CN116535124B - CNTs@microbead core-shell filler, cement-based composite material, preparation method and application - Google Patents
CNTs@microbead core-shell filler, cement-based composite material, preparation method and application Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
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- 239000000463 material Substances 0.000 claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 17
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims abstract description 13
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 16
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- 239000010881 fly ash Substances 0.000 claims description 14
- 229910021487 silica fume Inorganic materials 0.000 claims description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/10—Coating or impregnating
- C04B20/1055—Coating or impregnating with inorganic materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00241—Physical properties of the materials not provided for elsewhere in C04B2111/00
- C04B2111/00258—Electromagnetic wave absorbing or shielding materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00439—Physico-chemical properties of the materials not provided for elsewhere in C04B2111/00
- C04B2111/00465—Heat conducting materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a CNTs@microsphere core-shell filler, a cement-based composite material, a preparation method and application thereof, wherein the preparation method of the CNTs@microsphere core-shell filler comprises the following steps: uniformly dispersing GO in an organic solvent, and then adding pyrrole monomers into the organic solvent to obtain a mixed solution; cleaning the glass beads, adding the cleaned glass beads into the mixed solution, performing ultrasonic treatment for a set time, and transferring the glass beads to FeCl 3 Soaking in aqueous solution for a set time to obtain PPy+ GO@ microbeads; mixing PPy+ GO@ microbeads with ferrocene solution, adding hexane, and then carrying out microwave radiation with the power of 800-900W for 20-30s, and synthesizing CNTs on the glass microbeads in situ to prepare CNTs@microbead core-shell materials; the mass ratio of GO, pyrrole monomer, ferrocene, hexane and glass beads is 0.01-0.1:1-10:10-25:0.1-0.7:30-50. The visible material has excellent mechanical, electrical sensing, electromagnetic shielding and heat conducting properties and can be well applied to traffic&Structure intelligent monitoring, wallboard wave absorbing&Electromagnetic shielding and outdoor snow and ice melting engineering field.
Description
Technical Field
The invention relates to a preparation method of a cement-based composite material, in particular to a CNTs@microbead core-shell filler, a cement-based composite material, a preparation method and application.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
The cement-based composite material has the advantages of good compatibility with a concrete matrix, excellent intrinsic mechanical strength, excellent functional performance and the like. The cement-based conductive composite material mixed with the conductive filler can be developed into an intrinsic electrical sensor, and has great application potential in the aspects of infrastructure structural health monitoring and degradation early warning through an application or embedding means. The cement-based wave-absorbing composite material mixed with wave-absorbing filler can be developed into an intrinsic wall wave-absorbing component for high-grade buildings and military facilities.
In recent years, carbon Nanotubes (CNTs) have been widely studied for their excellent mechanical, electro/magnetic, thermal and other physical properties, but by adopting a direct addition method, nano-scale CNTs are prone to winding and agglomeration, and the conductive/magnetic properties of the corresponding CNTs are difficult to be effectively exerted in cement-based materials.
Attempts have been made to use cement clinker, sand, mineral admixture, polymer emulsion as a dispersion medium, and to adhere CNTs to cement clinker, sand, mineral admixture, polymer surface, etc. respectively, thereby attempting to achieve the dispersibility and functional performance of CNTs in the final cement matrix. However, this approach has the following problems: the surfaces of cement clinker, sand and stone and mineral admixture are difficult to be directly adhered with conductive/magnetic CNTs; the polymer emulsion belongs to insulating materials, and is difficult to ensure the realization of macroscopic electric conduction, magnetic conduction, heat conduction and other functions of the CNTs-based composite material.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide CNTs@microbead core-shell filler, a cement-based composite material, a preparation method and application.
In order to achieve the above object, the present invention is realized by the following technical scheme:
in a first aspect, the invention provides a preparation method of CNTs@microbead core-shell filler, comprising the following steps: uniformly dispersing GO in an organic solvent, and then adding pyrrole monomers into the organic solvent to obtain a mixed solution;
cleaning the glass beads, adding the cleaned glass beads into the mixed solution, performing ultrasonic treatment for a set time, and transferring the glass beads to FeCl 3 Soaking in aqueous solution for a set time to obtain PPy+ GO@ microbeads;
mixing PPy+ GO@ microbeads with ferrocene solution, adding hexane, and then carrying out microwave radiation with the power of 800-900W for 20-30s, and synthesizing CNTs on the glass microbeads in situ to prepare CNTs@microbead core-shell materials;
the mass ratio of GO, pyrrole monomer, ferrocene, hexane and glass beads is 0.01-0.1:1-10:10-25:0.1-0.7:30-50.
The ultrasonic treatment is used for better dispersing the GO and the pyrrole monomers and uniformly adsorbing the GO and the pyrrole monomers on the surfaces of the glass beads so as to facilitate subsequent polymerization; feCl 3 Oxidizing pyrrole monomers into polypyrrole by using the aqueous solution as an oxidant; iron atoms generated by the decomposition of ferrocene at high temperature are used as catalysts to promote the reaction, and hexane is a supplementary carbon source; the power and time of microwave irradiation are critical, too little or too short power results in insufficient reaction temperature, too high power or too long power results in ablative destruction of the CNTs structure.
The high surface area of GO is utilized to provide a large number of polymerization sites for pyrrole monomers, meanwhile, electrostatic interaction between negative charge and positive charge pyrrole of GO and pi-pi interaction between conjugated bonds of GO and pyrrole rings are utilized, polymerization of pyrrole on the surface of the GO sheet is promoted, and a stable and uniform GO@PPy layer is deposited on the surface of spherical glass body microbeads.
And (3) coating the microbeads of the GO@PPy layer in ferrocene solution (hexane) by microwave radiation, and growing CNTs with uniform diameter and good size distribution in situ to finally prepare the CNTs@microbead core-shell material.
When the CNTs@microbead core-shell material is doped into a cement-based system, the problem that CNTs are difficult to disperse and easy to agglomerate in the cement-based material by a direct addition method is effectively solved, the functions of self-sensing, electromagnetic shielding, wave absorption, heat conduction and the like of the corresponding cement-based composite material are greatly improved, and the CNTs@microbead core-shell material is developed to be applied to a high-performance intrinsic sensor for structural monitoring or an intrinsic wall wave absorption layer for high-grade buildings and military facilities.
In some embodiments, the glass microspheres are micron-sized glass microspheres.
Preferably, the glass beads have an average particle size of 2 to 10. Mu.m.
Further preferably, the glass beads have an average particle diameter of 2.3. Mu.m.
In some embodiments, the FeCl 3 The concentration of the aqueous solution is 0.1-0.15g/ml.
Preferably, the glass beads are in FeCl 3 The soaking time in the water solution is 10-30min.
In some embodiments, the GO has a number of layers ranging from 1 to 5, an oxygen content of greater than 40%, and% by mass. The number of layers and the oxygen content of GO are related to the dispersibility of GO in aqueous solution, the higher oxygen content can promote the dispersion of GO, and the fewer layers can play the role of GO as a nano material, so that agglomeration is avoided.
In some embodiments, the organic solvent is N-methylpyrrolidone (NMP).
Preferably, the mass ratio of N-methyl pyrrolidone to pyrrole monomer is 80-150:1-10.
In some embodiments, the glass beads are rinsed with acetone.
In some embodiments, the time of the sonication is from 0.5 to 1.5 hours and the temperature of the sonication is from 20 to 30 ℃.
In a second aspect, the invention provides a CNTs@microbead core-shell filler prepared by the preparation method.
In a third aspect, the invention provides a cement-based composite material comprising the following components in parts by weight: 100 parts of cement, 5-15 parts of fly ash, 4-9 parts of silica fume, 25-35 parts of water, 0.5-1.5 parts of water reducer and 0.4-5 parts of CNTs@microbead core-shell filler.
In some embodiments, an antifoaming agent is also included in the cementitious composite, the antifoaming agent being a silicone or tributyl phosphate.
In some embodiments, the cement is a type p.i.52.5, type p.ii 52.5, type p.i.62.5, or type p.ii 62.5 portland cement.
In some embodiments, the fly ash is a primary fly ash;
or the silica fume is S96 grade silica fume or above;
or the water reducing agent is a polycarboxylic acid high-efficiency water reducing agent with the water reducing rate of more than 30 percent.
In a fourth aspect, the present invention provides a method for preparing the cement-based composite material, comprising the steps of: mixing cement, fly ash, silica fume and CNTs@micro-bead core-shell filler in proportion in a dry manner to obtain a dry mixed material;
and mixing the dry mixed material with water dissolved with the water reducing agent, slowly stirring for 30-60s, and rapidly stirring for 2-5min to obtain the cement-based composite material.
In a fifth aspect, the invention provides application of the cement-based composite material in the fields of traffic and structural intelligent monitoring, wave-absorbing coating and electromagnetic shielding and outdoor snow melting and deicing.
The beneficial effects achieved by one or more embodiments of the present invention described above are as follows:
1. the CNTs are synthesized in situ on the microbeads by using a microwave radiation method to form CNTs@microbead core-shell materials by utilizing the characteristic that the microbeads can be uniformly dispersed in the cement-based material through full stirring, and the CNTs@microbead core-shell materials are added into the cement-based material as functional fillers, so that the CNTs can be uniformly dispersed in a cement matrix, the conductivity and the wave absorption performance of the CNTs are greatly exerted, and the force-electricity sensing and wave absorption performance of the cement-based material are greatly improved.
2. Because other dispersion methods can damage the structures of CNTs to a greater or lesser extent, the in-situ synthesis method can ensure that good dispersion effects are obtained by relying on the intermediation of CNTs@microbead core-shell under the condition that the CNTs are complete in structure, thereby maximizing the functional effect of CNTs.
3. GO is taken as an intermediate substance, and oxygen-containing groups are ablated under microwave radiation, so that the GO becomes CNTs, and the diameters of the CNTs finally generated are more consistent, and the size distribution is more uniform.
4. The CNTs@microsphere core-shell material reinforced cement-based composite material has the characteristics of excellent mechanical property, good durability, good compatibility with concrete materials and the like, has good intelligent power-electricity sensing, electromagnetic wave shielding performance and heat conducting performance, and can be widely applied to the technical fields of traffic and structure intelligent monitoring, wall material electromagnetic shielding and wave absorbing, outdoor snow melting and deicing and the like.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is a flow chart of the preparation of a CNTs@microbead core-shell material reinforced cement-based composite material;
FIG. 2 is a graph showing the conductivity test results of CNTs@microbead core-shell material reinforced cement-based composite material;
FIG. 3 is a graph showing the results of reflectance testing of CNTs@microbead core-shell material reinforced cement-based composite materials.
In the figure, 1-microbeads; a 2-pyrrole monomer; 3-GO-NMP dispersion; 4-FeCl 3 A solution; 5-ppy+ GO@ microbeads; 6-CNTs@microbead core-shell material; 7-dry mixing of the cementing material and sand; 8-a mixed solution of water and a water reducing agent; 9-CNTs@microbead core-shell material reinforced cement-based composite material; 10-ultrasonic dispersion; 11-oxidative polymerization; 12-microwave irradiation; 13-mixing and stirring; a-probe type ultrasonic cell grinder; b-constant temperature water bath; c-microwave oven.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The invention is further illustrated below with reference to examples.
Example 1
The CNTs@microbead core-shell material consists of the following raw materials in parts by weight: GO 0.01 part, pyrrole 1 part, feCl 3 Solution 5 parts, ferrocene 10 parts, hexane 0.1 parts, microbead 30 parts, NMP80 parts and acetone.
The preparation method of the CNTs@microbead core-shell material specifically comprises the following steps:
1) Deposition of GO and PPy on microbead surface: dispersing GO in NMP and performing ultrasonic treatment for 1h, adding purified pyrrole monomer into the dispersed GO solution, adding acetone-washed microbeads, performing ultrasonic treatment in water bath at 25 ℃ for 1h, taking out microbeads, and placing in FeCl 3 And (3) in the aqueous solution for 15min, finally, taking out the PPy+ GO@ microbeads after the coating treatment, washing and putting the microbeads in a containerDrying in an oven for 48h.
2) Ppy+ GO@ microbeads were deposited by microwave radiation: mixing PPy+ GO@ microbeads which are deposited step by step 11 with ferrocene solution, adding hexane, and carrying out microwave radiation on a sample in a microwave oven at 850W power for 30s so as to synthesize CNTs in situ on the microbeads, thereby preparing the CNTs@microbead core-shell material.
CNTs@microbead core-shell material reinforced cement-based composite material is composed of the following raw materials in parts by weight: 100 parts of P.I.52.5-type Portland cement, 5 parts of fly ash, 4 parts of silica fume, 25 parts of water, 1.5 parts of water reducer, 1 part of CNTs@microsphere core-shell material and 0.05 part of defoamer.
The preparation method of the CNTs@microbead core-shell material reinforced cement-based composite material specifically comprises the following steps:
1) The CNTs@microbead core-shell material is used as a functional filler to be doped into a cement-based material: adding the CNTs@microbead core-shell material obtained in step 12, a mineral admixture (fly ash and silica fume) and cement into a planetary stirrer, and rapidly dry-mixing for 5min to form a CNTs@microbead core-shell material reinforced cement-based dry mixture.
2) Adding the CNTs@microsphere core-shell material reinforced cement-based dry mixed material into water in which a water reducing agent is dissolved in advance, slowly stirring for 60s, then rapidly stirring for 3min, adding a proper amount of defoaming agent, then performing compression molding or pouring molding, and finally preparing the CNTs@microsphere core-shell material reinforced cement-based composite material through processes such as vibration curing.
Example 2
CNTs@microbead core-shell material consists of the following raw materials in parts by weight: GO 0.02 part, pyrrole 5 part, feCl 3 10 parts of solution, 20 parts of ferrocene, 0.2 part of hexane, 40 parts of microbeads, 120 parts of NMP and a plurality of acetone. The preparation method is the same as in example 1.
CNTs@microbead core-shell material reinforced cement-based composite material is composed of the following raw materials in parts by weight: 100 parts of P.I.52.5-type Portland cement, 5 parts of fly ash, 4 parts of silica fume, 25 parts of water, 1.5 parts of water reducer, 2 parts of CNTs@microsphere core-shell material and 0.06 part of defoamer. The preparation method is the same as in example 1.
Example 3
CNTs@microbead core-shell material is prepared from the following raw materials in parts by weightThe composition is as follows: GO 0.03 part, pyrrole 10 parts, feCl 3 15 parts of solution, 25 parts of ferrocene, 0.4 part of hexane, 50 parts of microbeads, 150 parts of NMP and a few of acetone. The preparation method is the same as in example 1.
CNTs@microbead core-shell material reinforced cement-based composite material is composed of the following raw materials in parts by weight: 100 parts of P.I.52.5-type Portland cement, 5 parts of fly ash, 4 parts of silica fume, 30 parts of water, 1 part of water reducer, 3 parts of CNTs@microsphere core-shell material and 0.07 part of defoamer. The preparation method is the same as in example 1.
Example 4
CNTs@microbead core-shell material consists of the following raw materials in parts by weight: GO 0.04 part, pyrrole 5 parts, feCl 3 15 parts of solution, 20 parts of ferrocene, 0.7 part of hexane, 50 parts of microbeads, 150 parts of NMP and a few of acetone. The preparation method is the same as in example 1.
CNTs@microbead core-shell material reinforced cement-based composite material is composed of the following raw materials in parts by weight: 100 parts of P.II.52.5-type Portland cement, 5 parts of fly ash, 4 parts of silica fume, 35 parts of water, 0.5 part of water reducer, 4 parts of CNTs@microsphere core-shell material and 0.08 part of defoamer. The preparation method is the same as in example 1.
Comparative example
CNTs@microbead core-shell material is not used;
the cement-based composite material of the control group consists of the following raw materials in parts by weight: 100 parts of P.II.52.5-type Portland cement, 5 parts of fly ash, 4 parts of silica fume, 35 parts of water, 0.5 part of water reducer and 0.08 part of defoamer. The preparation method is the same as in example 1.
The CNTs@microbead core-shell material, CNTs@microbead core-shell material reinforced cement-based composite material prepared in examples 1-4 and the performance test experimental method of the comparative example are as follows:
the characteristics and the purity of CNTs in the CNTs@microbead core-shell material are respectively characterized and detected by infrared spectrum and Raman spectrum means, and the result shows that the CNTs are 1750cm -1 Having a characteristic peak of carboxyl functional groups; at 1340cm respectively -1 、1580cm -1 The vicinity has typical D and G peaks.
Compression and bending test of materials: test reference Specification (ISO method) for testing the strength of cement mortar (GB/T17671-1999) tests the flexural strength and the compressive strength of mortar test blocks with different proportions and different ages (7 d and 28 d). The sample sizes were 160mm×40mm, three samples were grouped, and the test results were averaged.
The test results of mechanical properties of the samples of the comparative examples and examples 1-4 are shown in Table 1, and compared with the comparative example without CNTs@microsphere core-shell material, the mechanical properties of examples 1-4 are improved obviously, the doped CNTs@microsphere core-shell material ensures good dispersion of CNTs, plays the role of nano materials to the greatest extent, the CNTs with high slenderness ratio are easier to lap together, and expansion of microcracks in cement-based materials is prevented, so that the compressive strength of the macroscopic mechanical properties 7d can reach more than 70MPa, the flexural strength is generally about 10MPa, the compressive strength of 28d is more than 90MPa, and the flexural strength is about 13 MPa. The intrinsic sensing material has good compatibility with the engineering structure concrete material, does not damage the original structure, can even reinforce the original concrete structure, and has excellent mechanical properties so as to be capable of coping with more serious challenges in actual engineering.
TABLE 1 mechanical and thermal Properties of CNTs@microbead core-shell material reinforced Cement-based composite Material
CNTs@microbead core-shell material reinforced cement-based composite material conductivity test: and testing the conductivity of the dried CNTs@microbead core-shell material reinforced cement-based composite material sample by adopting a four-electrode method. The size of the sample is 60mm multiplied by 20mm, four copper meshes are manually inserted into the sample after the slurry is molded and vibrated to serve as electrodes, and the distance between the inner pair of electrodes and the outer pair of electrodes is 30mm and 50mm respectively. CNTs@microbead core-shell material reinforced cement-based composite material heat conductivity coefficient test: the thermal conductivity of the dried test pieces was measured by a flat plate thermal conductivity method, the test pieces were prismatic test pieces of 300mm×300mm×30mm in size, three test pieces were grouped, and the experimental results were averaged.
Intelligent force-electricity sensing test: the stress, strain and resistivity change of the sensor encapsulated by the CNTs@microbead core-shell material reinforced cement-based composite material when the sensor is embedded into a simply supported beam system to bear the action of three-point bending load are tested by combining the Wheatstone bridge technology and the dynamic signal acquisition technology.
The test of self-sensing performance is carried out on the samples of the control example and the examples 1-4, the change of the resistivity of the sensor formed by encapsulating the CNTs@microsphere core-shell material reinforced cement-based composite material when the CNTs@microsphere core-shell material is embedded into a simply supported beam system to bear three-point bending load in a midspan manner is researched by combining the Wheatstone bridge technology and the dynamic signal acquisition technology, and the result is shown in a table 2, compared with the control group, the maximum resistivity change rate, the stress sensitivity, the strain sensitivity, the linearity and the sensitivable sensing range of the sample are greatly improved after the CNTs@microsphere core-shell material is added, the maximum resistivity change rate of the example 1 can reach about 23.46%, the stress sensitivity is 0.45%/MPa, the strain sensitivity is 23, the linearity is 0.69%, the sensitively perceivable range is 0-60% peak stress, and the zero drift is 3.54% after 1 ten thousands of cyclic loads. The core-shell material of the doped CNTs@microbeads ensures good dispersion of the CNTs, so that the CNTs are easier to lap together when a test piece is stressed, and CNTs tunnel effect and contact conduction are facilitated.
Therefore, the CNTs@microbead core-shell material reinforced cement-based composite material has good intelligent force-electricity sensing performance.
TABLE 2 self-sensing Properties of CNTs@microbead core-shell material reinforced Cement-based composite Material
The preparation method of example 1 ensures that the ratios of other raw materials except GO are unchanged (the same as in example 1), CNTs@microbead core-shell filler reinforced cement-based composite materials with GO accounting for different ratios (0%, 0.02%,0.04%,0.06% and 0.08%) of pyrrole monomers are respectively prepared, and the conductivities are tested to obtain the graph 2. FIG. 2 shows that in the absence of GO, although ferrocene can produce cyclopentadienyl as a carbon source to form CNTs at high temperature, the resulting CNTs are not very good in diameter, length and uniformity due to macroscopic mixing between ferrocene and microbeads, and the corresponding sample conductivity is also relatively limited.
After adding GO, a large number of polymerization sites are provided for pyrrole monomers by utilizing the high surface area of GO, meanwhile, electrostatic interaction between negative charge and positive charge pyrrole of GO and pi-pi interaction between conjugated bonds of GO and pyrrole rings are utilized, polymerization of pyrrole on the surface of the GO sheet is promoted, a stable and uniform GO@PPy layer is deposited on the surface of spherical glass body microbeads, oxygen-containing groups carried by GO disappear and are converted into CNTs at high temperature, and thus, the obtained CNTs are good in size and uniformity, and the conductivity of the sample is greatly improved.
Reflectance test: according to the national military standard GJB2038A-2011, the reflectivity test method of the Radar Absorbing Material (RAM) comprises a radar scattering cross section (RCS) test method and an arch test method, and the reflectivity of a sample is tested by adopting the arch test method. The test samples were 200mm by 25mm, the test frequency was 2-18GHz, the test samples were dried before testing, three test samples per group, and the test results were an average of 3 test samples.
According to the preparation method of the embodiment 1, the proportions of other raw materials except GO are unchanged (the same as that of the embodiment 1), CNTs@microbead core-shell filler reinforced cement-based composite materials with GO accounting for different proportions of pyrrole monomers (0%, 0.01% and 0.05%) are respectively prepared, and a wave absorption performance test is carried out, so that each sample curve has a plurality of peaks lower than-10 dB in the range of 2-18GHz as shown in a graph 3, when the doping amount of GO is 0, the maximum absorption peak value of the sample appears at 3GHz, the frequency bandwidth lower than-10 dB is 5.1GHz, when the doping amount of GO is 0.01%, the maximum absorption peak value of the sample appears at 10GHz, the frequency bandwidth lower than-10 dB reaches 6.5GHz, when the doping amount of GO is 0.05%, the maximum absorption peak value of the sample appears at 4.7GHz, the frequency bandwidth lower than-10 dB reaches 11.5GHz, the frequency bandwidth of the sample reaches the maximum absorption peak value of 11.5GHz, the CNTs and the polarization degree of the CNTs under the action of a large pipe have more uniform polarization, and the dielectric loss is caused by the effect of the CNTs, and the dielectric loss is improved along with the addition of the CNTs, and the excellent performance is obtained.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (12)
1. A preparation method of CNTs@microbead core-shell filler is characterized by comprising the following steps: the method comprises the following steps: uniformly dispersing GO in an organic solvent, and then adding pyrrole monomers into the organic solvent to obtain a mixed solution;
cleaning the glass beads, adding the cleaned glass beads into the mixed solution, performing ultrasonic treatment for a set time, and transferring the glass beads to FeCl 3 Soaking in aqueous solution for a set time to obtain PPy+ GO@ microbeads;
mixing PPy+ GO@ microbeads with ferrocene solution, adding hexane, and then carrying out microwave radiation with the power of 800-900W for 20-30s, and synthesizing CNTs on the glass microbeads in situ to prepare CNTs@microbead core-shell materials;
the mass ratio of GO, pyrrole monomer, ferrocene, hexane and glass beads is 0.01-0.1:1-10:10-25:0.1-0.7:30-50;
the glass beads are micron-sized glass beads; the average particle size of the glass beads is 2-10 mu m.
2. The method for preparing the CNTs@microbead core-shell filler according to claim 1, which is characterized in that: the average particle diameter of the glass beads is 2.3 mu m.
3. The method for preparing the CNTs@microbead core-shell filler according to claim 1, which is characterized in that: the FeCl 3 The concentration of the aqueous solution is 0.1-0.15g/ml.
4. The CNTs@microbead core-shell filler according to claim 3The preparation method of (2) is characterized in that: glass bead in FeCl 3 The soaking time in the water solution is 10-30min.
5. The method for preparing the CNTs@microbead core-shell filler according to claim 1, which is characterized in that: the number of layers of the GO is 1-5, the oxygen content is more than 40%, and the percentage is mass percent.
6. The method for preparing the CNTs@microbead core-shell filler according to claim 1, which is characterized in that: the organic solvent is N-methyl pyrrolidone; the ultrasonic treatment time is 0.5-1.5h, and the ultrasonic treatment temperature is 20-30 ℃;
the mass ratio of N-methyl pyrrolidone to pyrrole monomer is (80-150): 1-10.
7. A CNTs@microbead core-shell filler is characterized in that: prepared by the preparation method of any one of claims 1 to 6.
8. A cement-based composite material, characterized in that: comprises the following components in parts by weight: 100 parts of cement, 5-15 parts of fly ash, 4-9 parts of silica fume, 25-35 parts of water, 0.5-1.5 parts of water reducer and 0.4-5 parts of CNTs@microbead core-shell filler according to claim 7.
9. The cement-based composite material of claim 8, wherein: the foam killer also comprises a foam killer, wherein the foam killer is organic silicon or tributyl phosphate.
10. The cement-based composite material of claim 8, wherein: the cement is P.I.52.5 type, P.II 52.5 type, P.I.62.5 type or P.II 62.5 type silicate cement;
the fly ash is first-grade fly ash.
11. The cement-based composite material of claim 8, wherein: the silica fume is S96 grade silica fume and above; the water reducing agent is a polycarboxylic acid high-efficiency water reducing agent with the water reducing rate of more than 30 percent.
12. A method of preparing a cement-based composite material as claimed in any one of claims 8 to 11, characterised by: the method comprises the following steps: mixing cement, fly ash, silica fume and CNTs@micro-bead core-shell filler in proportion in a dry manner to obtain a dry mixed material;
and mixing the dry mixed material with water dissolved with the water reducing agent, slowly stirring for 30-60s, and rapidly stirring for 2-5min to obtain the cement-based composite material.
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