CN107298563B - A kind of high-performance fiber concrete of C90 strength grade and preparation method thereof - Google Patents

A kind of high-performance fiber concrete of C90 strength grade and preparation method thereof Download PDF

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CN107298563B
CN107298563B CN201710702392.XA CN201710702392A CN107298563B CN 107298563 B CN107298563 B CN 107298563B CN 201710702392 A CN201710702392 A CN 201710702392A CN 107298563 B CN107298563 B CN 107298563B
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water
concrete
agent
carbon nano
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CN107298563A (en
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郑山锁
阮升
董方园
郑捷
王斌
张艺欣
董立国
周炎
龙立
陈家悦
王岱
曹琛
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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
    • 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
    • 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
    • C04B2111/34—Non-shrinking or non-cracking materials
    • C04B2111/343—Crack resistant 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
    • C04B2201/10—Mortars, concrete or artificial stone characterised by specific physical values for the viscosity
    • 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

Abstract

The invention discloses high-performance fiber concrete of a kind of C90 strength grade and preparation method thereof, the mass parts composition of the concrete is as follows: 385-410 parts of cement, 120-135 parts of water, 700-720 parts of river sand, 1020-1050 parts of rubble, 85-105 parts of flyash, 45-75 parts of rice hull ash, 7-8 parts of water-reducing agent, 11-13 parts of exciting agent, 1.1-1.8 parts of cellulose fibre, 28-30 parts of Carboxy polymer, 14-16 parts of hydroxyl modification carbon nano tube dispersion liquid, 2.0-2.1 parts of defoaming agent.The concrete of preparation toughness with higher and excellent endurance quality, the adhesion strength with higher between fashioned iron, its 28d cubic compressive strength is not less than 93.28MPa, split tensile strength is not less than 8.37MPa, flexural strength is not less than 21.19MPa, adhesion strength between fashioned iron is not less than 4.59MPa, 28d unstable state chloride ion transport coefficient DRCMNo more than 46 × 10‑14m2/s.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 C90 strength grade and preparation method thereof
Technical field
It is that one kind is mixed rice hull ash, cellulose fibre, Carboxy polymer and changed the invention belongs to the field of building materials High intensity, high tenacity and the high durability concrete of property carbon nanotube, and in particular to a kind of C90 strength grade with high tenacity High-performance 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, by the way that Carboxy polymer and modified carbon nano-tube both components are added in concrete, to improve concrete Toughness, and make cementitious material in hydration process aquation more sufficiently, improve the crystal shape or even coagulation of hydrated product The compactness extent of native internal structure reduces Cl-、SO4 2-、CO2The intrusion of equal harmful ions, is finally reached the intensity for improving concrete And endurance quality, and promote the target of its toughness, 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 C90 strength grade and preparation method thereof, originally Invention uses cellulose fibre, rice hull ash, modified carbon nano-tube, Carboxy polymer, cement, flyash, river sand, broken for the first time Stone, chemical admixture (including water-reducing agent, exciting agent, defoaming agent), water be prepared for it is a kind of have high volume stability, high tenacity, High-durability, superhigh intensity C90 strength grade fiber high performance concrete, overcome that normal concrete brittleness is big, Yi Kai It splits, the deficiencies of durability is poor.There is the rice hull ash of volcano ash effect, physics filing effect and " interior maintenance action " by adding, Cellulose fibre with toughening effect He " interior maintenance action " has the Carboxy polymer of decrement and toughening effect, with And the modified carbon nano-tube etc. of microfibre filled toughening effect can be played, collaboration improves concrete performance between each component, in turn It is configured to a kind of high-performance fiber of C90 strength grade with high intensity, high volume stability, high-durability and higher toughness Concrete.
To achieve the above object, technical solution disclosed by the invention is:
A kind of high-performance fiber concrete of C90 strength grade, the raw material including following mass fractions:
385-410 parts of cement, 120-135 parts of water, 700-720 parts of river sand, 1020-1050 parts of rubble, flyash 85-105 Part, 45-75 parts of rice hull ash, 7-8 parts of water-reducing agent, 11-13 parts of exciting agent, 1.1-1.8 parts of cellulose fibre, Carboxy polymer 28-30 parts, 14-16 parts of hydroxyl modification carbon nano tube dispersion liquid, 2.0-2.1 parts of defoaming agent.
Preferably, each component optimal match ratio content based on mass fraction in the concrete are as follows:
398 parts of cement, 127 parts of water, 710 parts of river sand, 1040 parts of rubble, 92 parts of flyash, 67 parts of rice hull ash, water-reducing agent 7.2 parts, 11.8 parts of exciting agent, 1.5 parts of cellulose fibre, 29 parts of Carboxy polymer, hydroxyl modification carbon nano tube dispersion liquid 15 parts, 2.1 parts of defoaming 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 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 Carboxy polymer is the organic polymer obtained after mixing by carboxyl styrene emulsion, water and auxiliary agent Object, raw material composition by percentage to the quality are as follows:
Carboxyl styrene emulsion 48-50%, water 48-50%, auxiliary agent 1-2%.
The carboxyl styrene emulsion solid content is 46%, and film-forming temperature is 15 DEG C, lotion pH=7；
The auxiliary agent is polyacrylate defoaming agent.
The present invention also provides a kind of preparation methods of the high-performance fiber concrete of C90 strength grade, including walk as follows It is rapid:
1) mass fraction is added to total water for 7-8 parts of water-reducing agent and 14-16 parts of hydroxyl modification carbon nano tube dispersion liquids In the water of amount 25%, it is denoted as aqueous solution 1；Load weighted 2.0-2.1 parts of defoaming agent is added in the water of total Water 25%, is denoted as Aqueous solution 2；
2) 700-720 parts of river sand will be weighed in mass ratio, 1020-1050 parts of rubbles, 1.1-1.8 parts of cellulose fibres add Enter into blender, uniform stirring 2-3min；
3) it is sharp that 385-410 parts of cement, 85-105 parts of flyash, 45-75 parts of rice hull ash and 11-13 parts then, are sequentially added Agent is sent out, 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 and 28-30 parts of Carboxies that will be prepared in step 1) Polymer, uniform stirring 3-5min discharge to get prepared concrete mix is arrived；And it forms, conserve.
There are two types of methods for concrete formation and maintenance in preparation method:
1) standard curing: being poured into cast iron die molding, jolt ramming for concrete batching system, temperature be 20 DEG C ± 2 DEG C, 1d-2d is stood in the standard curing room of relative humidity >=95%, then demoulding conserves in standard curing room to required age.
2) it is conserved in water: concrete batching system being poured into molding, jolt ramming in cast iron die, being placed in temperature is 20 ± 2 DEG C Environment in, test block surface covering wetting geotextiles, stand 1d, demoulding, then in the pond of standard curing room (in pond For saturated limewater solution) in maintenance 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 an a kind of carbon-free rice hull ash of active mineral admixture of interior maintenance action, and the modification with toughening and nano-filled effect is more Wall carbon nano tube.Synergistic effect between each component can promote cementitious material aquation more abundant, improve inside concrete Microcosmic composition reduces detrimental voids quantity, keeps concrete inner structure more closely knit, finally prepares with high-intensitive, high-ductility The high-performance fiber concrete material of property, high-durability, high volume stability.
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.
4) Carboxy polymer used can be improved toughness of concrete, endurance quality and concrete and type in the present invention Adhesion strength between steel.Firstly, the wetting that a large amount of surface reactive material can increase surface of aggregate in this kind of polymer is made With the cementitiousness that improvement is gathered materials between matrix effectively prevents the formation and development of microcrack and initial imperfection；In addition, should The continuous net-shaped structure of the space three-dimensional of quasi polymer is equivalent to microfibre in concrete, can enhance the anti-folding of concrete, resist Curved intensity improves the toughness of concrete；Polymer can hole inside fill concrete, reduce harmful hole number, improve mixed The compaction rate of soil is coagulated, and then improves the endurance quality of concrete.
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 C90 intensity that the method is prepared through the invention The high-performance fiber concrete of grade, 28d cubic compressive strength are not less than 93.28MPa, and split tensile strength is not less than 8.37MPa, Flexural strength is not less than 4.59MPa, 28d unstable state chloride ion transport not less than the adhesion strength between 21.19MPa, with fashioned iron Coefficient DRCMNo more than 46 × 10-14m2/s.The present invention prepared with superhigh intensity, high volume stability, high-durability and The high-performance fiber concrete of high tenacity, raw material are easy to get, preparation process is simple, meet sustainable development and Modern Green is built The requirement building material application and promoting is a kind of environmentally protective 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 C90 strength grade of the present invention, is prepared using following methods:
1) water-reducing agent and hydroxyl modification carbon nano tube dispersion liquid are added in 25% aqueous solution, are denoted as aqueous solution 1；It will Load weighted defoaming agent is added in 25% water, is denoted as aqueous solution 2；
2) it is added in blender river sand, rubble, cellulose fibre is weighed in mass ratio, uniform stirring 2-3min；
3) a part cement, flyash, rice hull ash and exciting agent then, are sequentially added, 50% water 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 of mixture is finally observed, the aqueous solution 2 and Carboxy polymer prepared in step 1) uniformly stir 3-5min is mixed, is discharged, prepared concrete mix, molding, maintenance are obtained.
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。
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.
The Carboxy polymer is the organic polymer obtained after mixing by carboxyl styrene emulsion, water and auxiliary agent Object, raw material composition by percentage to the quality are as follows:
Carboxyl styrene emulsion 48-50%, water 48-50%, auxiliary agent 1-2%；
Wherein, carboxyl styrene emulsion solid content is 46%, and film-forming temperature is 15 DEG C, carboxyl styrene emulsion pH=7；Auxiliary agent is Polyacrylate defoaming agent.
There are two types of methods for concrete formation and maintenance in preparation method used:
1) standard curing: being poured into molding, jolt ramming in cast iron die for concrete batching system, is 20 ± 2 DEG C, phase in temperature To 1-2d is stood in the standard curing room of humidity >=95%, then demoulding conserves in standard curing room to required age.
2) it is conserved in water: concrete batching system being poured into molding, jolt ramming in cast iron die, being placed in temperature is 20 ± 2 DEG C Environment in, test block surface covering wetting geotextiles, stand 1d, demoulding, then in the pond of standard curing room (in pond For saturated limewater solution) in maintenance 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 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 C90 strength grade of the present invention, 28d cube pressure resistance Degree is not less than 93.28MPa, and split tensile strength is not less than 8.37MPa, and flexural strength is not less than viscous between 21.19MPa, with fashioned iron Knotting strength is not less than 4.59MPa, 28d unstable state chloride ion transport coefficient DRCMNo more than 46 × 10-14m2/s.It is possible thereby to see Out, the high-performance fiber concrete of C90 strength grade prepared by the present invention is a kind of concrete of good performance, is suitable for existing For 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 (7)

1. a kind of high-performance fiber concrete of C90 strength grade, which is characterized in that fiber concrete includes following mass fractions Raw material:
385-410 parts of cement, 120-135 parts of water, 700-720 parts of river sand, 1020-1050 parts of rubble, 85-105 parts of flyash, rice 45-75 parts of shell ash, 7-8 parts of water-reducing agent, 11-13 parts of exciting agent, 1.1-1.8 parts of cellulose fibre, Carboxy polymer 28-30 Part, 14-16 parts of hydroxyl modification carbon nano tube dispersion liquid, 2.0-2.1 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；
The Carboxy polymer is the organic polymer obtained after mixing by carboxyl styrene emulsion, water and auxiliary agent, with The raw material composition of mass percent meter is as follows:
Carboxyl styrene emulsion 48-50%, water 48-50%, auxiliary agent 1-2%；
The carboxyl styrene emulsion solid content is 46%, and film-forming temperature is 15 DEG C, carboxyl styrene emulsion pH=7；
The auxiliary agent is polyacrylate defoaming agent.
2. the high-performance fiber concrete of C90 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:
398 parts of cement, 127 parts of water, 710 parts of river sand, 1040 parts of rubble, 92 parts of flyash, 67 parts of rice hull ash, 7.2 parts of water-reducing agent, 11.8 parts of exciting agent, 29 parts of Carboxy polymer, 15 parts of hydroxyl modification carbon nano tube dispersion liquid, disappears at 1.5 parts of cellulose fibre 2.1 parts of infusion.
3. the high-performance fiber concrete of C90 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 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 C90 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 C90 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. a kind of preparation method of the high-performance fiber concrete of the described in any item C90 strength grades of claim 1-5, special Sign is, includes the following steps:
1) mass fraction is added to total Water for 7-8 parts of water-reducing agent and 14-16 parts of hydroxyl modification carbon nano tube dispersion liquids In 25% water, it is denoted as aqueous solution 1；Load weighted 2.0-2.1 parts of defoaming agent is added in the water of total Water 25%, water is denoted as Solution 2；
2) 700-720 parts of river sand will be weighed in mass ratio, 1020-1050 parts of rubbles, 1.1-1.8 parts of cellulose fibres are added to In blender, uniform stirring 2-3min；
3) 385-410 parts of cement, 85-105 parts of flyash, 45-75 parts of rice hull ash and 11-13 parts of exciting agents then, are sequentially added, The water of total Water remaining 50% is added in blender again, 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) and 28-30 parts of Carboxy polymerizations Object, uniform stirring 3-5min discharge to get prepared concrete mix is arrived；And it forms, conserve.
7. a kind of blanks and moulding and conserving method of the high-performance fiber concrete of the described in any item C90 strength grades of claim 1-5, It is characterised in that it includes maintenance process in standard curing and water:
The standard curing method are as follows: concrete batching system is poured into cast iron die molding, jolt ramming, temperature be 20 ± 2 DEG C, 1d-2d is stood in the standard curing room of relative humidity >=95%, then demoulding conserves in standard curing room to required age；
Method of curing in the water are as follows: concrete batching system is poured into cast iron die molding, jolt ramming, be placed in temperature be 20 DEG C ± In 2 DEG C of environment, in the geotextiles of test block surface covering wetting, 1d, demoulding, then in the saturation lime of standard curing room are stood It conserves in the pond of aqueous solution to required age.
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