CN108892438A - A kind of high tenacity lightweight concrete and preparation method thereof - Google Patents

A kind of high tenacity lightweight concrete and preparation method thereof Download PDF

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CN108892438A
CN108892438A CN201811146918.1A CN201811146918A CN108892438A CN 108892438 A CN108892438 A CN 108892438A CN 201811146918 A CN201811146918 A CN 201811146918A CN 108892438 A CN108892438 A CN 108892438A
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boron nitride
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tube
nitride nano
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CN108892438B (en
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蒋国平
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Fujian Jiangxia University
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00Use 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
    • C04B14/02Granular materials, e.g. microballoons
    • C04B14/32Carbides; Nitrides; Borides ; Silicides
    • C04B14/325Nitrides
    • C04B14/327Boron nitride
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B20/00Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/02Treatment
    • C04B20/023Chemical treatment
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/08Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by adding porous substances
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength

Abstract

The invention discloses a kind of high tenacity lightweight concretes, by weight include following component:30-60 parts of cement,20-50 parts of haydite,20-40 parts of flyash,10-30 parts of fine sand,5-15 parts of nano silica,8-15 parts of desulfurized gypsum,5-10 parts of quartz sand,10-20 parts of composite toughening material,5-10 parts of polyacrylate,1-5 parts of water-reducing agent,1-3 parts of quick lime,2-4 parts of foaming agent,0.4-1.6 parts of swelling agent,2-9 parts of methacrylic acid,2-6 parts of calcium formate,2-8 parts and ultra-fine microballon 10-20 parts of neopentyl glycol,The boron nitride being had excellent performance with activeness and quietness is that basic material is surface modified to form concrete added material by series of chemical,The good micro interface of concrete is assigned to combine,Each same tropism,Toughness and fatigue resistance,It simultaneously can be fully dispersed in concrete,Increase toughness and the intensity of concrete to obtain the lightweight concrete of high-strength and high-ductility.

Description

A kind of high tenacity lightweight concrete and preparation method thereof
Technical field
The invention belongs to the field of building materials, and in particular to a kind of high tenacity lightweight concrete and preparation method thereof.
Background technique
?《Notice about several opinions for promoting modernization of the housing industry raising housing quality》Middle regulation:Coastal cities It is forbidden to use solid clay brick since in June, 2000 with the city of other land resource scarcities, to protect the limited soil in China Ground resource, development do not have to soil or few popular research for having become building field with haydites of book structure, the lytag etc. of soil, have Conducive to protection land resource, promote conservation culture.At abroad, haydite concrete has been widely used in building block and large-scale wall In plate, or even in load-carrying members, economic benefit to be fairly obvious.The progress of total number with the development of economy, people couple The requirement of construction material is also continuously improved, and concrete is not only required to have high intensity.Durable requirement, and concrete should also expire Sufficient lightweight, environmentally friendly requirement.
However, concrete and air entrained concrete belong to fragile material at present, it is easy to generate microcrack because of contraction, very It is destroyed to complete.In general the intensity of lightweight concrete is very low (generally below 5MPa), is unable to satisfy the requirement of building structure, The partition wall of non-bearing can only be done.Therefore, it needs to carry out intensity adjustment using lightweight concrete in load-carrying members, while needing to improve The toughness of concrete.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of high tenacity lightweight concrete and its preparation side Method is reacted for basic material by more surface modification with boron nitride nano-tube, respectively by boron nitride nano-tube with good Good water-soluble and interface compatibility polyethylene glycol oxide covalent bonding, with excellent interface compatibility and water-soluble hyperbranched Different modification boron nitride nano-tubes, then the toughening material that is combined is made in polymer chain, and two kinds of component materials effectively combine, Fully dispersed in concrete, making concrete integrally has good toughness, fatigue resistance and isotropism, so that high tenacity be made Lightweight concrete.
To achieve the above object, the present invention adopts the following technical scheme that:
A kind of high tenacity lightweight concrete includes following component by weight:30-60 parts of cement, 20-50 parts of haydite, It is 20-40 parts of flyash, 10-30 parts of fine sand, 5-15 parts of nano silica, 8-15 parts of desulfurized gypsum, 5-10 parts of quartz sand, compound 10-20 parts of toughening material, 5-10 parts of polyacrylate, 1-5 parts of water-reducing agent, 1-3 parts of quick lime, 2-4 parts of foaming agent, swelling agent 0.4-1.6 parts, 2-9 parts of methacrylic acid, 2-6 parts of calcium formate, 2-8 parts of neopentyl glycol and microballon 10-20 parts ultra-fine.
Wherein, the haydite is one or more of haydites of book structure, clay haydite, coal gangue haydite, lytag Mixture, a diameter of 10-20mm;The water-reducing agent is naphthalene series high-efficiency water-reducing agent, water-reducing rate 18-24%;It is described ultra-fine Microballon is the hollow glass micropearl sorted out from flyash, density 2.49g/cm3, specific surface area 1200m2/kg;Institute Stating fine sand is river sand, fineness modulus 2.5-3.5, bulk density 1500-1800kg/m3;The foaming agent is animals and plants One of protein foaming agent, rosin soap foaming agent or washing class surfactant;The swelling agent is low alkaline concrete Swelling agent.
Wherein, the composite toughening material is modified boron nitride nanometer tube material, by the modified boron nitride nano-tube of component A and The modified boron nitride nano-tube composition of B component;The modified boron nitride nano-tube of the component A uses the boron nitride nanometer of activated processing Pipe with trifunctional organic compound reaction, is then made with polyethylene glycol oxide nucleo philic substitution reaction first;The B component changes Property boron nitride nano-tube mixed in organic solvent N using the boron nitride nano-tube and initiator of activated processing, and and monomer Compound, ethyl alcohol are reacted with distilled water to be made;The modified boron nitride nano-tube of the B component and the modified boron nitride nano-tube of component A Quality proportioning be 0.3-0.6:1.
Wherein, the average length of the boron nitride nano-tube is 10 μm, average diameter 90nm, specific surface area 30m2/ g;The trifunctional organic compound is trichloro-triazine;The resin content of the polyethylene glycol oxide is greater than 98%, and viscosity is 92000, fusing point is 66-68 DEG C, and thermal decomposition temperature is 423-425 DEG C, and brittle point is -50 DEG C;The initiator is BF3·O (C2H5)2;The organic solvent N is dichloromethylene;The monomeric compound is 3- ethyl -3- hydroxymethyl-oxetane.
Wherein, the composite toughening material preparation method specifically includes following steps:
S1, the quality proportioning that boron nitride nano-tube and distilled water are modified by the modified boron nitride nano-tube of B component, component A 0.3-0.6:1:55 stocks;
S2, the modified boron nitride nano-tube of component A by above-mentioned steps S1, the modified boron nitride nano-tube of B component and distillation Set aside for use after 6-12h is stirred in water mixing under the conditions of 25-45 DEG C;
S3, by above-mentioned steps S2 reaction after mixture, after removing water under reduced pressure at 65-75 DEG C, the vacuum at 50-60 DEG C The i.e. modified boron nitride nanometer tube material of composite toughening material is made after dry 36-48h.
Wherein, the preparation method of the modified boron nitride nano-tube of the component A includes the following steps:
A1, activated 3-8kg boron nitride nano-tube and 0.2-2kg trichloro-triazine are mixed in 60-260L acetone, 12-15h is stirred at 12-15 DEG C, then reacts 80-85h at 11-15 DEG C, it is true under the conditions of 8-10 DEG C after acetone is cleaned The dry 15-20h of sky;
A2, will be through above-mentioned steps A1 treated N of the 3-8kg boron nitride nano-tube in 80-180L, N '-dimethyl formyl After being dissolved in amine, it is added in the 20-40L xylene solution dissolved with 0.5-1.5kg polyethylene glycol oxide, stirs 2- at 5 DEG C After 3h, isothermal reaction 18-20h after being warming up to 62 DEG C under nitrogen protection, then isothermal reaction 18-22h after being warming up to 80 DEG C;It is described Polyethylene glycol oxide need to be dried in vacuo 48-50h at 65 DEG C before use;
After A3, fully reacting, evaporating solvent under reduced pressure is cleaned with dimethylbenzene and acetone, is dried in vacuo 22-25h at 65 DEG C The modified boron nitride nano-tube of component A is made afterwards;Polyethylene glycol oxide and boron nitride nanometer in the modified boron nitride nano-tube of the component A The mass content ratio of pipe is 0.05-0.2:1.
Wherein, the preparation method of the modified boron nitride nano-tube of the B component includes the following steps:
B1, by the 1-10kg boron nitride nano-tube of activated processing and the BF of 0.3-0.6kg3·O(C2H5)2In 50-200L It is mixed in dichloromethylene, after stirring 1-1.5h under conditions of vacuum and 20 DEG C, the 3- second of 1-3kg is slowly added dropwise in 3-5h Isothermal reaction 40-45h after being warming up to 25 DEG C is added dropwise in base -3- hydroxymethyl-oxetane, and 30-100L ethyl alcohol is then added And continue to stir 1-2h;
B2,300-500L distilled water is added in the system after above-mentioned steps B2 reaction, is stayed after standing 28-36h filtering Solid is deposited, obtained solid is cleaned with distilled water, 24-48h is finally dried in vacuo at 55-75 DEG C, the modified nitrogen of B component is made Change boron nanotube.
Wherein, the activation process step of the boron nitride nano-tube is as follows:
C1, boron nitride nano-tube 8kg is chosen, is 350-400rpm and every automatic conversion rotation side 30-40 minutes in revolving speed Under conditions of after ball milling 24-36h, the boron nitride nano-tube that average length is 0.5-1.2 μm is obtained;After being eluted with water, in 80- It is dried in vacuo at 85 DEG C after 30-35h for use;
C2, the 3-6kg boron nitride nano-tube handled by above-mentioned steps C1 and 10-15kg thionyl chloride are had in 15-25L It is mixed in solvent M, after stirring 5-12h at 85-90 DEG C, 35-40min is centrifuged with the revolving speed of 6000-7000rpm, separation is solid Body cleans separating obtained solid using organic solvent P, then is dried in vacuo 18-20h at 25-30 DEG C;
C3, under nitrogen protection, will by above-mentioned steps C2 treated 3-6kg boron nitride nano-tube and 2-8L pyridine, 0.5-1.5kg organic diol compound mixes in 100-150L organic solvent Q, after reacting 10-15h at 85-90 DEG C, subtracts Organic solvent Q and pyridine is evaporated off in pressure, then after solvent P is cleaned, is dried in vacuo 20-32h at 20-25 DEG C, obtains activated place The boron nitride nano-tube of reason.
Wherein, the organic solvent M is N, one of N '-dimethyl formamide or N-Methyl pyrrolidone;It is described to have Solvent P is one of anhydrous propanone or tetrahydrofuran;The organic diol compound is ethylene glycol or 1,3- propylene glycol One of;The organic solvent Q is N-Methyl pyrrolidone or N, one of N '-dimethyl acetamide.
A method of high tenacity lightweight concrete is prepared, is specifically comprised the following steps:
D1, composite toughening materials for later use is prepared;
D2, the hollow glass micropearl sorted out from flyash are stand-by as ultra-fine microballon;
D3, by cement, haydite, flyash, fine sand, ultra-fine microballon, nano silica, desulfurized gypsum, quartz sand and multiple It closes toughening material and pours into dry mixing 2-3min in concrete mixer;
D4, polyacrylate, water-reducing agent, quick lime, foaming agent, swelling agent, methacrylic acid, calcium formate and new are added Pentanediol continues mix 15-20min;
D5, then the mixture being stirred is put into mold, is plugged and pounded, is compacted, atmospheric steam curing, demoulding and height High tenacity lightweight concrete can be obtained after pressure steam curing.
Beneficial effects of the present invention:
(1) the modification boron nitride nanometer tube material that can be used for the enhancing of concrete toughening of the invention, is with boron nitride nanometer Pipe is basic material.Boron nitride nano-tube is crimped by hexagonal boron, is a kind of monodimension nanometer material, is had very high Tensile strength and elasticity modulus and excellent thermal stability and chemical stability.On microcosmic, boron nitride nano-tube energy and water Mud substrate crystal grain forms bridging, bridging coupling and unique fracture mode;Further by bridging, crackle deflection, extract and The toughened and reinforced mechanism such as fracture can enhance interface cohesion, inhibit crack propagation, this is a kind of important composite material toughening increasing Rival's section.Therefore, boron nitride nano-tube is a kind of ideal preparation of high efficient concrete reinforcing material.
(2) present invention is basic material with boron nitride nano-tube, is reacted by more surface modification, by boron nitride nano-tube With the polyethylene glycol oxide covalent bonding with good aqueous solubility and interface compatibility, the modified boron nitride nanometer of component A is prepared Pipe;Meanwhile with boron nitride nano-tube being basic material, by surface chemical reaction, in boron nitride nanometer pipe surface covalent bonding With excellent interface compatibility and water-soluble dissaving polymer chain, the modified boron nitride nano-tube of B component is prepared.This hair In bright modification boron nitride nano-tube, the optimization quality of the modified boron nitride nano-tube of B component and the modified boron nitride nano-tube of component A Proportion is 0.3-0.6:1, in this way, two kinds of component materials are effectively combined, it is fully dispersed in concrete, to be formed a kind of only Special composite toughening enhances system, effectively plays the effect of the coordination plasticizing reinforcement of each component material, and it is good to assign concrete Micro interface combination, isotropism and fatigue resistance.
(3) modified boron nitride nano-tube and its altered contents (polyethylene glycol oxide and dissaving polymer chain) in the present invention, Belong to environmental-friendly, there is good dissolubility and dispersibility in water, preparation condition is content with very little and raw material sources are abundant;Change Property boron nitride nanometer tube material can be easily uniformly mixed with other concrete components, through mark support after concrete can be obtained Product is applied to the special buildings concrete material fields such as overpass bridge floor, tunnel arch wall.
Specific embodiment
Below in conjunction with specific embodiment, the present invention will be further described, but the present invention is not limited only to these embodiments.
Heretofore described ultra-fine microballon is the hollow glass micropearl sorted out from flyash, is in grayish powder Shape, density 2.49g/cm3, specific surface area 1200m2/kg;The fine sand is river sand, fineness modulus 2.5-3.5, accumulation Density is 1500-1800kg/m3;The adhesive is polyvinyl acetate;
Boron nitride nano-tube is commercial product, main specifications:Fibrous white powder, content 99.9% are average long Degree is 10 μm;Average diameter is 90nm;Specific surface area is 30m2/g。
The polyethylene glycol oxide is commercial product, main specifications:The resin content of white powder, polyethylene glycol oxide is greater than 98%, (mpa.s-25 DEG C/1%aq) of viscosity is 92000, and fusing point is 66-68 DEG C, and thermal decomposition temperature is 423-425 DEG C, brittle point It is -50 DEG C.
Initiator B F3·O(C2H5)2It is pure for commercially available analysis;
Dichloromethylene is that commercially available analysis is pure;
3- ethyl -3- hydroxymethyl-oxetane is that commercially available analysis is pure.
Embodiment 1
A kind of high tenacity lightweight concrete includes following component by weight:40 parts of cement, 30 parts of haydite, flyash 20 parts, 20 parts of fine sand, 10 parts of nano silica, 8 parts of desulfurized gypsum, 5 parts of quartz sand, 10 parts of composite toughening material, polypropylene It is 5 parts of acid esters, 2 parts of water-reducing agent, 1 part of quick lime, 2 parts of foaming agent, 0.4 part of swelling agent, 3 parts of methacrylic acid, 2 parts of calcium formate, new 10 parts of 2 parts of pentanediol and ultra-fine microballon.
Wherein, preparation high tenacity lightweight concrete specifically comprises the following steps:
D1, to prepare composite toughening material stand-by;
D2, the hollow glass micropearl sorted out from flyash are stand-by as ultra-fine microballon;
D3, by cement, haydite, flyash, fine sand, ultra-fine microballon, nano silica, desulfurized gypsum, quartz sand and multiple It closes toughening material and pours into dry mixing 2min in concrete mixer;
D4, polyacrylate, water-reducing agent, quick lime, foaming agent, swelling agent, methacrylic acid, calcium formate and new are added Pentanediol continues mix 15min;
D5, then the mixture being stirred is put into mold, is plugged and pounded, is compacted, atmospheric steam curing, demoulding and height High tenacity lightweight concrete can be obtained after pressure steam curing.
Wherein, the composite toughening material is modified boron nitride nanometer tube material, by the modified boron nitride nano-tube of component A and The modified boron nitride nano-tube composition of B component;The modified boron nitride nano-tube of the B component and component A are modified boron nitride nano-tube Mass content is than 0.5:1;The preparation method of the composite toughening material specifically includes following steps:
S1, the quality proportioning that boron nitride nano-tube and distilled water are modified by the modified boron nitride nano-tube of B component, component A 0.5:1:55 stocks;
The modified boron nitride nano-tube of S2, the component A for choosing above-mentioned steps S1, the modified boron nitride nano-tube of B component and distillation Water, it is stand-by after stirring 6h at 25 DEG C;
S3, will be through above-mentioned steps S2 treated mixture, after removing distilled water under reduced pressure at 70 DEG C, the vacuum at 60 DEG C Composite toughening material is made after dry 36h.
Then, the modified boron nitride nano-tube of preparation component A, specific step is as follows:
A1, the 4kg boron nitride nano-tube of activated processing and 1kg trichloro-triazine are mixed in 130L acetone, 12 12h is stirred at DEG C, after then reacting 80h at 15 DEG C, is cleaned through acetone, is dried in vacuo 15h at 8 DEG C;
A2, by by above-mentioned steps A1 treated 4kg boron nitride nano-tube 80L N, in N '-dimethyl formamide It after dissolution, is added in the 40L xylene solution dissolved with 0.5kg polyethylene glycol oxide, after stirring 2h at 5 DEG C, is protected in nitrogen After being warming up to 62 DEG C of isothermal reaction 18h under shield, then it is warming up to 80 DEG C of isothermal reaction 18h;The polyethylene glycol oxide is needed before use 48h is dried in vacuo at 65 DEG C;
After A3, fully reacting, evaporating solvent under reduced pressure is cleaned with dimethylbenzene and acetone, is obtained after 22h is dried in vacuo at 65 DEG C To the modified boron nitride nano-tube product of component A;Polyethylene glycol oxide and boron nitride nanometer in the modified boron nitride nano-tube of the component A The mass content ratio of pipe is 0.2:1.
Further, the modified boron nitride nano-tube of preparation B component, specific step is as follows:
B1, by the 1kg boron nitride nano-tube of activated processing and the BF of 0.3kg3·O(C2H5)2In the dichloro methylene of 50L It is mixed in base, after stirring 1h at vacuum and 20 DEG C, the 3- ethyl -3- hydroxymethyl-oxetane of 1kg is slowly added dropwise in 3h, It is warming up to 25 DEG C of isothermal reaction 40h after being added dropwise, 30L ethyl alcohol is then added and continues to stir 1h;
B2,300L distilled water is further added in the system of above-mentioned steps B1, is filtered after standing 28h, it is obtained solid Body is cleaned with distilled water, is finally dried in vacuo at 55 DEG C and the modified boron nitride nano-tube of B component is made for 24 hours.
Wherein, the activation process step of the boron nitride is as follows:
C1, boron nitride nano-tube 8kg is chosen, in the item that revolving speed is 350rpm and every 30 minutes automatic conversion direction of rotation Under part ball milling for 24 hours after, obtaining average length is 1.2 μm of boron nitride nano-tube;After being eluted with water, it is dried in vacuo at 85 DEG C It is stand-by after 30h.
C2, by by above-mentioned steps C1 processing 3kg boron nitride nano-tube and 10kg thionyl chloride 15L N- methyl pyrrole It is mixed in pyrrolidone, after stirring 5h at 85 DEG C, 35min is centrifuged with the revolving speed of 6000rpm, solid is separated and is washed through anhydrous propanone After net, then at 25 DEG C it is dried in vacuo 18h;
C3, under nitrogen protection, will be by 3kg boron nitride nano-tube, 2L pyridine and the 0.5kg second of above-mentioned steps C2 processing Glycol mixes in the N-Methyl pyrrolidone of 100L, after reacting 10h at 85 DEG C, removes pyridine and N- crassitude under reduced pressure Ketone, then after tetrahydrofuran is cleaned, be dried in vacuo 32h at 20 DEG C, obtain the boron nitride nano-tube of activated processing.
Finally obtained high tenacity lower shrinkage cracking resistance lightweight concrete, 28 days compression strength of regenerated aggregate concrete obtained are 60.7MPa, 28 days cleavage strengths are 6.75MPa.
Embodiment 2
A kind of high tenacity lightweight concrete includes following component by weight:40 parts of cement, 30 parts of haydite, flyash 30 parts, 10 parts of fine sand, 5 parts of nano silica, 9 parts of desulfurized gypsum, 8 parts of quartz sand, 15 parts of composite toughening material, polyacrylic acid 8 parts of ester, 4 parts of water-reducing agent, 2 parts of quick lime, 3 parts of foaming agent, 1 part of swelling agent, 6 parts of methacrylic acid, 4 parts of calcium formate, new penta 2 15 parts of 6 parts of alcohol and ultra-fine microballon.
Wherein, preparation high tenacity lightweight concrete specifically comprises the following steps:
D1, to prepare composite toughening material stand-by;
D2, the hollow glass micropearl sorted out from flyash are stand-by as ultra-fine microballon;
D3, by cement, haydite, flyash, fine sand, ultra-fine microballon, nano silica, desulfurized gypsum, quartz sand and multiple It closes toughening material and pours into dry mixing 3min in concrete mixer;
D4, polyacrylate, water-reducing agent, quick lime, foaming agent, swelling agent, methacrylic acid, calcium formate and new are added Pentanediol continues mix 18min;
D5, then the mixture being stirred is put into mold, is plugged and pounded, is compacted, atmospheric steam curing, demoulding and height High tenacity lightweight concrete can be obtained after pressure steam curing.
Wherein, the composite toughening material is modified boron nitride nanometer tube material, by the modified boron nitride nano-tube of component A and The modified boron nitride nano-tube composition of B component;The modified boron nitride nano-tube of the B component and component A are modified boron nitride nano-tube Mass content is than 0.6:1;The preparation method of the composite toughening material specifically includes following steps:
S1, by the quality proportioning by the modified boron nitride nano-tube of B component, component A modified boron nitride nano-tube and distilled water 0.6:1:60 stocks;
S2, the modified boron nitride nano-tube of component A of above-mentioned steps S1, the modified boron nitride nano-tube of B component and distilled water, It is stand-by after stirring 10h at 45 DEG C;
S3, will be through above-mentioned steps S2 treated mixture, after removing distilled water under reduced pressure at 75 DEG C, the vacuum at 55 DEG C Composite toughening material is made after dry 48h.
Then, the modified boron nitride nano-tube of preparation component A, specific step is as follows:
A1, the 6kg boron nitride nano-tube of activated processing and 2kg trichloro-triazine are mixed in 110L acetone, 15 15h is stirred at DEG C, after then reacting 85h at 11 DEG C, is cleaned through acetone, is dried in vacuo 18h at 10 DEG C;
A2, by by above-mentioned steps A1 treated 6kg boron nitride nano-tube 180L N, in N '-dimethyl formamide It after dissolution, is added in the 30L xylene solution dissolved with 1kg polyethylene glycol oxide, after stirring 3h at 5 DEG C, in nitrogen protection Under be warming up to 62 DEG C of isothermal reaction 20h after, then be warming up to 80 DEG C of isothermal reaction 22h;The polyethylene glycol oxide need to be before use 50h is dried in vacuo at 65 DEG C;
After A3, fully reacting, evaporating solvent under reduced pressure is cleaned with dimethylbenzene and acetone, is obtained after 25h is dried in vacuo at 65 DEG C To the modified boron nitride nano-tube product of component A;Polyethylene glycol oxide and boron nitride nanometer in the modified boron nitride nano-tube of the component A The mass content ratio of pipe is 0.1:1.
Further, the modified boron nitride nano-tube of preparation B component, specific step is as follows:
B1, by the 10kg boron nitride nano-tube of activated processing and the BF of 0.6kg3·O(C2H5)2It is sub- in the dichloro of 200L It is mixed in methyl, after stirring 1.5h at vacuum and 20 DEG C, the 3- ethyl -3- methylol oxa- ring of 3kg is slowly added dropwise in 5h Butane is warming up to 25 DEG C of isothermal reaction 45h after being added dropwise, 100L ethyl alcohol is then added and continues to stir 2h;
B2,500L distilled water is further added in the system of above-mentioned steps B1, is filtered after standing 36h, it is obtained solid Body is cleaned with distilled water, 48h is finally dried in vacuo at 60 DEG C, the modified boron nitride nano-tube of B component is made.
Wherein, the activation process step of the boron nitride is as follows:
C1, boron nitride nano-tube 8kg is chosen, in the item that revolving speed is 400rpm and every 40 minutes automatic conversion direction of rotation Under part after ball milling 36h, the boron nitride nano-tube that average length is 1.0 μm is obtained;After being eluted with water, it is dried in vacuo at 80 DEG C It is stand-by after 35h.
C2, N, N '-two by the 6kg boron nitride nano-tube and 15kg thionyl chloride by above-mentioned steps C1 processing in 25L It is mixed in methylformamide, after stirring 7h at 90 DEG C, 40min is centrifuged with the revolving speed of 7000rpm, separates solid and through tetrahydro furan It mutters after cleaning, then be dried in vacuo 20h at 30 DEG C;
C3, under nitrogen protection, will be by the 6kg boron nitride nano-tube of above-mentioned steps C2 processing, 8L pyridine and 1.5kg 1,3-PD mixes in the N-Methyl pyrrolidone of 150L, after reacting 15h at 90 DEG C, removes pyridine and N- methyl under reduced pressure Pyrrolidones, then after tetrahydrofuran is cleaned, be dried in vacuo 20h at 25 DEG C, obtain the boron nitride nano-tube of activated processing.
Finally obtained high tenacity lower shrinkage cracking resistance lightweight concrete, 28 days compression strength of regenerated aggregate concrete obtained are 66.8MPa, 28 days cleavage strengths are 7.25MPa.
Embodiment 3
A kind of high tenacity lightweight concrete includes following component by weight:60 parts of cement, 50 parts of haydite, flyash 40 parts, 30 parts of fine sand, 15 parts of nano silica, 15 parts of desulfurized gypsum, 10 parts of quartz sand, 20 parts of composite toughening material, poly- third 10 parts of olefin(e) acid ester, 5 parts of water-reducing agent, 3 parts of quick lime, 3 parts of foaming agent, 1.6 parts of swelling agent, 9 parts of methacrylic acid, 6 parts of calcium formate, 20 parts of 8 parts of neopentyl glycol and ultra-fine microballon.
Wherein, preparation high tenacity lightweight concrete specifically comprises the following steps:
D1, to prepare composite toughening material stand-by;
D2, the hollow glass micropearl sorted out from flyash are stand-by as ultra-fine microballon;
D3, by cement, haydite, flyash, fine sand, ultra-fine microballon, nano silica, desulfurized gypsum, quartz sand and multiple It closes toughening material and pours into dry mixing 2min in concrete mixer;
D4, polyacrylate, water-reducing agent, quick lime, foaming agent, swelling agent, methacrylic acid, calcium formate and new are added Pentanediol continues mix 20min;
D5, then the mixture being stirred is put into mold, is plugged and pounded, is compacted, atmospheric steam curing, demoulding and height High tenacity lightweight concrete can be obtained after pressure steam curing.
Wherein, the composite toughening material is by the modified boron nitride nano-tube of component A and the modified boron nitride nano-tube group of B component At;The mass content of the modified boron nitride nano-tube of the B component and the modified boron nitride nano-tube of component A is than 0.3:1;It is described compound The preparation method of toughening material specifically includes following steps:
S1, the quality proportioning that boron nitride nano-tube and distilled water are modified by the modified boron nitride nano-tube of B component, component A 0.3:1:55 stocks;
S2, the component X boron nitride added material of above-mentioned steps S1, Y component boron nitride added material and distilled water, at 30 DEG C It is stand-by after lower stirring 12h;
S3, will be through above-mentioned steps S2 treated mixture, after removing distilled water under reduced pressure at 65 DEG C, the vacuum at 60 DEG C Composite toughening material is made after dry 40h.
Then, the modified boron nitride nano-tube of preparation component A, specific step is as follows:
A1, the 8kg boron nitride nano-tube of activated processing and 0.2kg trichloro-triazine are mixed in 60L acetone, 13 14h is stirred at DEG C, after then reacting 82h at 13 DEG C, is cleaned through acetone, is dried in vacuo 20h at 9 DEG C;
A2, by by above-mentioned steps A1 treated 8kg boron nitride nano-tube 100L N, in N '-dimethyl formamide It after dissolution, is added in the 20L xylene solution dissolved with 1.5kg polyethylene glycol oxide, after stirring 2h at 5 DEG C, is protected in nitrogen After being warming up to 62 DEG C of isothermal reaction 19h under shield, then it is warming up to 80 DEG C of isothermal reaction 20h;The polyethylene glycol oxide is needed before use 49h is dried in vacuo at 65 DEG C;
After A3, fully reacting, evaporating solvent under reduced pressure is cleaned with dimethylbenzene and acetone, is dried in vacuo at 65 DEG C and is obtained afterwards for 24 hours To the modified boron nitride nano-tube product of component A;Polyethylene glycol oxide and boron nitride nanometer in the modified boron nitride nano-tube of the component A The mass content ratio of pipe is 0.05:1.
Further, the modified boron nitride nano-tube of preparation B component, specific step is as follows:
B1, by the 5kg boron nitride nano-tube of activated processing and the BF of 0.4kg3·O(C2H5)2In the dichloro methylene of 100L It is mixed in base, after stirring 1h at vacuum and 20 DEG C, the 3- ethyl -3- hydroxymethyl-oxetane of 2kg is slowly added dropwise in 4h, It is warming up to 25 DEG C of isothermal reaction 42h after being added dropwise, 70L ethyl alcohol is then added and continues to stir 1h;
B2,400L distilled water is further added in the system of above-mentioned steps B1, is filtered after standing 30h, it is obtained solid Body is cleaned with distilled water, 36h is finally dried in vacuo at 75 DEG C, the modified boron nitride nano-tube of B component is made.
Wherein, the activation process step of the boron nitride is as follows:
C1, boron nitride nano-tube 8kg is chosen, in the item that revolving speed is 380rpm and every 35 minutes automatic conversion direction of rotation Under part after ball milling 30h, the boron nitride nano-tube that average length is 0.8 μm is obtained;After being eluted with water, it is dried in vacuo at 82 DEG C It is stand-by after 32h.
C2, N, N '-two by the 5kg boron nitride nano-tube and 12kg thionyl chloride by above-mentioned steps C1 processing in 20L It is mixed in methylformamide, after stirring 12h at 88 DEG C, 38min is centrifuged with the revolving speed of 6800rpm, separates solid and through anhydrous After acetone is cleaned, then at 28 DEG C it is dried in vacuo 19h;
C3, under nitrogen protection, will be by 5kg boron nitride nano-tube, 6L pyridine and the 1.0kg second of above-mentioned steps C2 processing Glycol mixes in N '-dimethyl acetamide in the N of 120L, after reacting 12h at 88 DEG C, removes pyridine and N, N '-diformazan under reduced pressure Yl acetamide, then after tetrahydrofuran is cleaned, be dried in vacuo 19h at 28 DEG C, obtain the boron nitride nano-tube of activated processing.
Finally obtained high tenacity lower shrinkage cracking resistance lightweight concrete, 28 days compression strength of regenerated aggregate concrete obtained are 62.8MPa, 28 days cleavage strengths are 6.95MPa.
Performance test:Concrete mechanics are carried out according to GB50081-2002 standard for test methods of mechanical properties of ordinary concrete Test
28d bending strength (MPa) 8 days cleavage strengths (MPa)
Embodiment 1 60.7 6.75
Embodiment 2 66.8 7.25
Embodiment 3 62.8 6.95
In conclusion after composite toughening material is added in original concrete, compared to the 28d of existing lightweight concrete Bending strength, the 28d bending strength of concrete can reach 60MPa or more in the present invention, 28d cleavage strength can reach 6MPa with On, intensity has obtained significant raising.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention, It should be equivalent substitute mode, be included in protection scope of the present invention.

Claims (10)

1. a kind of high tenacity lightweight concrete, it is characterised in that:It by weight include following component:30-60 parts of cement, haydite 20-50 parts, 20-40 parts of flyash, 10-30 parts of fine sand, 5-15 parts of nano silica, 8-15 parts of desulfurized gypsum, quartz sand 5- 10 parts, 10-20 parts of composite toughening material, 5-10 parts of polyacrylate, 1-5 parts of water-reducing agent, 1-3 parts of quick lime, foaming agent 2-4 Part, 0.4-1.6 parts of swelling agent, 2-9 parts of methacrylic acid, 2-6 parts of calcium formate, 2-8 parts of neopentyl glycol and ultra-fine microballon 10-20 Part.
2. high tenacity lightweight concrete according to claim 1, it is characterised in that:The haydite is haydites of book structure, clay One or more of haydite, coal gangue haydite, lytag mixture, a diameter of 10-20mm;The water-reducing agent is naphthalene Series high-efficiency water-reducing agent, water-reducing rate 18-24%;The ultra-fine microballon is the hollow glass micropearl sorted out from flyash, Density is 2.49g/cm3, specific surface area 1200m2/kg;The fine sand is river sand, and fineness modulus 2.5-3.5 accumulates close Degree is 1500-1800kg/m3;The foaming agent is that animal/vegetable protein foaming agent, rosin soap foaming agent or washing class surface are living One of property agent;The swelling agent is low alkaline cement expansive material.
3. high tenacity lightweight concrete according to claim 2, it is characterised in that:The composite toughening material is modified nitridation Boron nano-tube material is made of the modified boron nitride nano-tube of component A and the modified boron nitride nano-tube of B component;The component A is modified Boron nitride nano-tube using activated processing boron nitride nano-tube first with trifunctional organic compound reaction, then with it is poly- Ethylene oxide nucleo philic substitution reaction is made;The modified boron nitride nano-tube of the B component is received using the boron nitride of activated processing Mitron and initiator mix in organic solvent N, and react and be made with monomeric compound, ethyl alcohol with distilled water;The B component changes Property boron nitride nano-tube and the quality proportioning of the modified boron nitride nano-tube of component A be 0.3-0.6:1.
4. high tenacity lightweight concrete according to claim 3, it is characterised in that:The average length of the boron nitride nano-tube Degree is 10 μm, average diameter 90nm, specific surface area 30m2/g;The trifunctional organic compound is trichloro-triazine; The resin content of the polyethylene glycol oxide is greater than 98%, and viscosity 92000, fusing point is 66-68 DEG C, thermal decomposition temperature 423-425 DEG C, brittle point is -50 DEG C;The initiator is BF3•O(C2H5)2;The organic solvent N is dichloromethylene;The monomer chemical combination Object is 3- ethyl -3- hydroxymethyl-oxetane.
5. high tenacity lightweight concrete according to claim 4, it is characterised in that:The composite toughening material preparation method Specifically include following steps:
S1, the quality proportioning 0.3- that boron nitride nano-tube and distilled water are modified by the modified boron nitride nano-tube of B component, component A 0.6:1:55 stocks;
S2, the modified boron nitride nano-tube of component A by above-mentioned steps S1, the modified boron nitride nano-tube of B component and distilled water mix It closes, set aside for use after 6-12h is stirred under the conditions of 25-45 DEG C;
S3, by above-mentioned steps S2 reaction after mixture, after removing water under reduced pressure at 65-75 DEG C, be dried in vacuo at 50-60 DEG C The i.e. modified boron nitride nanometer tube material of composite toughening material is made after 36-48h.
6. high tenacity lightweight concrete according to claim 5, it is characterised in that:The modified boron nitride nanometer of the component A The preparation method of pipe includes the following steps:
A1, activated 3-8kg boron nitride nano-tube and 0.2-2kg trichloro-triazine are mixed in 60-260L acetone, Stir 12-15h at 12-15 DEG C, then react 80-85h at 11-15 DEG C, through acetone clean after under the conditions of 8-10 DEG C vacuum Dry 15-20h;
A2, by through above-mentioned steps A1 treated 3-8kg boron nitride nano-tube 80-180L N, in N '-dimethyl formamide After dissolution, it is added in the 20-40L xylene solution dissolved with 0.5-1.5kg polyethylene glycol oxide, after stirring 2-3h at 5 DEG C, Isothermal reaction 18-20h after being warming up to 62 DEG C under nitrogen protection, then isothermal reaction 18-22h after being warming up to 80 DEG C;The polyoxy 48-50h need to be dried in vacuo at 65 DEG C before use by changing ethylene;
After A3, fully reacting, evaporating solvent under reduced pressure is cleaned with dimethylbenzene and acetone, is made after being dried in vacuo 22-25h at 65 DEG C Obtain the modified boron nitride nano-tube of component A;Polyethylene glycol oxide and boron nitride nano-tube in the modified boron nitride nano-tube of the component A Mass content ratio is 0.05-0.2:1.
7. high tenacity lightweight concrete according to claim 5, it is characterised in that:The modified boron nitride nanometer of the B component The preparation method of pipe includes the following steps:
B1, by the 1-10kg boron nitride nano-tube of activated processing and the BF of 0.3-0.6kg3•O(C2H5)2It is sub- in 50-200L dichloro It is mixed in methyl, after stirring 1-1.5h under conditions of vacuum and 20 DEG C, the 3- ethyl -3- of 1-3kg is slowly added dropwise in 3-5h Isothermal reaction 40-45h after being warming up to 25 DEG C is added dropwise in hydroxymethyl-oxetane, and 30-100L ethyl alcohol is then added and continues Stir 1-2h;
B2,300-500L distilled water is added in the system after above-mentioned steps B2 reaction, retention is solid after standing 28-36h filtering Body cleans obtained solid with distilled water, 24-48h is finally dried in vacuo at 55-75 DEG C, the modified boron nitride of B component is made Nanotube.
8. any high tenacity lightweight concrete of according to claim 6 or 7, it is characterised in that:The boron nitride nano-tube Activation process step it is as follows:
C1, boron nitride nano-tube 8kg is chosen, is 350-400rpm and every automatic conversion direction of rotation 30-40 minutes in revolving speed Under the conditions of after ball milling 24-36h, obtain the boron nitride nano-tube that average length is 0.5-1.2 μm;After being eluted with water, in 80-85 DEG C It is stand-by after lower vacuum drying 30-35h;
C2, by by above-mentioned steps C1 processing 3-6kg boron nitride nano-tube and 10-15kg thionyl chloride it is organic molten in 15-25L It is mixed in agent M, after stirring 5-12h at 85-90 DEG C, 35-40min is centrifuged with the revolving speed of 6000-7000rpm, separates solid, benefit Separating obtained solid is cleaned with organic solvent P, then is dried in vacuo 18-20h at 25-30 DEG C;
C3, under nitrogen protection, will be by above-mentioned steps C2 treated 3-6kg boron nitride nano-tube and 2-8L pyridine, 0.5- 1.5kg organic diol compound mixes in 100-150L organic solvent Q, and after reacting 10-15h at 85-90 DEG C, decompression is steamed Except organic solvent Q and pyridine, then after solvent P is cleaned, it is dried in vacuo 20-32h at 20-25 DEG C, obtains activated processing Boron nitride nano-tube.
9. high tenacity lightweight concrete according to claim 8, it is characterised in that:The organic solvent M is N, N '-diformazan One of base formamide or N-Methyl pyrrolidone;The organic solvent P is one of anhydrous propanone or tetrahydrofuran;Institute Stating organic diol compound is one of ethylene glycol or 1,3- propylene glycol;The organic solvent Q is N-Methyl pyrrolidone Or N, one of N '-dimethyl acetamide.
10. a kind of method for preparing high tenacity lightweight concrete as claimed in claim 9, specifically comprises the following steps:
D1, composite toughening materials for later use is prepared;
D2, the hollow glass micropearl sorted out from flyash are stand-by as ultra-fine microballon;
D3, by cement, haydite, flyash, fine sand, ultra-fine microballon, nano silica, desulfurized gypsum, quartz sand and compound increasing Tough material pours into dry mixing 2-3min in concrete mixer;
D4, polyacrylate, water-reducing agent, quick lime, foaming agent, swelling agent, methacrylic acid, calcium formate and new penta 2 are added Alcohol continues mix 15-20min;
D5, then the mixture being stirred is put into mold, is plugged and pounded, is compacted, atmospheric steam curing, demoulding and high pressure is steamed High tenacity lightweight concrete can be obtained after vapour maintenance.
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