CN107337197A - The method that CNT is scattered in cement matrix - Google Patents
The method that CNT is scattered in cement matrix Download PDFInfo
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- 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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- cnt
- scattered
- cement matrix
- cement
- rubber material
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- 239000004568 cement Substances 0.000 title claims abstract description 55
- 239000011159 matrix material Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000010881 fly ash Substances 0.000 claims description 22
- 238000012545 processing Methods 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002956 ash Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000000428 dust Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 6
- 230000008021 deposition Effects 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000005411 Van der Waals force Methods 0.000 description 4
- 239000002041 carbon nanotube Substances 0.000 description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 description 4
- 238000013019 agitation Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- -1 that is Chemical compound 0.000 description 1
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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Mechanical Engineering (AREA)
- Structural Engineering (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
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
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610272980.XA CN107337197A (en) | 2016-04-28 | 2016-04-28 | The method that CNT is scattered in cement matrix |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610272980.XA CN107337197A (en) | 2016-04-28 | 2016-04-28 | The method that CNT is scattered in cement matrix |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107337197A true CN107337197A (en) | 2017-11-10 |
Family
ID=60221773
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| CN201610272980.XA Pending CN107337197A (en) | 2016-04-28 | 2016-04-28 | The method that CNT is scattered in cement matrix |
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Citations (3)
| 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) |
-
2016
- 2016-04-28 CN CN201610272980.XA patent/CN107337197A/en active Pending
Patent Citations (3)
| 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)
| 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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