CN107337197A - The method that CNT is scattered in cement matrix - Google Patents

The method that CNT is scattered in cement matrix Download PDF

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Publication number
CN107337197A
CN107337197A CN201610272980.XA CN201610272980A CN107337197A CN 107337197 A CN107337197 A CN 107337197A CN 201610272980 A CN201610272980 A CN 201610272980A CN 107337197 A CN107337197 A CN 107337197A
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CN
China
Prior art keywords
cnt
scattered
cement matrix
cement
rubber material
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Pending
Application number
CN201610272980.XA
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Chinese (zh)
Inventor
戴建国
安晓鹏
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Shenzhen Research Institute HKUST
Shenzhen Research Institute HKPU
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Shenzhen Research Institute HKUST
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Priority to CN201610272980.XA priority Critical patent/CN107337197A/en
Publication of CN107337197A publication Critical patent/CN107337197A/en
Pending legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28C—PREPARING CLAY; PRODUCING MIXTURES CONTAINING CLAY OR CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28C5/00—Apparatus or methods for producing mixtures of cement with other substances, e.g. slurries, mortars, porous or fibrous compositions
    • B28C5/003—Methods for mixing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/13—Nanotubes

Abstract

The present invention relates to material dispersion technology field, specifically discloses a kind of method that CNT is scattered in cement matrix.This method comprises at least following steps：Including at least following steps：Step S01. is heated to 500~1000 DEG C in an inert atmosphere, by auxiliary gel rubber material；Step S02. is passed through gaseous carbon source, 500~1000 DEG C of keeping temperature, reaction generation CNT into institute's inert atmosphere；The auxiliary gel rubber material that deposited the CNT is carried out mixing treatment by step S03. with cement-based material.The process for dispersing can make CNT is good to be scattered in cement matrix, disperse fast and simple, dust dispersion quality height, be adapted to the large-scale application of architectural engineering practice, and improving brittle working process for architectural engineering concrete provides a kind of effective scheme.

Description

The method that CNT is scattered in cement matrix
Technical field
The present invention relates to dispersion technology field of the material in cement matrix, more particularly to a kind of CNT point Dissipate the method in cement matrix.
Background technology
Concrete is the material of most critical in civil engineering work, plays a part of core to the quality of building, But concrete enbrittles the features such as stronger.
Fiber etc. is added typically in Concrete is synthesized at present or is implanted into steel when concreting is molded Muscle, the tensile strength of concrete can be effectively lifted by both approaches.
CNT is as a kind of diameter about 50-100nm, the nano material of slenderness ratio about more than 1000.It is this Carbon nano-tube material has extremely strong wilfulness, after any angle is bent, when external force elimination, can recover State originally is without being broken.Therefore, CNT is added in concrete to improve agent on crack resistance of concrete Tensile strength and toughness, it is one and extremely has technology ingenious, and there is applications well prospect.Grind Study carefully data to show, added using CNT in cement-based material, the compression strength of cement-based material can carry 20%-30% is risen, tensile strength can lift 30%-40%.Meanwhile the introducing of CNT, Ke Yiyou The voltage-dependent characteristic of effect enhancing concrete.The concrete that with the addition of CNT can be used for the prison of structure stress situation Survey, monitoring of road and bridge flow etc..
But because carbon nanotube diameter is small, easily reunite in the presence of Van der Waals force between individual.Group It is polymerized to as CNT to be added to one of key issue faced in concrete.And relevant research shows, Performance of the dispersion effect of CNT to Mechanical Properties of Cement-based Materials and other performances has a significant impact.
The following two methods of generally use mix CNT in concrete now, one is being added in water Surfactant, to improve dispersiveness of the CNT in water；The second is by ultrasonic wave to CNT Suspension is shaken, and brings it about enough scattered, and both approaches often use simultaneously.But CNT it is scattered still undesirable, be mainly manifested in, dispersant can be to the aquation of concrete gel rubber material Adversely affect, and the intensity of ultrasonic wave and time are relatively difficult to hold, and easily cause the disconnected of CNT Split.In addition, under the conditions of current technology, two methods are cumbersome, and it is real to be not suitable for large-scale engineering Trample.
Therefore, it is necessary to find the method that new CNT is scattered in cement matrix.
The content of the invention
It is an object of the invention to for existing CNT in cement matrix disperse exist dispersion effect it is bad, Scattered the problems such as being unsuitable for engineering practice, there is provided a kind of method that CNT is scattered in cement matrix.
To achieve the above object of the invention, the embodiment of the present invention employs following technical scheme：
A kind of method that CNT is scattered in cement matrix, including at least following steps：
Step S01. is heated to 500~1000 DEG C in an inert atmosphere, by auxiliary gel rubber material；
Step S02. is passed through gaseous carbon source, 500~1000 DEG C of keeping temperature, reaction life into institute's inert atmosphere Into CNT；
Step S03. is mixed the auxiliary gel rubber material that deposited the CNT with cement-based material Material processing.
The method that the CNT that the above embodiment of the present invention provides is scattered in cement matrix, to aid in gel material Expect the attachment as CNT, carbon nano tube growth is aiding in gel rubber material surface, and CNT is with mixing Solidifying soil auxiliary gel rubber material be combined with each other so that CNT is not susceptible to reunite on a large scale, and slackens Van der Waals force between CNT individual, therefore CNT is scattered in cement matrix by this method, Simple and efficient, dispersion effect is good, dust dispersion quality is high and it is extensive to be adapted to disperseing for the CNT of acquisition The advantages that engineering practice, a kind of effective scheme is provided to improve the fragility of architectural engineering concrete.
Brief description of the drawings
Technical scheme in order to illustrate the embodiments of the present invention more clearly, below will be to required in embodiment The accompanying drawing used is briefly described, it should be apparent that, drawings in the following description are only the one of the present invention A little embodiments, for those of ordinary skill in the art, on the premise of not paying creative work, also Other accompanying drawings can be obtained according to these accompanying drawings.
Fig. 1 is that CNT of the embodiment of the present invention is scattered in the method CNT of cement matrix in flyash The SEM figures of grain surface attachment situation；
Fig. 2 is that CNT of the embodiment of the present invention is scattered in the method CNT of cement matrix in flyash The EDS figures of grain surface distributed situation；
Fig. 3 be CNT of the embodiment of the present invention be scattered in cement matrix method obtain be attached to carbon nanometer SEM figure of the fly ash grain of pipe in cement paste；
Fig. 4 is SEM figure of the comparative example CNT of the present invention in cement paste；
Fig. 5 be CNT of the embodiment of the present invention be scattered in cement matrix method obtain be attached to carbon nanometer The SEM figures that the fly ash grain of pipe is distributed in hardened cement paste；
Fig. 6 be CNT of the embodiment of the present invention be scattered in cement matrix method obtain be attached to carbon nanometer The EDS figures that the fly ash grain of pipe is distributed in hardened cement paste.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, below in conjunction with accompanying drawing and reality Example is applied, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only Only to explain the present invention, it is not intended to limit the present invention.
The embodiment of the present invention provides a kind of method that CNT is scattered in cement matrix, including at least following step Suddenly：
Step S01. is heated to 500~1000 DEG C in an inert atmosphere, by auxiliary gel rubber material；
Step S02. is passed through gaseous carbon source, 500~1000 DEG C of keeping temperature, reaction life into institute's inert atmosphere Into CNT；
Step S03. is mixed the auxiliary gel rubber material that deposited the CNT with cement-based material Material processing.
Wherein, in a preferred embodiment, auxiliary gel rubber material is first placed in reaction vessel by step S01, Air in extraction container, inert gas, such as nitrogen, argon gas are then filled with into reaction vessel, Pumping inflation repeatedly, finally keep the pressure and external pressure strongly consistent of the inert gas in reaction vessel.
In a preferred embodiment, it is any of flyash, miberal powder, silicon ash to aid in gel rubber material. The particle diameter of gel rubber material is wherein aided in be no more than 500 microns, the carbon of the gel rubber material generation less than 500 microns Nanotube particle diameter is small, and aggregation is few, advantageously allows CNT and is more fully scattered in cement matrix.
In any embodiment, the flow of gaseous carbon source is 200~500m3/h.In the range of flow, knot Time≤60min of deposition reaction is closed, the synthetic quantity of CNT can be effectively controlled, avoid deposition mistake CNT is caused to gather greatly.
In a preferred embodiment, to avoid gaseous carbon from being only deposited at some position of auxiliary gel rubber material, When step S02 carries out gaseous state Carbon deposition, it is also necessary to constantly agitation auxiliary gel rubber material, it is solidifying by stirring auxiliary Glue material, it can effectively realize the uniform attachment of CNT.
In step S03, the auxiliary gel rubber material of gaseous carbon, that is, carbon nano tube growth and auxiliary deposited Gel rubber material surface, class core shell structure is formed, has slackened the Van der Waals force between CNT individual.With When cement matrix is mixed, mechanical agitation can be used, can also manually be stirred, can be according to actual work Journey needs reasonable selection.
The method that the CNT that the above embodiment of the present invention provides is scattered in cement matrix, it is first solidifying using auxiliary Attachment of the glue material as gaseous state Carbon deposition generation CNT so that the CNT of gaseous carbon generation is attached In auxiliary gel rubber material surface, realize CNT with aiding in be combineding with each other for gel rubber material, and pass through Flow and the reactive deposition time of gaseous carbon are controlled, avoids the extensive reunion of CNT, also simultaneously The Van der Waals force between CNT individual is slackened.When will be attached to the auxiliary gel rubber material of CNT with When cement matrix is mixed, it can cause CNT that there is good dispersion effect and dust dispersion quality.Adopt CNT is disperseed in cement matrix with this method, is suitable in large-scale construction projects practice.
In order to better illustrate the method that CNT provided in an embodiment of the present invention is scattered in cement matrix, under Face is illustrated by the way that embodiment is further.
Embodiment
Flyash is placed in inert gas environment, 500-1000 DEG C is heated to, then with 300m3/ h is passed through) Gaseous carbon source, it is 500-1000 DEG C to keep reaction temperature, the flyash of upset agitation at any time, makes CNT It is uniformly synthesized on fly ash grain, it is 30min to control sedimentation time.
The flyash of CNT will be grown in ESEM, it is attached that scanning result refers to specification Fig. 1.
CNT is effectively grown in fly ash grain surface as can be seen from Figure 1, and fly ash grain can be used as carbon The attachment of nanotube.
Then the flyash that grown CNT is subjected to EDS energy spectrum analysis, analysis result refers to explanation Book accompanying drawing 2.
As can be seen from Figure 2, CNT is mainly attached to fly ash grain surface, seldom occurs in other regions Gather.
In the flyash that the deposited CNT incorporation cement-based material that the present embodiment is obtained, after mixing water Mix, after standing 30 minutes, electronic microscope photos is scanned to cement slurry, scanning result refers to Bright book accompanying drawing 3.
As can be seen from Figure 3, obvious CNT is not had to gather in cement paste, CNT can be by repairing Supplementary cementitious material (flyash) after decorations is uniformly dispersed in cement paste.
In the flyash that the deposited CNT incorporation cement that the present embodiment is obtained, mix uniformly adds afterwards Water carries out hydration reaction, obtains hardened cement paste.And surface sweeping Electronic Speculum is carried out to the hardened cement paste of acquisition Observation analysis, scanned picture is as shown in Figure of description 5.
As can be seen from Figure 5, fly ash grain is evenly distributed in hardened cement paste, and aquation occurs for flyash After reaction, CNT comes off from fly ash grain surface, is connected with hydrolysis product of cement.To hardened cement Slurry carries out EDS energy spectrum analysis, refers to Figure of description 6.
As can be seen from Figure 6, in away from the hydrated product at 5 μm of fly ash grain, CNT be present, It can be seen that the process for dispersing has preferable dispersion effect.
In order to which CNT more provided in an embodiment of the present invention is scattered in the method and conventional method of cement matrix Difference, the present invention also CNT is scattered in cement matrix using conventional method.Specifically, CNT is dissolved in water in the presence of dispersant, supersonic oscillations 5-10 minutes are used during being somebody's turn to do. And electronic microscope photos is scanned to the slurry of acquisition, scanning result refers to Figure of description 4.
As can be seen from Figure 4, there is the phenomenon that obvious CNT gathers in cement slurry, it is seen that the conventional method Middle CNT can not be dispersed in inside cement slurry well.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in this hair Any modification, equivalent substitution or improvement made within bright spirit and principle etc., should be included in the present invention Protection domain within.

Claims (6)

1. a kind of method that CNT is scattered in cement matrix, including at least following steps：
Step S01. is heated to 500~1000 DEG C in an inert atmosphere, by auxiliary gel rubber material；
Step S02. is passed through gaseous carbon source, 500~1000 DEG C of keeping temperature, reaction life into institute's inert atmosphere Into CNT；
Step S03. is mixed the auxiliary gel rubber material that deposited the CNT with cement-based material Material processing.
2. the method that CNT as claimed in claim 1 is scattered in cement matrix, it is characterised in that：Institute The flow for stating gaseous carbon source is 200-500m3/h。
3. the method that CNT as claimed in claim 1 is scattered in cement matrix, it is characterised in that：Institute State reaction time≤60min.
4. the method that CNT as claimed in claim 1 is scattered in cement matrix, it is characterised in that：Institute It is any of flyash, miberal powder, silicon ash to state auxiliary gel rubber material.
5. the method that the CNT as described in claim 1-4 is any is scattered in cement matrix, its feature exist In：The pressure of the inert atmosphere is identical with the atmospheric pressure at place.
6. the method that the CNT as described in claim 1-4 is any is scattered in cement matrix, its feature exist In：The content of air and other gases is less than 3% in the inert atmosphere.
CN201610272980.XA 2016-04-28 2016-04-28 The method that CNT is scattered in cement matrix Pending CN107337197A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110168089A1 (en) * 2007-01-03 2011-07-14 Lockheed Martin Corporation Cnt-infused carbon fiber materials and process therefor
CN102131744A (en) * 2008-04-30 2011-07-20 米纳斯吉拉斯联合大学 Process for continuous, large-scale synthesis of carbon nanotubes on cement clinker, and nanostructured products
US9034101B2 (en) * 2012-03-12 2015-05-19 Procedo Enterprises Etablissement Method for manufacturing of supplementary cementitious materials (SCMS)

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110168089A1 (en) * 2007-01-03 2011-07-14 Lockheed Martin Corporation Cnt-infused carbon fiber materials and process therefor
CN102131744A (en) * 2008-04-30 2011-07-20 米纳斯吉拉斯联合大学 Process for continuous, large-scale synthesis of carbon nanotubes on cement clinker, and nanostructured products
US9034101B2 (en) * 2012-03-12 2015-05-19 Procedo Enterprises Etablissement Method for manufacturing of supplementary cementitious materials (SCMS)

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
OSCARM . DUNENS, ET AL: "Synthesis of Multiwalled Carbon Nanotubes on Fly Ash Derived Catalysts", 《ENVIRON. SCI.TECHNOL》 *
SHENGWEI SUN ET AL: "In situ growth of carbon nanotubes/carbon nanofibers on cement/mineral admixture particles: A review", 《CONSTRUCTION AND BUILDING MATERIALS》 *

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