CN106495130A - A kind of preparation method of CNT - Google Patents
A kind of preparation method of CNT Download PDFInfo
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- CN106495130A CN106495130A CN201610937847.1A CN201610937847A CN106495130A CN 106495130 A CN106495130 A CN 106495130A CN 201610937847 A CN201610937847 A CN 201610937847A CN 106495130 A CN106495130 A CN 106495130A
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- flyash
- preparation
- polypyrrole
- hydrochloric acid
- oxidant
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The present invention relates to a kind of method for growing CNT on mineral admixture in concrete, 1). mineral admixture polypyrrole synthesizes：Mineral admixture and pyrrole monomer, magnetic agitation so as to dispersed are added in dilute hydrochloric acid, oxidant is subsequently added, magnetic agitation until there is atrament to generate, is washed, dries, obtain mineral admixture polypyrrole；2). batch mixing：Mineral admixture polypyrrole is mixed with presoma, its mass ratio is：Mineral admixture polypyrrole：Presoma=1:1‑1:10, mix 1 120min in a mixer and form mixture；3). microwave reaction：By step 2) mixed mixture is put in microwave oven carries out microwave radiation, and the response time is 10 3600s；4). finished product：Reaction is finished, sampling, you can obtain target product.The preparation method is convenient, fast, with low cost, and obtained CNT can be used for reinforcing material, absorbing material, magnetic shielding material and strengthen heat conducting material etc..
Description
Technical field
The present invention relates to a kind of preparation method of carbon nano-tube material, belongs to field of material preparation.
Background technology
CNT (CNTs) just got most of the attention from that day being found in 1991.CNTs is a kind of radial dimension
For nanoscale, axial dimension is a kind of micron-sized material with carbon element.Single or multiple lift Graphene is around same center according to certain
Angle is crimped, and the big fullerene of the hemispherical that two ends are formed by five-membered ring and heptatomic ring forms single or multiple lift by sealing
CNTs.In CNTs, the tube wall of every layer of nanotube is complete by 3 carbon atoms of sp2 hydridization and surrounding by a carbon atom to CNTs
The face of cylinder in the hexagonal network planar structure besieged city constituted after closing by full key board.The cylinder-like structure of this bending can produce quantum
Confinement and σ-π hydridization again, along with the pi-electron delocalization structure that sp2 hydridization is produced imparts the excellent optics of CNTs, electricity, magnetic
Learn property.Moreover, the axial arrangement of CNTs also causes CNTs that there is very high modulus and intensity vertically, is for strengthening
The ideal material of composite materials property.There is data to suggest that, the elastic modelling quantity of CNTs, more than 1TPa, is the steel of equal quality
Material 10-100 times (Thostenson E T, Ren Z, Chou T W.Composites science and technology,
2001,61(13):1899-1912.).
So far, the method for synthesis CNTs mainly has chemical vapour deposition technique, arc process, laser ablation method, gas phase to urge
Metaplasia regular way.But these method instrument costs are high, reaction condition harsh (high temperature, anaerobic) needs to be passed through during the course of the reaction
Gas (carbon source and noble gases), considerably increases the danger of operation；And the CNTs for synthesizing is being used as the increasing of composite
Easily reunite during strong body, be difficult to disperse, leverage reinforced effects.This undoubtedly limits widely using for CNTs, the present invention
CNTs is synthesized using microwave method, method is simple, with low cost, yet there are no domestic literature report.
Applied research of the CNT in cement-based material is relatively more at present, but CNT is in cement-based material
Degree of scatter be key which plays one's part to the full.Dispersion side of the nano material of existing document report in cement-based material
Method has physical dispersion method (including mechanical agitation, ultrasound wave dispersion, high power treatment method etc.) and chemical dispersion method (including surface chemistry
Modification method and dispersant method etc., surface chemical modification method are divided into modification by coupling, esterification reaction method, surface graft modification agent again
Method), the present invention realizes nano material in water using the method in the upper growth in situ nano material of mineral admixture (such as flyash)
Dispersion in cement-based material, such that it is able to scattering problem of the effectively solving CNT in cement-based material, and this dispersion
Method has no report at present.
Content of the invention
Technical problem：Present invention aims to the shortcoming that above-mentioned existing preparation method is present, proposes a kind of carbon and receives
The preparation method of mitron, the method is the preparation method that a kind of microwave grows CNTs, and the method is simple, with low cost, has
Hope large-scale production.
Technical scheme：The present invention is a kind of preparation method of carbon nano-tube material, and the method is comprised the following steps：
1), synthesize conductive material；
2), by step 1) conductive material that obtains and presoma be mixed to get mixture；
3), by step 2) mixture that obtains carries out microwave irradiation, prepares CNT.
2nd, a kind of preparation method of carbon nano-tube material as claimed in claim 1, it is characterised in that：Step 1) described in
Conductive material is polypyrrole or polyimides, and its synthesis step is as follows：Pyrrole or monomer * acyls is added in dilute hydrochloric acid
Imines, stirs, and adds oxidant afterwards, stirs to there is atrament to generate, and washing atrament is simultaneously dried, and obtains poly- pyrrole
Cough up or polyimides.
Wherein：
Step 1) described in conductive material be flyash-polypyrrole or flyash-polyimides, its synthesis step is such as
Under：Flyash ultrasound is added in dilute hydrochloric acid, is added pyrrole or monomer * acid imides afterwards, is stirred, add oxidation
Agent, stirs to there is atrament to generate, and washing atrament is simultaneously dried, and obtains flyash-polypyrrole or flyash-polyamides is sub-
Amine.
Described dilute hydrochloric acid：Pyrrole monomer：The mol ratio of oxidant is：10:1:1-1:1:1, described dilute hydrochloric acid：Single
Body * acid imides：The mol ratio of oxidant is：10:1:1-1:1:1, wherein described oxidant is Ammonium persulfate., hydrogen peroxide or chlorine
Change the one kind in ferrum.
Described flyash：Dilute hydrochloric acid：Pyrrole monomer：The mol ratio of oxidant is：10:10:1:1-1:1:1:1, described
Flyash：Dilute hydrochloric acid：Monomer * acid imides：The mol ratio of oxidant is：10:10:1:1-1:1:1:1, wherein described oxidation
Agent is the one kind in Ammonium persulfate., hydrogen peroxide or iron chloride.
Step 2) described in washing atrament and dry and refer to that hydrochloric acid respectively and acetone clean atrament 3 repeatedly
More than secondary, it is vacuum dried at being placed in 50-100 DEG C afterwards, the concentration of wherein described hydrochloric acid is 1-10mol/L.
Step 2) described in presoma be ferrocene, dicyclopentadienyl nickel, one or more in cobaltocene of compositionss.
Step 2) described in the mass ratio that mixes with presoma of conductive material be 1:1-1:10, incorporation time is 30-
3600s.
Step 3) described in the condition of microwave irradiation be：Microwave frequency 2.45GHz, a length of 10-3600s during irradiation.
Beneficial effect：Compared with the method for other synthesis CNTs, it is simple that this is synthesized condition, it is not necessary to high pressure and inertia
Gas shield, can be completed at ambient pressure, and equipment is simple, may be implemented in the growth of CNTs in household microwave oven.
Description of the drawings
The present invention is further illustrated below in conjunction with the accompanying drawings.
Fig. 1 is the SEM figures of prepared CNTs in the embodiment of the present invention one；
Fig. 2 is the SEM figures of prepared CNTs in the embodiment of the present invention two；
Fig. 3 is the SEM figures of prepared CNTs in the embodiment of the present invention three；
Note：Analysis schematic diagrams of the Fig. 1-3 of the present invention for product final state, word or the unintelligible not image pair of image in figure
The understanding of the present invention program.
Specific embodiment
In order to reach object above, the preparation method of the CNTs of the present invention includes following basic step：
1. mineral admixture-polypyrrole synthesizes in dilute hydrochloric acid solution (molar concentration, 0.1-10mol/L), adds
Mineral admixture (quality, 0.1-50g) and pyrrole monomer (molar concentration, 0.01-10mol/L) and Ammonium persulfate. (molar concentration,
0.01-10mol/L), magnetic agitation 0.5-48h, obtains mineral admixture-polypyrrole product；
2. batch mixing is by mineral admixture-polypyrrole, ferrocene/dicyclopentadienyl nickel/cobaltocene one of which or several groups
Close with certain proportion (mass ratio, mineral admixture-polypyrrole：Ferrocene/dicyclopentadienyl nickel/cobaltocene=1:1-1:10) in blender
Middle mixing 1-120min；
3. mixed mineral admixture-polypyrrole and ferrocene/dicyclopentadienyl nickel/cobaltocene are put into microwave by microwave reaction
Microwave radiation is carried out in stove, and the response time is 10-3600s；
4. finished product reaction is finished, and is sampled, you can obtain target product.
Embodiment one
Make flyash-CNTs composites：Flyash-polypyrrole is 1 with ferrocene mass ratio:1, microwave irradiation time
Flyash surface in situ for 15s grows the composite of CNTs：
1. flyash surface treatment adds 5g flyash in dilute hydrochloric acid (80mL, 0.1mol/L), ultrasonic 50min,
The pyrrole monomer of 0.01mol/L, magnetic agitation 10min (530r/min) is added to add the Ammonium persulfate. of 0.01mol/L, magnetic force
Stirring 1h, stopped reaction use 100mL, the washing with acetone of the hydrochloric acid and 100mL of 1mol/L 3 times to be vacuum dried at 50 DEG C respectively,
Obtain flyash-polypyrrole product；
2. batch mixing by flyash-polypyrrole, ferrocene with 1:1 ratio (mass ratio) mixes 1min in a mixer；
3. microwave reaction is put into the flyash-polypyrrole for mixing and ferrocene in crucible, microwave spoke under 800W
Penetrate 50s.
4. finished product sintering is finished, and is sampled, you can obtain target product.
Embodiment two
Make flyash-CNTs composites：Flyash-polypyrrole is 1 with ferrocene mass ratio:2, microwave irradiation time
Flyash surface in situ for 15s grows the composite of CNTs：
1. flyash surface treatment adds 5g flyash in dilute hydrochloric acid (80mL, 3mol/L), ultrasonic 50min, plus
Enter the pyrrole monomer of 0.3mol/L, magnetic agitation 10min adds the Ammonium persulfate. of 0.3mol/L, magnetic agitation 2h to stop anti-
Should, use 100mL, the washing with acetone of the hydrochloric acid and 100mL of 1mol/L 3 times to be vacuum dried at 50 DEG C respectively, obtain flyash-poly-
Pyrroles's product；
2. batch mixing by flyash-polypyrrole, ferrocene with 1:2 ratios (mass ratio) mix 1min in a mixer；
3. microwave reaction is put into the flyash-polypyrrole for mixing and ferrocene in crucible, microwave spoke under 800W
Penetrate 70s.
4. finished product sintering is finished, and is sampled, you can obtain target product.
Embodiment three
Make flyash-CNTs composites：Flyash-polypyrrole is 1 with ferrocene mass ratio:5, microwave irradiation time
Flyash surface in situ for 15s grows the composite of CNTs：
1. flyash surface treatment adds 5g flyash in dilute hydrochloric acid (80mL, 6mol/L), ultrasonic 50min, plus
Enter the pyrrole monomer of 0.6mol/L, magnetic agitation 10min adds the Ammonium persulfate. of 0.6mol/L, magnetic agitation 2h to stop anti-
Should, use 100mL, the washing with acetone of the hydrochloric acid and 100mL of 1mol/L 3 times to be vacuum dried at 50 DEG C respectively, obtain flyash-poly-
Pyrroles's product；
2. batch mixing by flyash-polypyrrole, ferrocene with 1:5 ratios (mass ratio) mix 1min in a mixer；
3. microwave reaction is put into the flyash-polypyrrole for mixing and ferrocene in crucible, microwave spoke under 800W
Penetrate 120s.
4. finished product sintering is finished, and is sampled, you can obtain target product.
In addition to the implementation, the present invention can also have other embodiment.All employing equivalents or equivalent transformation shape
Into technical scheme, such as adopt breeze, regenerative micro powder, other inorganic carriers such as glass microballoon belong to application claims
Protection domain.
Claims (9)
1. a kind of preparation method of carbon nano-tube material, it is characterised in that：The method is comprised the following steps：
1）, synthesis conductive material；
2）, by step 1）The conductive material for obtaining is mixed to get mixture with presoma；
3）, by step 2）The mixture for obtaining carries out microwave irradiation, prepares CNT.
2. a kind of preparation method of carbon nano-tube material as claimed in claim 1, it is characterised in that：Step 1）Described conduction
Property material be polypyrrole or polyimides, its synthesis step is as follows：In dilute hydrochloric acid, add pyrrole or monomer * acyls sub-
Amine, stirs, and adds oxidant afterwards, stirs to there is atrament to generate, and washing atrament is simultaneously dried, and obtains polypyrrole
Or polyimides.
3. a kind of preparation method of carbon nano-tube material as claimed in claim 1, it is characterised in that：Step 1）Described conduction
Property material be flyash-polypyrrole or flyash-polyimides, its synthesis step is as follows：Flyash is added in dilute hydrochloric acid
Ultrasound, adds pyrrole or monomer * acid imides afterwards, stirs, add oxidant, stirs to there is atrament to give birth to
Into washing atrament is simultaneously dried, and obtains flyash-polypyrrole or flyash-polyimides.
4. a kind of preparation method of carbon nano-tube material as claimed in claim 2, it is characterised in that：Described dilute hydrochloric acid：Pyrrole
Cough up monomer：The mol ratio of oxidant is：10:1:1-1:1:1, described dilute hydrochloric acid：Monomer * acid imides：The mol ratio of oxidant
For：10:1:1-1:1:1, wherein described oxidant is the one kind in Ammonium persulfate., hydrogen peroxide or iron chloride.
5. a kind of preparation method of carbon nano-tube material as claimed in claim 3, it is characterised in that：Described flyash：Dilute
Hydrochloric acid：Pyrrole monomer：The mol ratio of oxidant is：10:10:1:1-1:1:1:1, described flyash：Dilute hydrochloric acid：Monomer * acyls
Imines：The mol ratio of oxidant is：10:10:1:1-1:1:1:1, wherein described oxidant is Ammonium persulfate., hydrogen peroxide or chlorine
Change the one kind in ferrum.
6. a kind of preparation method of carbon nano-tube material as claimed in claim 2 or claim 3, it is characterised in that：Step 2）Described
Washing atrament drying refers to that hydrochloric acid respectively and acetone clean atrament more than 3 times repeatedly, is placed in 50- afterwards
It is vacuum dried at 100 DEG C, the concentration of wherein described hydrochloric acid is 1-10mol/L.
7. a kind of preparation method of carbon nano-tube material as claimed in claim 1, it is characterised in that：Step 2）Described forerunner
Body is ferrocene, dicyclopentadienyl nickel, one or more in cobaltocene of compositionss.
8. a kind of preparation method of carbon nano-tube material as claimed in claim 1, it is characterised in that：Step 2）Described conduction
Property the mass ratio that mixes with presoma of material be 1:1-1:10, incorporation time is 30-3600s.
9. a kind of preparation method of carbon nano-tube material as claimed in claim 1, it is characterised in that：Step
3）The condition of described microwave irradiation is：Microwave frequency 2.45GHz, a length of 10-3600s during irradiation.
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| CN201610937847.1A CN106495130A (en) | 2016-10-25 | 2016-10-25 | A kind of preparation method of CNT |
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| CN201610937847.1A CN106495130A (en) | 2016-10-25 | 2016-10-25 | A kind of preparation method of CNT |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107324311A (en) * | 2017-06-29 | 2017-11-07 | 陕西科技大学 | A kind of synthetic method of CNT |
| CN107986260A (en) * | 2018-01-08 | 2018-05-04 | 匡玉华 | A kind of microwave-heating formula coal carbon nanotube device |
| CN108191587A (en) * | 2018-01-08 | 2018-06-22 | 安徽理工大学 | A kind of method of in-situ preparation carbon fiber explosive and the explosive using this method |
| CN108558307A (en) * | 2018-04-02 | 2018-09-21 | 东南大学 | A kind of FA@CNTs enhanced foaming cement heat preserving plates |
| CN110562960A (en) * | 2019-09-05 | 2019-12-13 | 太原理工大学 | preparation and purification method of coal-based carbon nano tube |
| CN110627431A (en) * | 2019-09-09 | 2019-12-31 | 东南大学 | Ultrahigh-sensitivity pressure-sensitive cement-based composite material and preparation method and application thereof |
| CN116535124A (en) * | 2023-05-09 | 2023-08-04 | 青岛理工大学 | CNTs@microbead core-shell filler, cement-based composite material, preparation method and application |
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2016
- 2016-10-25 CN CN201610937847.1A patent/CN106495130A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107324311A (en) * | 2017-06-29 | 2017-11-07 | 陕西科技大学 | A kind of synthetic method of CNT |
| CN107986260A (en) * | 2018-01-08 | 2018-05-04 | 匡玉华 | A kind of microwave-heating formula coal carbon nanotube device |
| CN108191587A (en) * | 2018-01-08 | 2018-06-22 | 安徽理工大学 | A kind of method of in-situ preparation carbon fiber explosive and the explosive using this method |
| CN108558307A (en) * | 2018-04-02 | 2018-09-21 | 东南大学 | A kind of FA@CNTs enhanced foaming cement heat preserving plates |
| CN110562960A (en) * | 2019-09-05 | 2019-12-13 | 太原理工大学 | preparation and purification method of coal-based carbon nano tube |
| CN110562960B (en) * | 2019-09-05 | 2022-08-02 | 太原理工大学 | Preparation and purification method of coal-based carbon nano tube |
| CN110627431A (en) * | 2019-09-09 | 2019-12-31 | 东南大学 | Ultrahigh-sensitivity pressure-sensitive cement-based composite material and preparation method and application thereof |
| CN116535124A (en) * | 2023-05-09 | 2023-08-04 | 青岛理工大学 | CNTs@microbead core-shell filler, cement-based composite material, preparation method and application |
| CN116535124B (en) * | 2023-05-09 | 2024-04-12 | 青岛理工大学 | CNTs@microbead core-shell filler, cement-based composite material, preparation method and application |
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Application publication date: 20170315 |