CN107512889B - A kind of high-performance fiber concrete of C130 strength grade and preparation method thereof - Google Patents

A kind of high-performance fiber concrete of C130 strength grade and preparation method thereof Download PDF

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CN107512889B
CN107512889B CN201710703020.9A CN201710703020A CN107512889B CN 107512889 B CN107512889 B CN 107512889B CN 201710703020 A CN201710703020 A CN 201710703020A CN 107512889 B CN107512889 B CN 107512889B
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water
concrete
carbon nano
fiber concrete
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CN107512889A (en
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郑山锁
董立国
董方园
郑捷
蔡永龙
刘巍
秦卿
宋明辰
王斌
尚志刚
阮升
郑淏
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Xian University of Architecture and Technology
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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
    • 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
    • C04B14/026—Carbon of particular shape, e.g. nanotubes
    • 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
    • C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B16/02—Cellulosic 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
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/06—Combustion residues, e.g. purification products of smoke, fumes or exhaust gases
    • C04B18/10—Burned or pyrolised refuse
    • C04B18/101—Burned rice husks or other burned vegetable material
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Civil Engineering (AREA)
  • Environmental & Geological Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Nanotechnology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Revetment (AREA)

Abstract

The invention discloses high-performance fiber concrete of a kind of C130 strength grade and preparation method thereof, the mass parts composition of the concrete is as follows: 450-470 parts of cement, 100-110 parts of water, 720-750 parts of river sand, 1010-1050 parts of rubble, 60-95 parts of flyash, 50-70 parts of rice hull ash, 50-70 parts of silicon ash, 12-13 parts of water-reducing agent, 14-15 parts of exciting agent, 1.1-1.8 parts of cellulose fibre, 27-29 parts of hydroxyl modification carbon nano tube dispersion liquid, 2.3-2.5 parts of defoaming agent.The concrete of preparation toughness with higher and excellent endurance quality, the adhesion strength with higher between fashioned iron.For can effectively play the cooperative work performance between fashioned iron and concrete in reinforced concrete composite structure, the deficiency that bond between steel and concrete performance is poor, is unable to give full play the respective mechanical property of the two is made up.

Description

A kind of high-performance fiber concrete of C130 strength grade and preparation method thereof
Technical field
It is that one kind mixes rice hull ash, cellulose fibre and modified carbon nano-tube the invention belongs to New Building Materials field High intensity, high tenacity and high durability concrete, and in particular to a kind of high-performance of the C130 strength grade with high tenacity Fiber concrete and preparation method thereof.
Background technique
The tensile strength of normal concrete and cement-based material is low, poor toughness, in hardening process or under external loads effect A large amount of microcracks can be generated, the durability of concrete or cement-base composite material structure is seriously affected, reduce structure service life. In order to overcome the brittleness of normal concrete and high performance concrete, asbestos fibre, steel fibre, carbon fiber with toughening effect, Vinal, polypropylene fibre and the biggish fiber of basalt fibre equal length are used in concrete, but above-mentioned Long stapled a large amount of uses are easy agglomerating in concrete, are unfavorable for the evenly dispersed of aggregate, limit fiber mixed containing coarse aggregate Application in solidifying soil.
Carbon nanotube is a kind of one dimension fibre material with Nano grade diameter and micron level length, and draw ratio is high Up to 100-1000, elasticity modulus (can reach 1TPa or so) is about 5 times of steel and density is the 1/6 of steel；Carbon is received The tensile strength of mitron then can reach 60GPa-150GPa, and compressive strength 100GPa-170GPa, breaking strain is in 30%- 50% range.Because of its excellent Physical and mechanical properties, carbon nanotube is made to become ideal composite material reinforcing fiber.But by In carbon nano tube surface it is complete it is smooth, defect is few, lacks active group, relatively molten in water and various solution or composite material Xie Du is lower, and there are there is very big surface free energy, therefore carbon at biggish Van der Waals force, surface between carbon nanotube in addition Spontaneous reunion or winding easily occur between nanotube, it is evenly dispersed in certain polymer to seriously affect carbon nanotube. The present invention is dispersed and is ultrasonically treated to multi-walled carbon nanotube using surfactant, is not being cut off carbon nanotube and is not being destroyed On the basis of its surface texture, the modified multiwalled carbon nanotube dispersion liquid for capableing of stable dispersion in water is obtained, thus can It is enough in concrete, gives full play to its microfibre toughening effect.
Using the cellulose fibre with water storage function and toughening effect and the (tool of the rice hull ash with ultrafine micropore structure Have porous structure rice hull ash can absorb moisture), " the interior maintenance action " of two kinds of materials can promote the aquation of cementitious material into Journey；In addition, to improve the toughness of concrete, and making to be gelled by the way that both components of modified carbon nano-tube are added in concrete Material in hydration process aquation more sufficiently, improve the densification of the crystal shape or even concrete inner structure of hydrated product Degree reduces Cl-、SO4 2-、CO2The intrusion of equal harmful ions, is finally reached the intensity and endurance quality for improving concrete, and mention Rise its toughness, the target of plasticity and tensile strength.
Summary of the invention
The purpose of the present invention is to provide high-performance fiber concrete of a kind of C130 strength grade and preparation method thereof, originally Invention uses cellulose fibre, rice hull ash, modified carbon nano-tube, cement, flyash, river sand, rubble, chemical admixture for the first time (including water-reducing agent, exciting agent, defoaming agent), water are prepared for a kind of with high volume stability, high tenacity, high-durability, superelevation The fiber high performance concrete of the C130 strength grade of intensity overcomes normal concrete brittleness is big, easy to crack, durability is poor etc. It is insufficient.By add have volcano ash effect, physics filing effect and " interior maintenance action " rice hull ash, have toughening effect and The cellulose fibre of " interior maintenance action ", and the modified carbon nano-tube etc. of microfibre filled toughening effect, each component can be played Between collaboration improve concrete performance, and then be configured to a kind of there is high intensity, high volume stability, high-durability and compared with high-ductility The high-performance fiber concrete of the C130 strength grade of property.
To achieve the above object, technical solution disclosed by the invention is:
A kind of high-performance fiber concrete of C130 strength grade, the raw material including following mass fractions:
450-470 parts of cement, 100-110 parts of water, 720-750 parts of river sand, 1010-1050 parts of rubble, flyash 60-95 Part, 50-70 parts of rice hull ash, 50-70 parts of silicon ash, 12-13 parts of water-reducing agent, 14-15 parts of exciting agent, 1.1-1.8 parts of cellulose fibre, 27-29 parts of hydroxyl modification carbon nano tube dispersion liquid, 2.3-2.5 parts of defoaming agent.
Preferably, each component calculates optimal match ratio content with mass fraction in the concrete are as follows:
458 parts of cement, 106 parts of water, 740 parts of river sand, 1040 parts of rubble, 70 parts of flyash, 65 parts of rice hull ash, silicon ash 65 Part, 12.6 parts of water-reducing agent, 14.2 parts of exciting agent, 1.6 parts of cellulose fibre, 29 parts of hydroxyl modification carbon nano tube dispersion liquid, defoaming 2.4 parts of agent.
The cement is PO52.5R grades of ordinary portland cements.
Thick river sand during the river sand selection gradation is good, fineness modulus 2.8-3.2.
Artificial rubble based on the rubble selection lime stone, particle size range 5-16mm, according to continuous size fraction gradation.
The flyash uses the high-quality I grade of flyash of power plant, and 45 μm of square hole screens are tailed over no more than 12%, water demand ratio No more than 95%, specific surface area should be greater than 400m2/kg。
The mass percent of silica is not less than 93% in the silicon ash, and pozzolanic activity index is greater than 90%, averagely 0.1-0.15 μm of partial size, specific surface area is greater than 15m2/g。
The water-reducing agent is polycarboxylate high performance water-reducing agent, and solid content 20%, water-reducing rate is 25% or more.
The defoaming agent uses U.S.'s Hexion AXILAT DF6352DD defoaming agent.
The rice hull ash be by rice husk 650-800 DEG C at a temperature of burn, be made using ball mill grinding 20-30min Powder grey powder, dioxide-containing silica are 90% or more, and partial size is 10-75 μm, and specific surface area is in 40-100m2Between/g.
The exciting agent use Organic-inorganic composite exciting agent, composite exciting agent according to following mass percent meters original Material compounds:
Sodium sulphate 60-68%, calcium chloride 30-38%, triethanolamine 1.5-2%.
The cellulose fibre is UF500 cellulose fibre, and length 2-3mm, diameter is 15-20 μm, tensile strength >= 900MPa, elasticity modulus >=8.5GPa, fracture elongation reach 10%, specific gravity 1.1g/cm3。
The hydroxyl modification carbon nano tube dispersion liquid is as made from following methods:
1) compound concentration is the NaOH aqueous solution of 2.0M, weighs the NaOH water that 100 parts of preparations are added in 2 parts of multi-walled carbon nanotubes In solution, it is ultrasonically treated 5min；Carbon nano tube dispersion liquid is poured into autoclave, 180 DEG C of reaction 120min after sealing；It is cold afterwards But to room temperature, centrifuge separation is added deionized water and dilutes and wash, removes clear liquid；Ultrasound 10min again, stirring, vinylidene chloride filter Film filtering, gained solid product are washed to filtrate as neutrality；Dry 12h, obtains the oxygen-containing functional groups such as surface hydroxyl at 40 DEG C Modified multiwalled carbon nanotube；
2) modified multiwalled carbon nanotube, the surface-active of the oxygen-containing functional groups such as the surface hydroxyl prepared in step 1) are weighed 0.5 part of agent, 0.1 part of defoaming agent and 98 parts of deionized water, surfactant, defoaming agent and modified carbon nano-tube are successively distributed to In deionized water, stirring soaks carbon nanotube completely by aqueous surfactant solution；It is ultrasonically treated 30min；Later to dispersion Liquid carries out centrifugal sedimentation；
3) supernatant liquid is crossed into 300 mesh filter clothes, obtains carbon nano tube dispersion liquid 1；The carbon nanotube that bottom precipitation is reunited It carries out ultrasound 60min again according to step 2), obtains carbon nano tube dispersion liquid 2, hydroxyl modification in carbon nano tube dispersion liquid 1 and 2 Multi-walled carbon nanotube uniform and stable can disperse in water.
The multi-walled carbon nanotube is averaged caliber as 40-50nm, and length is 10-20 μm, purity >=98%；
The surfactant is Triton X-100；The defoaming agent uses U.S.'s Hexion AXILAT DF6352DD defoaming agent.
The present invention also provides a kind of preparation methods of the high-performance fiber concrete of C130 strength grade, including walk as follows It is rapid:
1) 12-13 parts of water-reducing agents and 27-29 parts of hydroxyl modification carbon nano tube dispersion liquids are added to the 25% of total Water In water, it is denoted as aqueous solution 1；Load weighted 2.3-2.5 parts of defoaming agent is added in the water of total Water 25%, aqueous solution 2 is denoted as；
2) 720-750 parts of river sands, 1010-1050 parts of rubbles, 1.1-1.8 parts of cellulose fibres will be weighed in mass ratio to be added Into blender, uniform stirring 2-3min；
3) 450-470 parts of cement, 60-95 parts of flyash, 50-70 parts of rice hull ash, 50-70 parts of silicon ashes then, are sequentially added With 14-15 parts of exciting agents, then the water of total Water remaining 50% is added in blender, uniform stirring 2-3min；
4) then to the aqueous solution 1 being added in blender in step 1), uniform stirring 3-4min；
5) mobility for finally observing mixture, continues the aqueous solution 2 that will be prepared in step 1), uniform stirring 3-5min, Discharging obtains prepared concrete mix；And it forms, conserve.
In preparation method concrete curing method be water in conserve: by concrete batching system be poured into cast iron die at Type, jolt ramming, being placed in temperature is in 20 ± 2 DEG C of environment, in the geotextiles of test block surface covering wetting, stands 1d, demoulding, then It conserves in the pond of the saturated limewater solution of standard curing room to required age.
Novelty of the invention ties up to cellulose fibre, the tool being mixed in concrete with toughening and interior maintenance action There is a kind of carbon-free rice hull ash of novel active mineral admixture of interior maintenance action, and changing with toughening and nano-filled effect Property multi-walled carbon nanotube.Synergistic effect between each component can promote cementitious material aquation more abundant, improve in concrete The microcosmic composition in portion reduces detrimental voids quantity, keeps concrete inner structure more closely knit, finally prepare with it is high-intensitive, High tenacity, high-durability, high volume stability novel high-performance fiber concrete material.
Compared with the prior art, the beneficial effects of the present invention are:
1) cellulose fibre used in the present invention has natural hydrophily and high-elastic model point, can effectively inhibit mixed The formation and development of microcrack caused by the factors such as solidifying soil plastic shrinkage, drying shrinkage, temperature change；Cellulose fiber surface has very Strong bond stress has good cementitiousness with cement matrix, prevents spike protein gene in concrete cracking, prevent crack Further development, and the fracture of fiber can increase the energy dissipation capacity of concrete；In addition, cellulose fibre has unique fiber Cavity structure and huge specific surface area, cavity structure can store partial moisture, play " interior maintenance action ", promote coagulation The heat evolution velocity of soil.Therefore, it is resistance to can be improved mechanical property and cracking resistance, impervious and freeze thawing resistance of concrete etc. for cellulose fibre Long performance.
2) silica for containing 90% or more in the present invention by the rice hull ash that combusting rice hull, grinding obtain, has higher Pozzolanic activity, the particle of rice hull ash is tiny (particle be 10-75 μm), the porous and net road structure inside rice hull ash particle Huge specific surface area is made it have, 40-100m can be reached2/g.Therefore, incorporation rice hull ash can make gelling material particles more Uniformly, gradation is good, can play filling role, and then increase the cohesiveness of concrete；Secondly as big inside rice hull ash The microcellular structure of amount can water storage, play " interior maintenance action "；In addition, since rice hull ash is living with volcanic ash similar with silicon ash Property, the Ca (OH) in partially or completely silicon ash, with concrete system can be replaced2Reaction generates fine and close hard aquation sulphur aluminium Sour calcium improves flexural strength, compression strength, the tensile splitting strength, endurance quality of concrete；Finally, rice hull ash is as agricultural Waste material is used as construction material replacing partial cement after being processed to, can reduce due in rice husk burning and cement production process CO2Discharge amount, and then concrete cost is reduced, it realizes the recycling of agricultural wastes, reaches energy-saving and environment-friendly purpose.
3) present invention is dispersed and is ultrasonically treated to multi-walled carbon nanotube using surfactant, is not cutting off carbon nanometer It pipe and does not destroy on the basis of its surface texture, obtains the modified multiwalled carbon nanotube dispersion liquid for capableing of stable dispersion in water. Due to the nanometer size effect and skin effect of carbon nanotube, bridge linking effect is played as nano-scale fiber, control nanoscale is split The emergence and development of seam increase the intensity etc. of concrete base material；In addition, the micro-packing effect of carbon nanotube, can fill Most of detrimental voids of inside concrete increase the compactness of concrete, improve the various aspects such as toughness of concrete, endurance quality Performance.
Above-mentioned measure can effectively improve compression strength, toughness, deformability, the endurance quality etc. of concrete, and enhance Adhesion strength and cooperative transformation ability between concrete and fashioned iron.The C130 intensity that the method is prepared through the invention The high-performance fiber concrete of grade, flexural strength are not less than 29.96MPa, and 28d cubic compressive strength is not less than 131.21MPa, split tensile strength not less than between 11.54MPa, with fashioned iron adhesion strength be not less than 5.81MPa, unstable state chlorine from Sub- transport coefficient DRCMNo more than 18 × 10-14m2/s.The present invention has prepared resistance to superhigh intensity, high volume stability, height The high-performance fiber concrete of long property and high tenacity, raw material are easy to get, preparation process is simple, meet sustainable development and modern times Requirement green construction material application and promoted is a kind of environmentally protective novel high-performance fiber concrete material.
Specific embodiment
With reference to embodiment, the present invention is described in further detail using embodiment, so that advantage of the invention is easier to In the protection scope for being readily appreciated by one skilled in the art, but being not intended to restrict the invention.
The high-performance fiber concrete of C130 strength grade of the present invention, is prepared using following methods:
1) 12-13 parts of water-reducing agents and 27-29 parts of hydroxyl modification carbon nano tube dispersion liquids are added to the 25% of total Water In water, it is denoted as aqueous solution 1；Load weighted 2.3-2.5 parts of defoaming agent is added in the water of total Water 25%, aqueous solution 2 is denoted as；
2) 720-750 parts of river sands, 1010-1050 parts of rubbles, 1.1-1.8 parts of cellulose fibres will be weighed in mass ratio to be added Into blender, uniform stirring 2-3min；
3) 450-470 parts of cement, 60-95 parts of flyash, 50-70 parts of rice hull ash, 50-70 parts of silicon ashes then, are sequentially added With 14-15 parts of exciting agents, then the water of total Water remaining 50% is added in blender, uniform stirring 2-3min；
4) then to the aqueous solution 1 being added in blender in step 1), uniform stirring 3-4min；
5) mobility for finally observing mixture, continues the aqueous solution 2 that will be prepared in step 1), uniform stirring 3-5min, Discharging obtains prepared concrete mix；And it forms, conserve.
Wherein:
Cement used is PO52.5R grades of ordinary portland cements, good with poly carboxylic acid series water reducer compatibility.
Thick river sand during river sand selection gradation used is good, fineness modulus 2.8-3.2, preferably fineness modulus are 2.9, Apparent density is 2.59g/cm3, bulk density 1.48g/cm3。
Artificial rubble based on rubble selection lime stone used, particle size range 5-16mm, according to continuous size fraction gradation, table Sight density is 2.7g/cm3。
Flyash used uses the high-quality I grade of flyash of power plant, and 45 μm of square hole screens are tailed over no more than 12%, and water demand ratio is not Greater than 95%, specific surface area is greater than 400m2/kg。
The mass percent of silica is not less than 93% in the silicon ash, and pozzolanic activity index is greater than 90%, averagely 0.1 μm -0.15 μm of partial size, specific surface area is greater than 15m2/g。
Rice hull ash used be by rice husk 650-800 DEG C at a temperature of through burning, using ball mill grinding 20-30min It is made, dioxide-containing silica 93.6%, partial size is 10-75 μm, and specific surface area is in 40-100m2Between/g.
Water-reducing agent used is polycarboxylate high performance water-reducing agent, and solid content 20%, pH value is 8.0 or so, and water-reducing rate exists 25% or more, 7d, 28d compressive strength rate are not less than 150%.
Exciting agent used uses Organic-inorganic composite exciting agent, compounds according to the raw material of following mass percent meters:
Sodium sulphate 60-68%, calcium chloride 30-38%, triethanolamine 1.5-2%.
Defoaming agent used is U.S.'s Hexion AXILAT DF6352DD defoaming agent.
UF500 cellulose fibre of the cellulose fibre used for the research and development of U.S. Burkeye company, length 2-3mm, tension are strong Degree >=900MPa, elasticity modulus 8.5GPa, specific gravity 1.1g/cm3, there is good hydrophily, higher bond stress and resistance to Soda acid performance.
Carbon nano tube dispersion liquid used is hydroxyl modification carbon nano tube dispersion liquid, is successively to pass through alkali by multi-walled carbon nanotube Hydro-thermal reaction under the conditions of property obtains hydroxyl modification multi-wall carbon nano-tube pipe powder, then with surfactant and auxiliary agent in deionization It is obtained after decentralized processing in water.The preparation method is as follows:
1) compound concentration is the sodium hydrate aqueous solution of 2.0M, weighs the hydrogen that 100 parts of preparations are added in 2 parts of multi-walled carbon nanotubes In aqueous solution of sodium oxide, it is ultrasonically treated 5min；Carbon nano tube dispersion liquid is poured into the height of the stainless steel with politef liner Press reaction kettle, 180 DEG C of reaction 120min after sealing；After be cooled to room temperature (centrifugation rate 2000r/ be centrifuged Min, centrifugation time 30min), deionized water is then added and dilutes and washs, removing clear liquid, 2 times repeatedly；It is then ultrasonic again 10min, the vinylidene chloride membrane filtration for being 0.2 μm by diameter after stirring, gained solid product are cleaned with deionized water to filter Liquid pH=7；Dry 12h at 40 DEG C, obtains the modification multi-wall carbon nano-tube of the oxygen-containing functional groups such as surface hydroxyl in vacuum drying oven Pipe.
2) modified multiwalled carbon nanotube, the surface-active of the oxygen-containing functional groups such as the surface hydroxyl prepared in step 1) are weighed 0.5 part of agent, 0.1 part of defoaming agent and 98 parts of deionized water, surfactant, defoaming agent and modified carbon nano-tube are successively distributed to In deionized water, stirring soaks carbon nanotube completely by aqueous surfactant solution；It is ultrasonically treated 30min；Later to dispersion Liquid carries out centrifugal sedimentation (centrifugation rate 2000r/min, centrifugation time 30min).
3) after being centrifuged, supernatant liquid is crossed into 300 mesh filter clothes, obtains carbon nano tube dispersion liquid 1；(i.e. by bottom precipitation The carbon nanotube of reunion) carry out ultrasound 60min again according to step 2), obtain carbon nano tube dispersion liquid 2, carbon nano tube dispersion liquid Hydroxyl modification multi-walled carbon nanotube uniform and stable can disperse in water in 1 and 2.
Multi-walled carbon nanotube used is averaged caliber as 40-50nm, and length is 10-20 μm, purity >=98%.
Surfactant used is Triton X-100, and pH=7.0,63 DEG C of cloud point, be a kind of non-ionic table Face activating agent；Adjuvant used is U.S.'s Hexion AXILAT DF6352DD defoaming agent.
Concrete curing method is to conserve in water in preparation method used: concrete batching system is poured into cast iron die Middle molding, jolt ramming are placed in the environment that temperature is 20 DEG C ± 2 DEG C, in the geotextiles of test block surface covering wetting, are stood 1d, are torn open Then mould conserves in the pond of the saturated limewater solution of standard curing room to required age.
Specific embodiment is given below to further illustrate preparation method of the present invention.
The match ratio of high-performance fiber concrete in 1 embodiment 1-3 of table (in terms of the mass fraction of each component)
The results are shown in Table 2 for the performance comparison of high-performance fiber concrete in embodiment 1-3.
The performance of high performance concrete in 2 embodiment 1-3 of table
As can be seen from the above Table 2, the high-performance fiber concrete of C130 strength grade of the present invention, 28d cube resistance to compression Intensity is not less than 131.21MPa, and split tensile strength is not less than 11.54MPa, and flexural strength is not less than between 29.96MPa, with fashioned iron Adhesion strength be not less than 5.81MPa, unstable state chloride ion transport coefficient DRCMNo more than 18 × 10-14m2/s.It is possible thereby to see Out, the high-performance fiber concrete of C130 strength grade prepared by the present invention is a kind of concrete of good performance, is suitable for Modern Green construction material application.
The above description is only an embodiment of the present invention, be in conjunction with specific optimal enforcement mode to it is of the invention it is further in detail It describes in detail bright, cannot therefore limit the scope of the invention, those skill in the art related utilize present disclosure With method, or under the premise of not departing from present inventive concept, simple change or replacement is made, all should be considered as of the invention In protection scope.Protection scope of the present invention should be subject to the protection scope that disclosed claim defines.

Claims (8)

1. a kind of high-performance fiber concrete of C130 strength grade, which is characterized in that fiber concrete includes following mass parts Several raw materials:
450-470 parts of cement, 100-110 parts of water, 720-750 parts of river sand, 1010-1050 parts of rubble, 60-95 parts of flyash, rice 50-70 parts of shell ash, 50-70 parts of silicon ash, 12-13 parts of water-reducing agent, 14-15 parts of exciting agent, 1.1-1.8 parts of cellulose fibre, hydroxyl 27-29 parts of modified carbon nano-tube dispersion liquid, 2.3-2.5 parts of defoaming agent；
The rice hull ash be by rice husk 650-800 DEG C at a temperature of burn, using ball mill grinding 20-30min be made powder ash Color powder, dioxide-containing silica are 90% or more, and partial size is 10-75 μm, and specific surface area is in 40-100m2Between/g；
The cellulose fibre is UF500 cellulose fibre, and length 2-3mm, diameter is 15-20 μm, tensile strength >= 900MPa, elasticity modulus >=8.5GPa, fracture elongation reach 10%, specific gravity 1.1g/cm3。
2. the high-performance fiber concrete of C130 strength grade according to claim 1, which is characterized in that the concrete Middle each component calculates match ratio content with mass fraction are as follows:
458 parts of cement, 740 parts of river sand, 1040 parts of rubble, 70 parts of flyash, 65 parts of rice hull ash, 65 parts of silicon ash, subtracts 106 parts of water 12.6 parts of aqua, 14.2 parts of exciting agent, 1.6 parts of cellulose fibre, 29 parts of hydroxyl modification carbon nano tube dispersion liquid, defoaming agent 2.4 Part.
3. the high-performance fiber concrete of C130 strength grade according to claim 1, which is characterized in that the cement is PO52.5R grades of ordinary portland cements；
Thick river sand during the river sand selection gradation is good, fineness modulus 2.8-3.2；
Artificial rubble based on the rubble selection lime stone, particle size range 5-16mm, according to continuous size fraction gradation；
The flyash uses the high-quality I grade of flyash of power plant, and 45 μm of square hole screens are tailed over no more than 12%, and water demand ratio is little In 95%, specific surface area should be greater than 400m2/kg；
The mass percent of silica is not less than 93% in the silicon ash, and pozzolanic activity index is greater than 90%, average grain diameter 0.1 μm -0.15 μm, specific surface area is greater than 15m2/g；
The water-reducing agent is polycarboxylate high performance water-reducing agent, and solid content 20%, water-reducing rate is 25% or more；
The defoaming agent uses U.S.'s Hexion AXILAT DF6352DD defoaming agent.
4. the high-performance fiber concrete of C130 strength grade according to claim 1, which is characterized in that the exciting agent Using Organic-inorganic composite exciting agent, composite exciting agent is compounded according to the raw material of following mass percent meters:
Sodium sulphate 60-68%, calcium chloride 30-38%, triethanolamine 1.5-2%.
5. the high-performance fiber concrete of C130 strength grade according to claim 1, which is characterized in that the hydroxyl changes Property carbon nano tube dispersion liquid is as made from following methods:
1) compound concentration is the NaOH aqueous solution of 2.0M, weighs the NaOH aqueous solution that 100 parts of preparations are added in 2 parts of multi-walled carbon nanotubes In, it is ultrasonically treated 5min；Carbon nano tube dispersion liquid is poured into autoclave, 180 DEG C of reaction 120min after sealing；After be cooled to Room temperature, centrifuge separation are added deionized water and dilute and wash, remove clear liquid；Ultrasound 10min again, stirring, vinylidene chloride filter membrane mistake Filter, gained solid product are washed to filtrate as neutrality；Dry 12h, obtains the modification of surface hydroxyl oxygen-containing functional group at 40 DEG C Multi-walled carbon nanotube；
2) modified multiwalled carbon nanotube, the surfactant 0.5 of the surface hydroxyl oxygen-containing functional group prepared in step 1) are weighed Part, 0.1 part of defoaming agent and 98 parts of deionized water, by surfactant, defoaming agent and modified carbon nano-tube be successively distributed to from In sub- water, stirring soaks carbon nanotube completely by aqueous surfactant solution；It is ultrasonically treated 30min；Later to dispersion liquid into Row centrifugal sedimentation；
3) supernatant liquid is crossed into 300 mesh filter clothes, obtains carbon nano tube dispersion liquid 1；By bottom precipitation reunite carbon nanotube according to Step 2) carries out ultrasound 60min again, obtains carbon nano tube dispersion liquid 2, hydroxyl modification multi wall in carbon nano tube dispersion liquid 1 and 2 Carbon nanotube uniform and stable can disperse in water；
The multi-walled carbon nanotube is averaged caliber as 40-50nm, and length is 10-20 μm, purity >=98%；
The surfactant is Triton X-100；The defoaming agent is that U.S.'s Hexion AXILAT DF6352DD disappears Infusion.
6. the high-performance fiber concrete of C130 strength grade according to claim 1, which is characterized in that the high-performance The flexural strength of fiber concrete is not less than 29.96MPa, and 28d cubic compressive strength is not less than 131.21MPa, split tensile strength It is not less than 5.81MPa, unstable state chloride ion transport coefficient D not less than the adhesion strength between 11.54MPa, with fashioned ironRCMLess In 18 × 10-14m2/s。
7. a kind of preparation method of the high-performance fiber concrete of C130 strength grade described in any one of claims 1-6, It is characterized in that, includes the following steps:
1) 12-13 parts of water-reducing agents and 27-29 parts of hydroxyl modification carbon nano tube dispersion liquids are added in 25% water of total Water, It is denoted as aqueous solution 1；Load weighted 2.3-2.5 parts of defoaming agent is added in the water of total Water 25%, aqueous solution 2 is denoted as；
2) 720-750 parts of river sands, 1010-1050 parts of rubbles, 1.1-1.8 parts of cellulose fibres will be weighed in mass ratio to be added to and stir It mixes in machine, uniform stirring 2-3min；
3) 450-470 parts of cement, 60-95 parts of flyash, 50-70 parts of rice hull ash, 50-70 parts of silicon ashes and 14- then, are sequentially added 15 parts of exciting agents, then the water of total Water remaining 50% is added in blender, uniform stirring 2-3min；
4) then to the aqueous solution 1 being added in blender in step 1), uniform stirring 3-4min；
5) mobility for finally observing mixture, continues the aqueous solution 2 that will be prepared in step 1), uniform stirring 3-5min, discharging, Obtain prepared concrete mix；And it forms, conserve.
8. a kind of blanks and moulding and conserving side of the high-performance fiber concrete of C130 strength grade described in any one of claims 1-6 Method, which is characterized in that specific as follows using maintenance process in water:
Concrete batching system is poured into molding, jolt ramming in cast iron die, is placed in the environment that temperature is 20 ± 2 DEG C, in test block The geotextiles of surface covering wetting, stand 1d, then demoulding conserves in the pond of the saturated limewater solution of standard curing room To required age.
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CN1843904A (en) * 2006-03-30 2006-10-11 复旦大学 Method for conducting modification of surface hydroxy group of carbon nanotube
CN104030634A (en) * 2014-06-12 2014-09-10 杭州固华复合材料科技有限公司 High-strength and high-toughness reactive powder concrete of carbon doped nano-tube and preparation method of high-strength and high-toughness reactive powder concrete
CN106396555A (en) * 2016-09-08 2017-02-15 东南大学 Cellulose fiber internal curing-based ultra-high-performance cement-based composite material and preparation method thereof

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CN1843904A (en) * 2006-03-30 2006-10-11 复旦大学 Method for conducting modification of surface hydroxy group of carbon nanotube
CN104030634A (en) * 2014-06-12 2014-09-10 杭州固华复合材料科技有限公司 High-strength and high-toughness reactive powder concrete of carbon doped nano-tube and preparation method of high-strength and high-toughness reactive powder concrete
CN106396555A (en) * 2016-09-08 2017-02-15 东南大学 Cellulose fiber internal curing-based ultra-high-performance cement-based composite material and preparation method thereof

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