprise the following steps: (a) is by carbon nanometer
Pipe joins according to a certain percentage in concentrated sulphuric acid, concentrated nitric acid mixed acid solution and stirs, and obtains CNT mixed acid solution；
B the heating of step (a) gained CNT mixed acid solution is carried out condensing reflux by ()；C CNT that step (b) is obtained by ()
Suspension cools down, with deionized water dilution washing for several times；D carbon nano tube suspension centrifugation that step (c) is obtained by (),
CNT after surface modification；E CNT after surface modification and deionized water are hybridly prepared into suspension by (), adjust
Joint pH to alkalescence and get final product.
According to such scheme, in the described mixed acid solution of step (a), concentrated sulphuric acid, the volume ratio of concentrated nitric acid are 3:2, carbon nanometer
Pipe is 1g:20-50mL with the amount ratio of mixed acid solution.
According to such scheme, CNT mixed acid solution is heated to by step (b) 80-100 DEG C of condensing reflux 6-8h.
According to such scheme, in step (d) during carbon nano tube suspension centrifugation, centrifuge speed is 10000rpm,
Centrifugal number of times is 4-6 time, and each centrifugation time is 10min.
According to such scheme, carbon nano tube suspension pH that step (e) is prepared is at 7-12, and concentration is at more than 10wt%.
According to such scheme, the mass concentration of described concentrated sulphuric acid is 95-98%, and the mass concentration of described concentrated nitric acid is 65-
68%.
CNT described in such scheme is multi-walled carbon nano-tubes.
Compared with common carbon nano tube surface modification process, the inventive method has the advantages that prepared by (1)
Carbon nano tube suspension is the purest, without unnecessary surfactant, does not interferes with its excellent physical and chemical performance；(2) carbon is received
Mitron mixes according to the ratio of 1g:20-50ml with mixed acid, and in preferred mixed acid, the volume ratio of concentrated sulphuric acid and concentrated nitric acid is 3:
2, it is ensured that CNT is effectively aoxidized and surface modification；(3) little in selected temperature 80～100 DEG C of condensing refluxes 6～8
Time, not only can guarantee that CNT is fully oxidized but also do not destroy the structure of itself；(4) acid of diluted strong it is washed with deionized
Property；(5) the most centrifugal, obtain pure modified carbon nano-tube；(6) the carbon nano tube suspension concentration one that traditional method is prepared
As at 1-5wt%, carbon nano tube suspension concentration prepared by the present invention is excellent at more than 10wt% and dispersibility, stands 3 months
Below do not settle.
Detailed description of the invention
For making those of ordinary skill in the art fully understand technical scheme and beneficial effect, below in conjunction with specifically
Embodiment is further described.
CNT used in the present invention is general commercial multi-walled carbon nano-tubes, the concentrated sulphuric acid that preparation mixed acid is used
Mass concentration is 95-98%, and the mass concentration of concentrated nitric acid is 65-68%.
Embodiment 1
The mixed acid (concentrated sulphuric acid and concentrated nitric acid volume ratio are 3:2) of 250ml is poured into 5g many according to the proportioning of 1g:50mL
In wall carbon nano tube, mix homogeneously obtains CNT mixed acid solution, CNT mixed acid solution is heated to 80 DEG C and condenses back
Stop heating, after flowing 6 hours after its natural cooling with deionized water dilution washing for several times.By the CNT after dilution washing
Suspension is placed in a centrifuge, and is centrifuged 4 times under the rotating speed of 10000rpm, and the most centrifugal 10 minutes, the carbon obtaining surface modification was received
Mitron.In the CNT of centrifugal precipitation, add 40ml deionized water be configured to multi-walled carbon nano-tubes suspension, followed by
Its PH is adjusted to 7 by a small amount of strong aqua ammonia, finally obtains the multi-walled carbon nano-tubes suspension that homodisperse concentration is more than 10wt%.
Embodiment 2
The mixed acid (concentrated sulphuric acid and concentrated nitric acid volume ratio are 3:2) of 100ml is poured into 5g many according to the proportioning of 1g:20mL
In wall carbon nano tube, mix homogeneously obtains CNT mixed acid solution, and CNT mixed acid solution is heated to 100 DEG C of condensations
Stop heating, after refluxing 8 hours after its natural cooling with deionized water dilution washing for several times.By the carbon nanometer after dilution washing
Pipe suspension is placed in a centrifuge, and is centrifuged 6 times under the rotating speed of 10000rpm, and the carbon obtaining surface modification in the most centrifugal 10 minutes is received
Mitron.In the CNT of centrifugal precipitation, add 40ml deionized water be configured to multi-walled carbon nano-tubes suspension, followed by
Its PH is adjusted to 12 by a small amount of strong aqua ammonia, finally obtains the multi-walled carbon nano-tubes that homodisperse concentration is more than 10wt% and suspends
Liquid.
Embodiment 3
The mixed acid (concentrated sulphuric acid and concentrated nitric acid volume ratio are 3:2) of 150ml is poured into 5g many according to the proportioning of 1g:30mL
In wall carbon nano tube, mix homogeneously obtains CNT mixed acid solution, CNT mixed acid solution is heated to 90 DEG C and condenses back
Stop heating, after flowing 7 hours after its natural cooling with deionized water dilution washing for several times.By the CNT after dilution washing
Suspension is placed in a centrifuge, and is centrifuged 5 times under the rotating speed of 10000rpm, the carbon nanometer obtaining surface modification in the most centrifugal 10 minutes
Pipe.In the CNT of centrifugal precipitation, add 40ml deionized water be configured to multi-walled carbon nano-tubes suspension, followed by few
Its PH is adjusted to 10 by amount strong aqua ammonia, finally obtains the multi-walled carbon nano-tubes suspension that homodisperse concentration is more than 10wt%.
In order to analyze the impact on carbon nano tube suspension stability of the mixed acid of different proportion, We conducted corresponding
Contrast experiment.Experiment condition is: pour the mixed acid (concentrated sulphuric acid and concentrated nitric acid) of 150ml into 5g according to the proportioning of 1g:30mL
In multi-walled carbon nano-tubes, mix homogeneously obtains CNT mixed acid solution, and CNT mixed acid solution is heated to 80 DEG C of condensations
Stop heating, after refluxing 6 hours after its natural cooling with deionized water dilution washing for several times.By the carbon nanometer after dilution washing
Pipe suspension is placed in a centrifuge, and is centrifuged 5 times under the rotating speed of 10000rpm, and the carbon obtaining surface modification in the most centrifugal 10 minutes is received
Mitron.In the CNT of centrifugal precipitation, add 40ml deionized water be configured to multi-walled carbon nano-tubes suspension, followed by
Its PH is adjusted to 7 by a small amount of strong aqua ammonia, finally obtains the multi-walled carbon nano-tubes suspension that homodisperse concentration is more than 10wt%.
In A group, concentrated sulphuric acid is that in 3:3, B group, the volume ratio of concentrated sulphuric acid and concentrated nitric acid is concentrated sulphuric acid in 3:1, C group with the volume ratio of concentrated nitric acid
It is 3:2 with the volume ratio of concentrated nitric acid.
Take the carbon nano tube suspension that 5mLA, B, C group and embodiment 1-3 prepare respectively and load in test tube, at room temperature condition
Lower standing, observes and records the change of suspension every day.It was found that after the carbon nano tube suspension of A group and B group stands 7 days
There occurs sedimentation, all sedimentation is complete soon；And C group and the carbon nano tube suspension of embodiment 1-3, stand so far (more than 3
Month) all settle.
Claims (7)
1. a high concentration, finely dispersed carbon nano tube suspension preparation method, it is characterised in that comprise the following steps: (a)
CNT joined according to a certain percentage in concentrated sulphuric acid, concentrated nitric acid mixed acid solution and stir, obtaining CNT and mix
Close acid solution；B the heating of step (a) gained CNT mixed acid solution is carried out condensing reflux by ()；C step (b) is obtained by ()
Carbon nano tube suspension cooling, with deionized water dilution washing for several times；D carbon nano tube suspension that step (c) is obtained by ()
Centrifugation, obtains the CNT after surface modification；E () is by the CNT after surface modification and deionized water mixed preparing
Suspension, regulation pH is become to alkalescence and to get final product.
2. a kind of high concentration, finely dispersed carbon nano tube suspension preparation method as claimed in claim 1, its feature exists
In: in step (a) mixed acid solution, concentrated sulphuric acid, the volume ratio of concentrated nitric acid are 3:2, CNT and the amount ratio of mixed acid solution
For 1g:20-50mL.
3. a kind of high concentration, finely dispersed carbon nano tube suspension preparation method as claimed in claim 1, its feature exists
In: CNT mixed acid solution is heated to 80-100 DEG C of condensing reflux 6-8h by step (b).
4. a kind of high concentration, finely dispersed carbon nano tube suspension preparation method as claimed in claim 1, its feature exists
In: during carbon nano tube suspension centrifugation in step (d), centrifuge speed is 10000rpm, and centrifugal number of times is 4-6 time, often
Secondary centrifugation time is 10min.
5. a kind of high concentration, finely dispersed carbon nano tube suspension preparation method as claimed in claim 1, its feature exists
In: carbon nano tube suspension pH that step (e) is prepared is at 7-12, and concentration is at more than 10wt%.
6. a kind of high concentration, finely dispersed carbon nano tube suspension preparation method as claimed in claim 1, its feature exists
In: the mass concentration of described concentrated sulphuric acid is 95-98%, and the mass concentration of described concentrated nitric acid is 65-68%.
7. a kind of high concentration, finely dispersed carbon nano tube suspension preparation method as claimed in claim 1, its feature exists
In: described CNT is multi-walled carbon nano-tubes.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108314011A (en) * | 2018-04-13 | 2018-07-24 | 武汉工程大学 | A kind of stable dispersion method of carbon nanotube |
| 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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| US20060006367A1 (en) * | 2004-07-06 | 2006-01-12 | Chun-Yen Hsiao | Carbon nanotube suspension |
| CN103147074A (en) * | 2013-03-18 | 2013-06-12 | 厦门大学 | Method for chemically plating silver on surface of carbon nanotube |
| CN103613171A (en) * | 2013-11-26 | 2014-03-05 | 三峡大学 | Preparation method of stainless steel wire mesh electrode loading single-walled carbon nanotubes |
| CN104277674A (en) * | 2014-09-22 | 2015-01-14 | 南京航空航天大学 | Multi-wall carbon nanotube filled photocuring antistatic material and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20060006367A1 (en) * | 2004-07-06 | 2006-01-12 | Chun-Yen Hsiao | Carbon nanotube suspension |
| CN103147074A (en) * | 2013-03-18 | 2013-06-12 | 厦门大学 | Method for chemically plating silver on surface of carbon nanotube |
| CN103613171A (en) * | 2013-11-26 | 2014-03-05 | 三峡大学 | Preparation method of stainless steel wire mesh electrode loading single-walled carbon nanotubes |
| CN104277674A (en) * | 2014-09-22 | 2015-01-14 | 南京航空航天大学 | Multi-wall carbon nanotube filled photocuring antistatic material and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108314011A (en) * | 2018-04-13 | 2018-07-24 | 武汉工程大学 | A kind of stable dispersion method of carbon nanotube |
| 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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