CN109231914A - A kind of concrete and preparation method thereof that graphene/fibrous composite is modified - Google Patents
A kind of concrete and preparation method thereof that graphene/fibrous composite is modified Download PDFInfo
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- CN109231914A CN109231914A CN201811145872.1A CN201811145872A CN109231914A CN 109231914 A CN109231914 A CN 109231914A CN 201811145872 A CN201811145872 A CN 201811145872A CN 109231914 A CN109231914 A CN 109231914A
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- 239000004567 concrete Substances 0.000 title claims abstract description 78
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 67
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims description 7
- 229920005594 polymer fiber Polymers 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000003638 chemical reducing agent Substances 0.000 claims description 12
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- -1 polyethylene Polymers 0.000 claims description 9
- 239000011398 Portland cement Substances 0.000 claims description 8
- 239000005457 ice water Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000002518 antifoaming agent Substances 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 235000010344 sodium nitrate Nutrition 0.000 claims description 6
- 239000004317 sodium nitrate Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 239000012286 potassium permanganate Substances 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000006004 Quartz sand Substances 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 239000002956 ash Substances 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000002893 slag Substances 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims 1
- GTTYPHLDORACJW-UHFFFAOYSA-N nitric acid;sodium Chemical compound [Na].O[N+]([O-])=O GTTYPHLDORACJW-UHFFFAOYSA-N 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 238000005452 bending Methods 0.000 abstract description 3
- 239000004035 construction material Substances 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000004615 ingredient Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 7
- 239000000835 fiber Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
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- 230000000052 comparative effect Effects 0.000 description 4
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- 239000000243 solution Substances 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 208000037656 Respiratory Sounds Diseases 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920005573 silicon-containing polymer Polymers 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
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- 238000013459 approach Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 230000005587 bubbling Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011083 cement mortar Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 239000011396 hydraulic cement Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
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- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
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- 239000010453 quartz Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000003469 silicate cement Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
Classifications
-
- 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
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/022—Carbon
- C04B14/024—Graphite
-
- 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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- 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
- C04B2111/90—Electrical properties
- C04B2111/94—Electrically 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
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
-
- 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
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
- C04B2201/52—High compression strength concretes, i.e. with a compression strength higher than about 55 N/mm2, e.g. reactive powder concrete [RPC]
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Civil Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of modified concrete of graphene/fibrous composite, contain graphene/polymer fiber composites.The present invention can be such that graphene uniform is dispersed in concrete using graphene/polymer fiber composites as the modifying agent of concrete, solve the problems, such as that graphene is easy to reunite in block materials.The mechanical performance of modified concrete prepared by the present invention, including impact resistance, tensile property and bending property greatly improve., ingredient good as construction material quality uniformly, be easy to industrialization.
Description
Technical field
The present invention relates to technical field of composite materials, and in particular to a kind of coagulation that graphene/fibrous composite is modified
The preparation method of soil and the modified concrete.
Background technique
Concrete is widely used in the field of civil engineering such as industry and civil buildings, bridge, harbour.It is reported that from
The whole world produces 3,600,000,000 tons of cement every year since 2011, wherein 55 or more percent comes from China.Concrete has higher
Compression strength, but have high brittleness, tensile strength is low, ductility and toughness are poor, anti-permeability performance easy to crack and low, in mechanical lotus
It carries under the collective effects of factors such as environmental load, endurance quality reduces, structure premature degradation or failure.Meanwhile green and
Sustainable development is the certainty in epoch, largely uses concrete, needs to produce a large amount of cement, seriously affect environment.
Countries in the world scientist has carried out extensive research, seeks the method solved these problems and approach.It is main at present
Concrete is modified at grading mode by reducing the ratio of mud, addition fiber and addition Separate Fine-grained Minerals matter.However, above-mentioned add
Addition point can not fundamentally improve gel microstructure, thus limited to the effect for improving concrete strength and durability.
Graphene (Graphene) is a kind of two dimension for forming hexangle type in honeycomb lattice with sp2 hybridized orbit by carbon atom
Carbon nanomaterial.Graphene has excellent optics, electricity, mechanical characteristic, such as high-tensile, large scale surface area and big
Surface area.Since graphene surface is there are fold, mechanical self-latching can be produced with cement gel, in graphene and concrete
Strong collective effect between portion's crackle inhibits the extension of crackle.Therefore graphene promotes hydrated cementitious and strong interface effect
The formation of power fundamentally improves tensile strength, flexural strength, the compression strength etc. of concrete.Meanwhile being suitably incorporated graphene
The microporous structure of concrete is improved, normal concrete chloride-penetration resistance, anti-carbonation and anti-freezing property etc. are improved.But mesh
Before, it is difficult to solve the dispersion of the graphene in concrete.
In consideration of it, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of concrete that graphene/fibrous composite is modified.
The second object of the present invention is to provide the preparation method of the modified concrete.
To achieve the above object, technical scheme is as follows:
The present invention relates to a kind of modified concrete of graphene/fibrous composite, contain graphene/polymer fiber
Composite material.
Preferably, mass percentage of the graphene/polymer fiber composites in the modified concrete
It is 0.5%~5%.
Preferably, the polymer fiber is selected from least one of polyethylene, polypropylene, vinal.
Preferably, the modified concrete is prepared by the raw material of following parts by weight:
Preferably, the portland cement is the portland cement of strength grade 52.5 or more.
Preferably, the industrial residue in silicon ash, slag, flyash, kaolin, zeolite powder and mine tailing at least
It is a kind of.
Preferably, the water-reducing agent is the water-reducing agent that water-reducing rate is not less than 35%.
Preferably, the defoaming agent is silicone fluid and/or dimethyl silicone polymer.
Preferably, the fine aggregate is selected from least one of yellow ground, quartz sand and the tailings that partial size is less than 2.5mm.
Preferably, the graphene/polymer fiber composites are prepared by the following method to obtain:
[1] graphite powder is mixed with sodium nitrate, obtains mixture;
[2] in ice-water bath, the mixture that step [1] obtains is added into the concentrated sulfuric acid, permanganic acid is added after being stirred
Potassium;
[3] reaction system that step [2] obtains is removed from ice-water bath, and is warming up to 35 DEG C, keep the temperature 30~50min;
[4] hydrogen peroxide solution is added in the reaction system obtained to step [3], and reaction filters after 2 hours, filter residue is dried
To graphene oxide;
[5] after being dispersed in water the graphene oxide, hydro-thermal reaction is carried out after polymer fiber is added, reaction terminates
After obtain graphene/polymer fiber composites.
Preferably, in step [1] and step [2], graphite powder, sodium nitrate, the concentrated sulfuric acid, potassium permanganate additional proportion be (1
~2g): (1~2g): (20~25ml): (2~3g).
Preferably, in step [5], the mass ratio of graphene oxide and polymer fiber is (20~30): (70~80), water
The condition of thermal response is to react 6~12 hours at 150~200 DEG C.
The invention further relates to the preparation methods of the modified concrete, the described method comprises the following steps:
(1) portland cement, industrial residue and fine aggregate are uniformly mixed, obtain mixture;
(2) water-reducing agent and defoaming agent are dissolved in water, obtain mixed solution;
(3) mixed solution that step (2) obtains is added in the mixture that step (1) obtains, after being uniformly mixed,
Graphene/polymer fiber composites are added, continues after being uniformly mixed, obtains modified concrete;
(4) modified concrete is poured in a mold, is conserved after jolt ramming molding.
Beneficial effects of the present invention:
The present invention is using graphene/polymer fiber composites as the modifying agent of concrete.Wherein, polymer fiber had been both
Has the function of toughening, and can be used as the carrier of graphene solve dispersion problem of the graphene in concrete.Graphite
The electric conductivity of inside concrete can be improved in alkene, can also be used as nano-particles filled in the internal interstices of concrete, improves
The integral strength of concrete.The mechanical performance of modified concrete prepared by the present invention, including impact resistance, tensile property and curved
Qu Xingneng is greatly improved., ingredient good as construction material quality uniformly, be easy to industrialization.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, technical solution of the present invention will be carried out below
Detailed description.Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Base
Embodiment in the present invention, those of ordinary skill in the art are obtained all without making creative work
Other embodiment belongs to the range that the present invention is protected.
The present embodiments relate to a kind of modified concrete of graphene/fibrous composite, contain in modified concrete
There are graphene/polymer fiber composites, can be improved the mechanical performance of concrete.
In one embodiment of the invention, quality of the graphene/polymer fiber composites in modified concrete
Percentage composition is 0.5%~5%.
In one embodiment of the invention, polymer fiber in polyethylene, polypropylene, vinal extremely
Few one kind.Above-mentioned fiber be pencil synthetic fibers, pull open it is rear network-like, can also be cut into length be 10~60mm fiber
Section uses.Above-mentioned polymer fiber, which can efficiently control the factors such as concrete/mortar plastic shrinkage, drying shrinkage, temperature change, to be caused
Micro-crack, prevent and inhibit the formation and development of concrete pre-existing fracture, substantially improve the waterproofing and anti-leakage of concrete/mortar
Energy, scour & wear resistance energy, increase the toughness of concrete, to improve the service life of concrete.
In one embodiment of the invention, modified concrete is prepared by the raw material of following parts by weight:
Further, the portland cement used is the portland cement of strength grade >=52.5.
Further, the industrial residue used is in silicon ash, slag, flyash, kaolin, zeolite powder and mine tailing
At least one, the partial size of above-mentioned industrial residue is in the micron-scale.Industrial residue, which is added, can not only turn waste into wealth, and reduce silicate cement
The dosage of mud, additionally it is possible to which the setting time for shortening concrete improves its resistance to compression and flexural strength.
Further, the water-reducing agent used is the water-reducing agent that water-reducing rate is not less than 35%.In the condition that cement consumption is constant
Under, water-reducing agent can reduce mixing water amount, improve concrete strength.By material point including lignin sulfonate water-reducing agent,
Ppolynuclear aromatic salt water-reducing agent and water-soluble resin Sulfonates water-reducing agent.
Further, the defoaming agent used is silicone fluid and/or dimethyl silicone polymer.Can be had using defoaming agent
The generation of foam, makes the finer and close light of concrete component in effect control cement mortar system.Facilitate carrier and bubbling system
Combination and inhibit foam to generate, and cost can be reduced.
Further, the fine aggregate used is selected from partial size less than at least one in the yellow ground of 2.5mm, quartz sand and tailings
Kind.Fine aggregate is the construction material opposite with coarse aggregate, is partial size usually in 4.75mm granular loose material below.Fine aggregate
Skeleton or filling effect are played in concrete.
Since graphene has high specific surface area, heating conduction outstanding and mechanical property and its outstanding electron transmission
A series of excellent properties such as performance, if can be reduced inside it using graphene as in lubricating type material incorporation concrete
Coefficient of friction, effectively improve its intensity, toughness, wearability and corrosion resistance.However since the effect of interlayer Van der Waals force is led
It causes graphene to be easy to occur to reunite even to stack, thus loses advantage possessed by extra specific surface area and two-dimensional structure.Shen
It asks someone the study found that if graphene and polymer fiber progress is compound then obtained graphene/polymer fiber is compound
Additive of the material as concrete can improve dispersibility of the graphene in concrete, play the interface interaction of graphene.
In one embodiment of the invention, graphene/polymer fiber composites are prepared by the following method to obtain:
[1] graphite powder is mixed with sodium nitrate, obtains mixture.
[2] in ice-water bath, the mixture that step [1] obtains is added into the concentrated sulfuric acid, permanganic acid is added after being stirred
Potassium.
In one embodiment of the invention, in step (1) and step (2), graphite powder, sodium nitrate, the concentrated sulfuric acid, permanganic acid
The additional proportion of potassium is (1~2g): (1~2g): (20~25ml): (2~3g).
[3] reaction system that step [2] obtains is removed from ice-water bath, and is warming up to 35 DEG C, keep the temperature 30~50min,
The process can carry out under oil bath or water bath condition.
[4] hydrogen peroxide solution that mass concentration is 30% is added in the reaction system obtained to step [3], after reaction 2 hours,
System bubble-free generates at this time.Reaction solution is filtered using miillpore filter, will filter obtained precipitating deionized water into
Row repeatedly washing, until sulfate radical-free detects.Graphene oxide is obtained after precipitating is dried in vacuo.
[5] after being dispersed in water the graphene oxide that step [4] obtains, polymer fiber is added and carries out hydro-thermal reaction,
Graphene/polymer fiber composites are obtained after reaction.
In one embodiment of the invention, the mass ratio of graphene oxide and polymer fiber is (20~30): (70~
80), the condition of hydro-thermal reaction is to react 6~12 hours at 150~200 DEG C, is reacted 8 hours preferably at 170~180 DEG C.
The embodiment of the present invention further relates to the preparation method of above-mentioned modified concrete, method includes the following steps:
(1) that portland cement, industrial residue and fine aggregate are put into stirrer for mixing is uniform, obtains mixture.It can also
Other additives, such as glass fibre, reinforcing agent, pigment etc. to be added in the whipping process.
(2) water-reducing agent and defoaming agent are dissolved in water, obtain mixed solution.
(3) mixed solution that step (2) obtains is added in the mixture that step (1) obtains, stirring 3~5min mixing
After uniformly, graphene/polymer fiber composites are added, continues to be stirred 3~5min, makes solid material from dispersity
Become viscous paste state, obtains modified concrete.
(4) modified concrete that step (3) obtains is poured in a mold, is conserved after jolt ramming molding.
Embodiment 1
Prepare graphene/polymer fiber composites:
(1) 1g graphite powder is mixed with 1g sodium nitrate, obtains mixture.
(2) in ice-water bath, it is slowly added to the mixture that step (1) obtains into the 20ml concentrated sulfuric acid, delays after being stirred
It is slow that 2g potassium permanganate is added, continue to stir 20min.
(3) reaction system that step (2) obtains is removed from ice-water bath, be placed in water-bath and be warming up to 35 DEG C, heat preservation
30min。
(4) hydrogen peroxide solution that mass concentration is 30% is added in the reaction system obtained to step (3), after reaction 2 hours,
System bubble-free generates at this time.Reaction solution is filtered using miillpore filter, will filter obtained precipitating deionized water into
Row repeatedly washing, until sulfate radical-free detects.Graphene oxide is obtained after precipitating is dried in vacuo.
(5) after being dispersed in water the graphene oxide that step (4) obtains, progress hydro-thermal is anti-after polypropylene fibre is added
It answers, obtains graphene/polymer fiber composites after reaction.The condition and graphene oxide of hydro-thermal reaction and poly-
The mass ratio for closing fibres is shown in Table 1.
Prepare modified concrete:
(1) portland cement, 20 weight parts of fine coal ash and the 50 parts by weight quartz for being 52.5 by 30 parts by weight strength grades
It is uniform that sand is put into stirrer for mixing, obtains mixture.
(2) water-reducing agent (production of Zibo City Zichuan Pian Gui factory) and defoaming agent (Tianjin Jin Feng production) are dissolved in water, are obtained
To mixed solution.
(3) mixed solution that step (2) obtains is added in the mixture that step (1) obtains, stirring 3~5min mixing
After uniformly, graphene/polymer fiber composites are added, continues to be stirred 3~5min, makes solid material from dispersity
Become viscous paste state, obtains modified concrete.Mass content of the graphene/polymer fiber composites in concrete
It is shown in Table 1.
Table 1
Comparative example 1
Graphene/polymer fiber composites are replaced with to the graphene of identical weight, other operations are the same as embodiment 1-
1。
Comparative example 2
Graphene/epoxy resin composite material is replaced with to the polypropylene fibre of identical weight, other same embodiments of operation
1-1。
Comparative example 3
Graphene and polypropylene fibre in (3) while being added the step of preparing modified concrete, other operations are the same as real
Apply a 1-1.
Test case
Obtained modified concrete is poured into mold, and places hardening at ambient temperature, obtain having a size of 4 × 4 ×
The cuboid of 16cm.It is conserved under field conditions (factors) by 28 days, according to GB 17671-1999 Test method for strength of hydraulic cement mortar to it
Crooked experiment and the test of simple crush test are carried out, the electric flux of harbor work's standard JTJ-275 test concrete, knot are showed according to China
Fruit is shown in Table 2.
Table 2
It can be seen that the ultra-dispersed type that embodiment 1-1 to 1-11 is prepared using the present invention from above-mentioned test result
Additive of the graphene/polymer fiber composites as concrete, tensile strength, bending strength and electric flux are obviously good
In comparative example 1-3.And the two is directly used in concrete without compound, performance boost is unobvious.It should be noted that electricity is logical
It measures smaller, illustrates that concrete durability is better.It, can be with by mixing a certain amount of graphene in concrete as conducting medium
The electric conductivity for substantially improving concrete can be used for the non-damaged inspection and evaluation of concrete structure, such as the fine fisssure of large scale structure
Line monitoring etc..
Further, the ultra-dispersed type graphene being prepared for hydro-thermal reaction 8 hours at 170~180 DEG C/polymer is fine
When tieing up composite material for concrete, there is best bending strength, compression strength and electric conductivity.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain
Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (10)
1. a kind of modified concrete of graphene/fibrous composite, which is characterized in that it contains graphene/polymer fiber
Composite material.
2. modified concrete according to claim 1, which is characterized in that the graphene/polymer fiber composites
Mass percentage in the modified concrete is 0.5%~5%.
3. modified concrete according to claim 1, which is characterized in that the polymer fiber is selected from polyethylene, poly- third
At least one of alkene, vinal.
4. modified concrete according to claim 1, which is characterized in that the modified concrete by following parts by weight original
Material is prepared:
5. modified concrete according to claim 4, which is characterized in that the industrial residue is selected from silicon ash, slag, fine coal
At least one of ash, kaolin, zeolite powder and mine tailing.
6. modified concrete according to claim 4, which is characterized in that the fine aggregate is selected from partial size less than 2.5mm's
At least one of yellow ground, quartz sand and tailings.
7. modified concrete according to claim 1, which is characterized in that the graphene/polymer fiber composites
It is prepared by the following method to obtain:
[1] graphite powder is mixed with sodium nitrate, obtains mixture;
[2] in ice-water bath, the mixture that step [1] obtains is added into the concentrated sulfuric acid, potassium permanganate is added after being stirred;
[3] reaction system that step [2] obtains is removed from ice-water bath, and is warming up to 35 DEG C, keep the temperature 30~50min;
[4] hydrogen peroxide solution is added in the reaction system obtained to step [3], and reaction filters after 2 hours, filter residue is dried to obtain oxygen
Graphite alkene;
[5] after being dispersed in water the graphene oxide, hydro-thermal reaction is carried out after polymer fiber is added, after reaction
To graphene/polymer fiber composites.
8. modified concrete according to claim 7, which is characterized in that in step [1] and step [2], graphite powder, nitric acid
Sodium, the concentrated sulfuric acid, potassium permanganate additional proportion be (1~2g): (1~2g): (20~25ml): (2~3g).
9. modified concrete according to claim 7, which is characterized in that in step [5], graphene oxide and polymer are fine
The mass ratio of dimension is (20~30): (70~80), and the condition of hydro-thermal reaction is to react 6~12 hours at 150~200 DEG C.
10. according to claim 1 to the preparation method of any one of 9 modified concretes, which is characterized in that the method includes
Following steps:
(1) portland cement, industrial residue and fine aggregate are uniformly mixed, obtain mixture;
(2) water-reducing agent and defoaming agent are dissolved in water, obtain mixed solution;
(3) mixed solution that step (2) obtains is added in the mixture that step (1) obtains, after being uniformly mixed, is added
Graphene/polymer fiber composites continues after being uniformly mixed, obtains modified concrete;
(4) modified concrete is poured in a mold, is conserved after jolt ramming molding.
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