CN107512886B - A kind of super high strength high performance fiber concrete of C200 strength grade and preparation method thereof - Google Patents

A kind of super high strength high performance fiber concrete of C200 strength grade and preparation method thereof Download PDF

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CN107512886B
CN107512886B CN201710702342.1A CN201710702342A CN107512886B CN 107512886 B CN107512886 B CN 107512886B CN 201710702342 A CN201710702342 A CN 201710702342A CN 107512886 B CN107512886 B CN 107512886B
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concrete
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CN107512886A (en
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郑山锁
董方园
周炎
董立国
郑捷
李健
龙立
陈家悦
黄威曾
张晓辉
裴培
左河山
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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
    • C04B14/024—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
    • 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)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Civil Engineering (AREA)
  • Environmental & Geological Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Nanotechnology (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The invention discloses super high strength high performance fiber concretes of a kind of C200 strength grade and preparation method thereof, the mass parts composition of the concrete is as follows: 520 parts of cement, 66 parts of water, 990 parts of rubble, 760 parts of fine aggregate, 65 parts of flyash, 72 parts of rice hull ash, 126 parts of silicon ash, 15.6 parts of water-reducing agent, 10.2 parts of exciting agent, 1.7 parts of cellulose fibre, 46 parts of hydroxyl modification carbon nano tube dispersion liquid, 47 parts of graphene oxide dispersion, 2.8 parts of defoaming agent.The concrete of preparation toughness with higher and excellent endurance quality, the adhesion strength with higher between fashioned iron, compression strength reaches 207.87MPa, flexural strength reaches 37.69MPa, split tensile strength reaches 18.32MPa, adhesion strength between fashioned iron reaches 8.75MPa, and chloride ion resistance grade reaches VI grade.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 super high strength high performance fiber concrete of C200 strength grade and preparation method thereof
Technical field
It is that one kind mixes rice hull ash, cellulose fibre, modified carbon nano-tube and oxygen the invention belongs to New Building Materials field High intensity, high tenacity and the high durability concrete of graphite alkene, and in particular to a kind of C200 strength grade with high tenacity Super high strength 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, Cl is made-、SO4 2-Equal harmful ions and CO2Equal pernicious gases invade inside concrete, accelerate concrete The erosion of structure seriously affects the durability of concrete or cement-base composite material structure, reduces structure service life.
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 60-150GPa, and compressive strength 100-170GPa, 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 due to carbon nanometer Pipe surface it is complete it is smooth, defect is few, lacks active group, the relative solubility in water and various solution or composite material compared with Low, there are there is very big surface free energy, therefore carbon nanotube at biggish Van der Waals force, surface between carbon nanotube in addition Between spontaneous reunion or winding easily occurs, it is evenly dispersed in certain polymer to seriously affect carbon nanotube.The present invention Multi-walled carbon nanotube is dispersed and is ultrasonically treated using surfactant, carbon nanotube is not being cut off and is not destroying its surface On the basis of structure, the modified multiwalled carbon nanotube dispersion liquid for capableing of stable dispersion in water is obtained, to can be used for In concrete, its microfibre toughening effect is given full play to.
And graphene is also intensity and the highest crystal structure of hardness in current material, tensile strength and elasticity modulus difference It can reach 125GPa and 1.1TPa.Single-layer graphene thickness is only about 0.35nm, is most thin by two in presently found nature Material is tieed up, specific surface area with higher can be well in conjunction with polymer.But due to being sp2 hydridization knot in graphene face Structure causes mutually to adsorb between nanoparticle there are very strong molecular attraction, causes graphene to reunite together, is unable to stable dispersion In the polymer and its effect is played, or even intrinsic silicon can be caused defect occur.And the graphene monolithic Jing Guo oxidation processes Surface introduces the oxygen-containing functional groups such as many hydroxyls, carboxyl, can it is evenly dispersed in water, but graphene oxide is in alkali It is easy to happen flocculation under the conditions of property, it is unfavorable that this disperses graphene oxide in cement, or even can cause the intensity of concrete Loss.The present invention by add dispersing agent be prepared for can in cement stable dispersion graphene oxide dispersion, can It is enough in concrete, improves the comprehensive performance of concrete.
In order to overcome normal concrete and high performance concrete brittleness and existing fiber concrete and cement base it is compound The shortcomings that material, using the cellulose fibre with water storage function and toughening effect and the rice hull ash with ultrafine micropore structure (rice hull ash with porous structure can absorb moisture), " the interior maintenance action " of two kinds of materials can promote the aquation of cementitious material Process；In addition, by the way that modified carbon nano-tube and graphene oxide 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 concrete of hydrated product The compactness extent of internal structure is finally reached the intensity and endurance quality for improving concrete, and promotes its toughness, plasticity and tension The target of intensity.
Summary of the invention
The object of the present invention is to provide a kind of super high strength high performance fiber concrete of C200 strength grade and its preparation sides Method, novelty of the invention, which ties up in concrete, to be mixed with cellulose fibre with toughening and interior maintenance action, has interior support A kind of carbon-free rice hull ash of novel active mineral admixture of shield effect, and the modification multi wall with toughening and nano-filled effect Carbon nanotube and graphene oxide.Synergistic effect between each component can promote cementitious material aquation more abundant, improve mixed Microcosmic composition inside solidifying soil, reduces detrimental voids quantity, keeps concrete inner structure more closely knit, finally prepares with super High intensity, high tenacity, high-durability, high volume stability novel high-performance fiber concrete material.
To achieve the above object, technical solution disclosed by the invention is:
A kind of super high strength high performance fiber concrete of C200 strength grade, the raw material including following mass fractions:
520 parts of cement, 66 parts of water, 990 parts of rubble, 760 parts of fine aggregate, 65 parts of flyash, 72 parts of rice hull ash, silicon ash 126 Part, 15.6 parts of water-reducing agent, 10.2 parts of exciting agent, 1.7 parts of cellulose fibre, 46 parts of hydroxyl modification carbon nano tube dispersion liquid, oxidation 47 parts of graphene dispersing solution, 2.8 parts of defoaming agent.
The cement is I 62.5R portland cement of P, good with poly carboxylic acid series water reducer compatibility.
The fine aggregate uses mass ratio for the good high grade quartz sand of the scleroid river sand and gradation of 8:2, river sand Fineness modulus is 2.8-3.2, and dioxide-containing silica is not less than 98% in quartz sand, partial size 0.3-0.6mm, density 2.62g/ cm3。
Rubble selection gradation is good, fine and close hard, shaggy basaltic broken stone, by the 5- of continuous size fraction The rubble of 10mm, 10-16mm are used in mixed way according to the mass ratio of 7:3, and parent rock strength is not less than 250MPa, and maximum particle diameter is not More than 16mm.
The flyash is not more than 95% using high-quality I grade special fine powdered coal of power plant, water demand ratio, and specific surface area should be greater than 600m2/kg。
The mass percent of silica is not less than 93% in the silicon ash, and pozzolanic activity index is greater than 95%, averagely 0.1-0.3 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%, pH value 7-8, water-reducing rate is 30% More than, 7d, 28d compressive strength rate are not less than 180%；
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 through burning, using ball mill grinding 30-40min Ash purple powder obtained, dioxide-containing silica 93.6%, partial size are 5-25 μm, and specific surface area is greater than 70m2/g。
The exciting agent is Organic-inorganic composite exciting agent, is compounded according to the raw material of following mass percent meters:
98% waterglass, 2% triethanolamine；
The modulus of the water glass solution is 1.2, is molten for 3.4 waterglass by industrial sodium hydroxide and commercially available modulus What liquid was formulated.
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, there is good hydrophily, compared with High bond stress and acid-proof alkaline.
The carbon nano tube dispersion liquid 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 hydroxyl modification carbon nano tube dispersion liquid the preparation method is as follows:
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, and pH=7.0,63 DEG C of cloud point, be a kind of non-ionic table Face activating agent；The defoaming agent is U.S.'s Hexion AXILAT DF6352DD defoaming agent.
The graphene oxide dispersion is obtained by following methods:
(1) 100 parts of deionized waters are added in 1 part of graphene oxide powder to obtain using ultrasonic machine ultrasonic disperse 30min To finely dispersed graphene oxide dispersion；
(2) 0.1 part of water-reducing agent is added in 50 parts of deionized waters, is stirred evenly, the oxygen of step (1) preparation is then added Graphite alkene dispersion liquid stirs 90s using special-purpose stirring machine, finally obtains graphene oxide that can be evenly dispersed in cement Dispersion liquid.
The graphene oxide is powdered, purity >=98%, and 10 μm -20 μm of diameter, surface has a large amount of oxygen-containing Group, in water dispersion degree with higher；
The water-reducing agent is polycarboxylate high performance water-reducing agent, solid content 20%, pH value 7.
The invention also discloses a kind of preparation methods of the super high strength high performance fiber concrete of C200 strength grade, including Following steps:
1) it is that 10.2 exciting agents and 2.8 parts of defoaming agents dissolve in 25% water of total Water by mass fraction, is denoted as water-soluble 15.6 parts of water-reducing agents, 46 parts of hydroxyl modification carbon nano tube dispersion liquids and 47 parts of graphene oxide dispersions are added to total water by liquid 1 In 50% aqueous solution of amount, it is denoted as aqueous solution 2；
2) weighing 760 parts in mass ratio is the river sand and quartz sand, 990 parts of rubbles and 1.7 parts of cellulose fibres of 8:2 configuration It is added sequentially in blender, uniform stirring 2-3min；
3) 520 parts of cement, 65 parts of flyash, 72 parts of rice hull ash, 126 parts of silicon ashes then, are sequentially added, then will be in step 1) The aqueous solution 1 of preparation is added in blender, uniform stirring 2-3min；
4) then to the aqueous solution 2 being added in blender in step 1), uniform stirring 3-4min；
5) mobility for finally observing mixture, continuously adds the water of total Water remaining 25%, uniform stirring 3-5min, Discharging obtains prepared concrete mix；And it forms, conserve.
Concrete uses steam curing in the preparation method, forms as follows with maintenance process:
Concrete batching system is poured into cast iron die molding, jolt ramming, temperature be 20 DEG C ± 2 DEG C, relative humidity >= 1d is stood in 95% standard curing room, demoulding moves to concrete in High Temperature Curing equipment, and (heating rate is for heating heating 10 DEG C per hour) to 90 DEG C, thermostatic curing 2d, after cooling (cooling rate is 10 DEG C per hour) to room temperature, in standard curing room Pond (being saturated limewater solution in pond, solution temperature is 20 DEG C ± 2 DEG C) in maintenance to required age.
The present invention use for the first time cellulose fibre, rice hull ash, modified carbon nano-tube, graphene oxide, cement, flyash, Quartz sand, river sand, rubble, chemical admixture (including water-reducing agent, exciting agent, defoaming agent), water are prepared for a kind of with high volume Stability, high tenacity, high-durability C200 strength grade super high strength high performance fiber concrete, overcome normal concrete The deficiencies of brittleness is big, easy to crack, durability is poor.
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 5-25 μm), the porous and net road structure inside rice hull ash particle Huge specific surface area is made it have, 70m can be reached2/ g or more.Therefore, incorporation rice hull ash can make gelling material particles more Uniformly, gradation is good, can play filling role, increases the cohesiveness of concrete；Secondly as a large amount of inside rice hull ash Microcellular structure can water storage, play " interior maintenance action "；In addition, since rice hull ash has pozzolanic activity similar with silicon ash, It can replace the Ca (OH) in partially or completely silicon ash, with concrete system2Reaction generates fine and close hard aquation sulphur aluminic acid Calcium improves concrete flexural strength, compression strength, tensile splitting strength, endurance quality；Finally, rice hull ash is as agricultural residue, It is used as construction material replacing partial cement after being processed to, can reduce since rice husk burns and the CO in cement production process2Row High-volume, and then concrete cost is reduced, 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) present invention by addition dispersing agent be prepared for can in cement stable dispersion graphene oxide dispersion.Oxygen On the one hand graphite alkene plays the role of nano-filled, on the other hand the oxygen-containing functional group on its surface can be with hydrolysis product of cement hydrogen Calcium oxide, entringite, hydrated calcium silicate etc. further react, and change the shape of hydrated cementitious crystalline product, enhance cement matrix Toughness, make concrete structure anti-folding with higher with compression strength etc., and enhance the caking property between concrete and fashioned iron Energy.
There is the rice hull ash of volcano ash effect, physics filing effect and " interior maintenance action " by adding, there is toughening to make With the cellulose fibre with " interior maintenance action ", and modified carbon nano-tube and the oxidation of microfibre filled toughening effect can be played Graphene etc., collaboration improves concrete performance between each component, is configured to a kind of resistance to high intensity, high volume stability, height The super high strength high performance fiber concrete of the C200 strength grade of long property and higher toughness.
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 C200 intensity that the method is prepared through the invention The superhigh intensity high performance concrete of grade, compression strength reach 207.87MPa, and flexural strength reaches 37.69MPa, and it is strong to split drawing Degree reaches 18.32MPa, and the adhesion strength between fashioned iron reaches 8.75MPa, and chloride ion resistance grade reaches VI grade, and (28d is non-steady State chloride ion transport coefficient DRCM< 10 × 10-14m2/s).The present invention, which has prepared, has superhigh intensity, high volume stability, height The high-performance fiber concrete of durability and high tenacity, raw material are easy to get, preparation process is simple, meet sustainable development and show The requirement applied and promoted for green construction material 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 preparation method of the super high strength high performance fiber concrete of C200 strength grade of the present invention, includes the following steps:
1) it is that 10.2 exciting agents and 2.8 parts of defoaming agents dissolve in 25% water of total Water by mass fraction, is denoted as water-soluble 15.6 parts of water-reducing agents, 46 parts of hydroxyl modification carbon nano tube dispersion liquids and 47 parts of graphene oxide dispersions are added to total water by liquid 1 In 50% aqueous solution of amount, it is denoted as aqueous solution 2；
2) weighing 760 parts in mass ratio is the river sand and quartz sand, 990 parts of rubbles and 1.7 parts of cellulose fibres of 8:2 configuration It is added sequentially in blender, uniform stirring 2-3min；
3) 520 parts of cement, 65 parts of flyash, 72 parts of rice hull ash, 126 parts of silicon ashes then, are sequentially added, then will be in step 1) The aqueous solution 1 of preparation is added in blender, uniform stirring 2-3min；
4) then to the aqueous solution 2 being added in blender in step 1), uniform stirring 3-4min；
5) mobility for finally observing mixture, continuously adds the water of total Water remaining 25%, uniform stirring 3-5min, Discharging obtains prepared concrete mix；And it forms, conserve.
Concrete uses steam curing in preparation method used, forms as follows with maintenance process:
Concrete batching system is poured into cast iron die molding, jolt ramming, temperature be 20 ± 2 DEG C, relative humidity >= 1d is stood in 95% standard curing room, demoulding moves to concrete in High Temperature Curing equipment, and (heating rate is for heating heating 10 DEG C per hour) to 90 DEG C, thermostatic curing 2d, after cooling (cooling rate is 10 DEG C per hour) to room temperature, in standard curing room Pond (being saturated limewater solution in pond, solution temperature is 20 ± 2 DEG C) in maintenance to required age.
Cement used is I 62.5R portland cement of P, good with poly carboxylic acid series water reducer compatibility.
Fine aggregate used uses mass ratio for the good high grade quartz sand of the scleroid river sand and gradation of 8:2, river sand Fineness modulus is 2.8-3.2, and dioxide-containing silica is not less than 98% in quartz sand, partial size 0.3mm-0.6mm, and density is 2.62g/cm3。
Rubble used selection gradation is good, fine and close hard, shaggy basaltic broken stone, by the 5- of continuous size fraction The rubble of 10mm, 10-16mm are used in mixed way according to the mass ratio of 7:3, and parent rock strength is not less than 250MPa, and maximum particle diameter is not More than 16mm.
Flyash used is not more than 95% using high-quality I grade special fine powdered coal of power plant, water demand ratio, and specific surface area should be greater than 600m2/kg。
The mass percent of silica is not less than 93% in silicon ash used, and pozzolanic activity index is greater than 95%, averagely 0.1-0.3 μm of partial size, specific surface area is greater than 15m2/g。
Water-reducing agent used is polycarboxylate high performance water-reducing agent, and solid content 20%, pH value 7-8, water-reducing rate is 30% More than, 7d, 28d compressive strength rate are not less than 180%.
The defoaming agent uses U.S.'s Hexion AXILAT DF6352DD defoaming agent.
Rice hull ash used be by rice husk 650-800 DEG C at a temperature of through burning, using ball mill grinding 30-40min Ash purple powder obtained, dioxide-containing silica 93.6%, partial size are 5-25 μm, and specific surface area is greater than 70m2/g。
Exciting agent used is Organic-inorganic composite exciting agent, is compounded according to the raw material of following mass percent meters:
98% waterglass, 2% triethanolamine；
Wherein, the modulus of water glass solution is 1.2, is the waterglass for being 3.4 by industrial sodium hydroxide and commercially available modulus Solution is formulated.
Cellulose fibre used is the UF500 cellulose fibre of U.S. Burkeye company research and development, length 2-3mm, diameter It is 15-20 μm, tensile strength >=900MPa, elasticity modulus >=8.5GPa, fracture elongation reaches 10%, specific gravity 1.1g/ cm3, there is good hydrophily, higher bond stress and acid-proof alkaline.
Hydroxyl modification carbon nano tube dispersion liquid used is as made from following methods:
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) according to step 2) ultrasonic treatment 60min is carried out again, obtain carbon nano tube dispersion liquid 2, carbon nanotube point Hydroxyl modification multi-walled carbon nanotube uniform and stable can disperse in water in dispersion liquid 1 and 2.
Wherein, multi-walled carbon nanotube is averaged caliber as 40-50nm, and length is 10-20 μm, purity >=98%；Surface-active Agent is Triton X-100, pH=7.0,63 DEG C of cloud point；Defoaming agent is U.S.'s Hexion AXILAT DF6352DD defoaming Agent.
Graphene oxide dispersion used is obtained by following methods:
(1) 100 parts of deionized waters are added in 1 part of graphene oxide powder to obtain using ultrasonic machine ultrasonic disperse 30min To finely dispersed graphene oxide dispersion；
(2) 0.1 part of water-reducing agent is added in 50 parts of deionized waters, is stirred evenly, the oxygen of step (1) preparation is then added Graphite alkene dispersion liquid stirs 90s using special-purpose stirring machine, finally obtains graphene oxide that can be evenly dispersed in cement Dispersion liquid.
Wherein, graphene oxide used is powdered, purity >=98%, and 10 μm -20 μm of diameter, surface has a large amount of Oxygen-containing group, in water dispersion degree with higher；Water-reducing agent used is polycarboxylate high performance water-reducing agent, and solid content is 20%, pH value 7.
Specific embodiment is given below to further illustrate preparation method of the present invention.
The match ratio of the super high strength high performance fiber concrete of C200 strength grade described in the present embodiment (presses each component quality Number meter) it is as follows:
520 parts of cement, 66 parts of water, 990 parts of rubble, 760 parts of fine aggregate, 65 parts of flyash, 72 parts of rice hull ash, silicon ash 126 Part, 15.6 parts of water-reducing agent, 10.2 parts of exciting agent, 1.7 parts of cellulose fibre, 46 parts of hydroxyl modification carbon nano tube dispersion liquid, oxidation 47 parts of graphene dispersing solution, 2.8 parts of defoaming agent.
The performance test results of the super high strength high performance fiber concrete of C200 strength grade described in the present embodiment such as 1 institute of table Show:
The super high strength high performance fiber concrete basic performance of 1 C200 strength grade of table
As can be seen from the above Table 1, the super high strength high performance fiber concrete of C200 strength grade of the present invention is a kind of property The good concrete of energy, can be used as 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 super high strength high performance fiber concrete of C200 strength grade, which is characterized in that fiber concrete includes following The raw material of mass fraction:
520 parts of cement, 990 parts of rubble, 760 parts of fine aggregate, 65 parts of flyash, 72 parts of rice hull ash, 126 parts of silicon ash, subtracts 66 parts of water 15.6 parts of aqua, 10.2 parts of exciting agent, 1.7 parts of cellulose fibre, 46 parts of hydroxyl modification carbon nano tube dispersion liquid, graphene oxide 47 parts of dispersion liquid, 2.8 parts of defoaming agent；
The rice hull ash be by rice husk 650-800 DEG C at a temperature of by burning, being made using ball mill grinding 30-40min Grey purple powder, dioxide-containing silica 93.6%, partial size be 5-25 μm, specific surface area be greater than 70m2/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 graphene oxide be powdered, purity >=98%, 10 μm -20 μm of diameter.
2. the super high strength high performance fiber concrete of C200 strength grade according to claim 1, which is characterized in that described Cement is I 62.5R portland cement of P, good with poly carboxylic acid series water reducer compatibility；
The fine aggregate uses mass ratio for the good high grade quartz sand of the scleroid river sand and gradation of 8:2, river sand fineness Modulus is 2.8-3.2, and dioxide-containing silica is not less than 98% in quartz sand, partial size 0.3-0.6mm, density 2.62g/cm3；
Rubble selection gradation is good, fine and close hard, shaggy basaltic broken stone, by 5-10mm, 10- of continuous size fraction The rubble of 16mm is used in mixed way according to the mass ratio of 7:3, and parent rock strength is not less than 250MPa, and maximum particle diameter is no more than 16mm；
The flyash is not more than 95% using high-quality I grade special fine powdered coal of power plant, water demand ratio, and specific surface area should be greater than 600m2/kg；
The mass percent of silica is not less than 93% in the silicon ash, and pozzolanic activity index is greater than 95%, average grain diameter 0.1-0.3 μm, specific surface area is greater than 15m2/g；
The water-reducing agent is polycarboxylate high performance water-reducing agent, solid content 20%, pH value 7-8, water-reducing rate 30% or more, 7d, 28d compressive strength rate are not less than 180%；
The defoaming agent uses U.S.'s Hexion AXILAT DF6352DD defoaming agent.
3. the super high strength high performance fiber concrete of C200 strength grade according to claim 1, which is characterized in that described Exciting agent is Organic-inorganic composite exciting agent, is compounded according to the raw material of following mass percent meters:
98% waterglass, 2% triethanolamine；
The modulus of the water glass solution is 1.2, is that the water glass solution for being 3.4 by industrial sodium hydroxide and commercially available modulus is matched It makes.
4. the super high strength high performance fiber concrete of C200 strength grade according to claim 1, which is characterized in that described 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 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.
5. the super high strength high performance fiber concrete of C200 strength grade according to claim 4, which is characterized in that described Multi-walled carbon nanotube is averaged caliber as 40-50nm, and length is 10-20 μm, purity >=98%；
The surfactant be Triton X-100, pH=7.0,63 DEG C of cloud point；
The defoaming agent is U.S.'s Hexion AXILAT DF6352DD defoaming agent.
6. the super high strength high performance fiber concrete of C200 strength grade according to claim 1, which is characterized in that described Graphene oxide dispersion is obtained by following methods:
(1) 100 parts of deionized waters are added in 1 part of graphene oxide powder to be divided using ultrasonic machine ultrasonic disperse 30min Dissipate uniform graphene oxide dispersion；
(2) 0.1 part of water-reducing agent is added in 50 parts of deionized waters, is stirred evenly, the oxidation stone of step (1) preparation is then added Black alkene dispersion liquid stirs 90s, obtains graphene oxide dispersion；
The water-reducing agent is polycarboxylate high performance water-reducing agent, solid content 20%, pH value 7.
7. a kind of preparation side of the super high strength high performance fiber concrete of C200 strength grade described in any one of claims 1-6 Method, which comprises the steps of:
1) it is that 10.2 exciting agents and 2.8 parts of defoaming agents dissolve in 25% water of total Water by mass fraction, is denoted as aqueous solution 1, 15.6 parts of water-reducing agents, 46 parts of hydroxyl modification carbon nano tube dispersion liquids and 47 parts of graphene oxide dispersions are added to total Water In 50% aqueous solution, it is denoted as aqueous solution 2；
2) weigh 760 parts in mass ratio for 8:2 configuration river sand and quartz sand, 990 parts of rubbles and 1.7 parts of cellulose fibres successively It is added in blender, uniform stirring 2-3min；
3) 520 parts of cement, 65 parts of flyash, 72 parts of rice hull ash, 126 parts of silicon ashes then, are sequentially added, then will be prepared in step 1) Aqueous solution 1 be added in blender, uniform stirring 2-3min；
4) then to the aqueous solution 2 being added in blender in step 1), uniform stirring 3-4min；
5) mobility for finally observing mixture, continuously adds the water of total Water remaining 25%, uniform stirring 3-5min, out Material obtains prepared concrete mix；And it forms, conserve.
8. a kind of molding of the super high strength high performance fiber concrete of C200 strength grade described in any one of claims 1-6 is supported Maintaining method, which is characterized in that
Using steam curing method, include the following steps:
Concrete batching system is poured into cast iron die molding, jolt ramming, temperature be 20 ± 2 DEG C, relative humidity >=95% 1d is stood in standard curing room, demoulding moves to concrete in High Temperature Curing equipment, is heated to 10 DEG C of heating rates per hour It is 90 DEG C, thermostatic curing 2d, molten in the saturated limewater of standard curing room after being cooled to room temperature with speed identical with heating rate Liquid, solution temperature are to conserve in 20 ± 2 DEG C of ponds to required age.
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CN110407539A (en) * 2019-07-31 2019-11-05 大连理工大学 A kind of surface functional group processing carbon nano-tube modification Reactive Powder Concrete of high impact properties
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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
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