CN108069665A - A kind of graphene concrete and its preparation process - Google Patents

A kind of graphene concrete and its preparation process Download PDF

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Publication number
CN108069665A
CN108069665A CN201810068302.0A CN201810068302A CN108069665A CN 108069665 A CN108069665 A CN 108069665A CN 201810068302 A CN201810068302 A CN 201810068302A CN 108069665 A CN108069665 A CN 108069665A
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parts
graphene
concrete
lignosulfonates
cement
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Inventor
李正坤
李文涛
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Shandong Shengyun International Trade Co., Ltd.
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Weihai Nanhai Carbon Materials Science And Technology Research Institute Co Ltd
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Priority to CN201810068302.0A priority Critical patent/CN108069665A/en
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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
    • C04B28/02Compositions 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
    • C04B28/04Portland 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
    • C04B24/00Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/16Sulfur-containing compounds
    • C04B24/18Lignin sulfonic acid or derivatives thereof, e.g. sulfite lye
    • 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
    • C04B40/00Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028Aspects relating to the mixing step of the mortar preparation
    • 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
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20Resistance against chemical, physical or biological attack
    • 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
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20Resistance against chemical, physical or biological attack
    • C04B2111/27Water resistance, i.e. waterproof or water-repellent materials
    • 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 present invention relates to a kind of graphene concrete and its preparation process, solve the prior art prepare concrete with it is durability difference, perishable the technical issues of.The present invention provides a kind of novel graphite alkene concrete, and by weight, raw material is made of following components:150~220 parts of cement, 150~220 parts of sea sand, 225~330 parts of rubble, 5~18 parts of lignosulfonates, 40~100 parts of water, 10~40 parts of silica flour, 15~45 parts of flyash, 2~5 parts of graphene, 3~6 parts of graphene oxide, 1~2.5 part of magnesium powder, 2~12 parts of polypropylene fibre, 5~15 parts of carbon fiber, 0.5~1 part of ethylene glycol;Also provide its preparation process simultaneously.The present invention is widely used in building material field.

Description

A kind of graphene concrete and its preparation process
Technical field
The present invention relates to building material field, more particularly to a kind of graphene concrete and its preparation process.
Background technology
With industrial development and the quickening of urbanization process, concrete also becomes the buildings such as road, dam and bridge Preferred material.With the proposition of concrete high-performance, concrete durability has increasingly caused the extensive concern of each side.
In field of civil engineering, the construction material using cement concrete as representative be still be most widely used, using most into The Structural Engineering material of work(.However, with the high stratification, enlargement, multifunction of modern project structure, cement concrete conduct Most large structural material, also gradually from traditional only structural material with bearing capacity to green with it is sustainable, onlap conjunction The directions such as change, Super-ageing resistance, high-strength and high performance, high function, intelligence are developed.It is maximum existing for cement-base composite material to lack The problems such as being high brittleness, infiltration is fallen into, substantial amounts of crack is often generated in engineering, has seriously affected the security of structure and long-term Durability.This is to cause its mechanical properties decrease and the main reason for reduced service life in use.With regard to concrete material For material, although the unit total energy consumption of production is very low, huge dosage and general technical low SI make it generally to money Source, the energy and environment cause very big pressure.Extremely frigid zones winter it is general in order to ensure the quality of construction material and construction matter Amount, general winter building construction be difficult carry out, so not only delay the duration, even if but also by force construction also be difficult to ensure building Quality causes security risk.
With carrying forward vigorously for China's infrastructure so that have that high-strength, workability is good, is easy to construction molding, cost The dosage benefit of cheap concrete increases.Yet with concrete itself there are the defects of, cause inside concrete retained permitted More microcracks and hole etc..The presence of hole and micro-crack so that the vapor after oxygen and cement drying shrinkage remains in concrete In, cause the corrosion of reinforcing bar;On the other hand, these cracks will also greatly accelerate some corrosive mediums such as villaumite, sulfate etc. Intrusion, so as to substantially reduce the service life of concrete structure.How to ensure that concrete structure is made in various complicated factors With lower also there is high anti-corrosion, endurance quality to become the great theoretical puzzle in current development.
The content of the invention
The purpose of the present invention is exactly in order to overcome the above-mentioned deficiencies of the prior art, to provide a kind of durability height, anticorrosive property It can superior graphene concrete and its preparation process.
The technical proposal for solving the technical problem of the invention is:
A kind of graphene concrete, by weight, raw material is made of following components:150~220 parts of cement, sea sand 150~220 parts, 225~330 parts of rubble, 5~18 parts of lignosulfonates, 40~100 parts of water, 10~40 parts of silica flour, flyash 15~45 parts, 2~5 parts of graphene, 3~6 parts of graphene oxide, 1~2.5 part of magnesium powder, 2~12 parts of polypropylene fibre, carbon fiber 5 ~15 parts, 0.5~1 part of ethylene glycol.
Preferably, by weight, raw material is made of following components:It is 180~200 parts of cement, 180~200 parts of sea sand, broken 250~300 parts of stone, 8~15 parts of lignosulfonates, 60~80 parts of water, 20~30 parts of silica flour, 20~40 parts of flyash, graphite 3~4 parts of alkene, 4~5 parts of graphene oxide, 1.5~2.0 parts of magnesium powder, 5~10 parts of polypropylene fibre, 8~12 parts of carbon fiber, second two 0.6~0.9 part of alcohol.
Preferably, raw material is made of following components:190 parts of cement, 190 parts of sea sand, 270 parts of rubble, lignosulfonates 12 parts, 70 parts of water, 25 parts of silica flour, 30 parts of flyash, 3.5 parts of graphene, 4.5 parts of graphene oxide, 1.8 parts of magnesium powder, polypropylene 7 parts of fiber, 10 parts of carbon fiber, 0.8 part of ethylene glycol.
Preferably, strength of cement grade is 42.5 Portland cements.
Preferably, flyash is I grade of flyash, and specific surface area is more than 400cm2/ g, density are 2.6~2.8g/cm3
Preferably, ballast grain sizes size is 5~10mm, 10~20mm and 20~25mm any of which or several.
A kind of preparation process of above-mentioned graphene concrete, step are as follows:
1) number weighs raw material according to the required weight:Cement, sea sand, rubble, lignosulfonates, water, silica flour, flyash, Graphene, graphene oxide, magnesium powder, polypropylene fibre, carbon fiber, ethylene glycol;
2) after step 1) being weighed lignosulfonates and water mixed dissolution, graphene and oxygen that step 1) is added to weigh respectively Graphite alkene, ultrasonic disperse are stirred at room temperature to it and are completely dissolved, and obtain mixture solution;
3) cement, sea sand, the rubble weighed step 1) is first added in mixer after mixing, under stirring, then will Mixture solution is poured slowly into mixer made from step 2), continues to stir evenly, be eventually adding silica flour that step 1) weighs, Flyash, magnesium powder, polypropylene fibre, carbon fiber, ethylene glycol stirring, obtain graphene concrete mix;
4) it is concrete prefabricated, pour.
Preferably, the preparation method of lignosulfonates is:Industrial lignin is weighed, adds in water and sodium hydroxide stirring, 45~55 DEG C are heated to, adjusts pH to 3~5, concentration is added to be more than 27% 1~2mL of hydrogen peroxide and ferrous sulfate 1~2h of reaction, Adjust pH to 6~7;It is continuously heating to 70~80 DEG C and adjusts pH to 8~9, add ferric trichloride, react 1~1.5h;Continue to heat up To 85~95 DEG C, add sodium sulfite, until the reaction was complete, then stop stirring and heating, and be cooled to room temperature, spray drying, obtain wooden Plain sulfonate.
Preferably, the weight ratio that industrial lignin, water and sodium hydroxide add in is 1 ︰, 20 ︰ 0.04~0.1;Industrial wood Element, ferrous sulfate, the weight ratio of addition of ferric trichloride and sodium sulfite are 5 ︰, 0.5~0.7 ︰, 0.5~1 ︰ 1~5.
Beneficial effects of the present invention:Compatibility science of the present invention, it is synergistic, the graphene concrete durability height of preparation, Corrosion Protection is superior.
(1) the dispersion mixing liquid of the invention by preparing lignosulfonates and graphene and graphene oxide, realizes Grapheme material is homodisperse in concrete, and wherein lignosulfonates itself carry a large amount of active groups and graphite oxide Reactivity site is played in the active group interaction of alkene itself jointly;Simultaneous oxidation graphene and graphene are again cement Curing the reaction template that rule is provided, graphene oxide plays the catalytic action of structure connection lignosulfonates and graphene, The lignosulfonates that ultimately join, graphene oxide, graphene three synergistic effect, promote Behavior of Hardened Cement Paste to form small, shape Unified crystal structure, forming concrete, arrangement is fine and close, and the neat acicular crystals of shape reduces micro pore volume, effectively subtracts Few cracks add the compaction rate of concrete.Wherein magnesium powder is as air-entrainment, because of physics in concrete preparation process Chemical action generates gas, is evenly distributed in slurry, is allowed to the gap being filled with while volume expansion between concrete, into One step improves its compactness, reduces the shrinkage of concrete, so as to restrained effectively vapor, oxygen and other salt Class substance further improves the durability of armored concrete to the action of rust of reinforcing bar.
(2) a kind of graphene concrete of the invention has good mobile performance in preparation process, in filling Complicated Steel During muscle structure, CH grain refinements in cement are enabled to, so as to effectively regulate and control the microstructure of hydrolysis product of cement, Whole reinforcing bars can be coated, the gap between concrete and rebar structure is completely filled, without generating honeycomb, cavity etc. Defect reduces air, moisture corrosion effect, improves frost resistance, crushing resistance, impermeability and the durability of concrete.
(3) in a kind of preparation process of graphene concrete of the invention, point three steps mixing of design, the first step is by water Mud, sea sand, rubble mixing make the frame in concrete early period construct first mixing, can not only make subsequently mixing evenly, but also ensure Mobility after follow-up raw material addition;Second adds lignosulfonates, graphene and graphene oxide water solution mixing Uniformly, make it that with the uniform hybrid reaction of frame early period, the reactivity provided evenly more fully is added in for subsequent raw material Site, the defects of ensureing last concrete density obtained and do not generate honeycomb, cavity;It is eventually adding silica flour, flyash, magnesium Powder, polypropylene fibre, carbon fiber, ethylene glycol, on the basis that two steps in early period mix, the addition of final step raw material can be with Evenly light position reaction in each reaction active site, ensure the mobility of slurry in overall process, to final concrete Durability has important influence with corrosion resistance.
(4) in the present invention, using the industrial wastes such as industrial lignin, silica flour, flyash, environmental protection and energy saving, both savings are handled The cost of industrial waste, and the cost for itself preparing concrete is saved, while the frost resistance of the concrete prepared and durability are shown It writes and improves, meet environmentally friendly idea of development.
During paper-making pulping, the lignin in plant, which is often dissolved, out becomes waste liquid, because causing largely to provide Source wastes and environmental pollution.The application of industrial lignin, the clean manufacturing and Xun Huan for being beneficial to promote pulping and paper-making industry pass through Ji, solves the problems, such as fossil resource increasingly depleted, meets the target of sustainable development, has positive Significance for Environment and society Meaning.
Specific embodiment
With reference to specific embodiment, the invention will be further described, to help present disclosure is understood.The present invention Used in method unless otherwise required, be conventional production method;Used raw material unless otherwise required, is Conventional commercial product.
Embodiment 1
A kind of preparation process of graphene concrete of the present invention, step are as follows:
1) preparation of lignosulfonates:5g industrial lignins are weighed, add in 100mL water and the stirring of 0.2g sodium hydroxides; Be heated to 45 DEG C, adjust pH to 3, add in hydrogen peroxide 1mL and the 0.5g ferrous sulfate that concentration is 27% and react 1h, adjust pH to 6;It is continuously heating to 70 DEG C and adjusts pH to 8, add in 0.5g ferric trichlorides, react 1h;85 DEG C are continuously heating to, adds in the Asia of 1g Sodium sulphate;To the reaction was complete, then stop stirring and heating, and be cooled to room temperature, spray drying obtains lignosulfonates.
2) weigh by weight, raw material:Intensity is that grade is 150 parts of 42.5 Portland cement, 150 parts of sea sand, grain Footpath size is 225 parts of 5~10mm rubbles, 10 parts, I grade of silica flour and specific surface area more than 400cm2/ g, density are 2.6~2.8g/ cm315 parts of flyash, 2 parts of graphene, 3 parts of graphene oxide, 1 part of magnesium powder, 2 parts of polypropylene fibre, 5 parts of carbon fiber, ethylene glycol 0.5 part, 5 parts of lignosulfonates obtained, 40 parts of water in step 1).
3) after the lignosulfonates and water mixed dissolution that weigh step 2) are complete, the graphite weighed in step 2) is added in Alkene and graphene oxide, ultrasonic disperse are stirred at room temperature to it and are completely dissolved, and obtain mixture solution.
4) after the cement that weighs step 2), sea sand, rubble elder generation mixing, under stirring, then will step 3) it is obtained Mixture solution is poured slowly into mixer, continues to stir evenly, be eventually adding silica flour, flyash, magnesium powder that step 2) weighs, Polypropylene fibre, carbon fiber, ethylene glycol stir in concrete mixer, obtain graphene concrete mix.
5) it is concrete prefabricated, pour:Graphene concrete mix made from step 4) is delivered in mold, fills slurry It smoothes out and is covered with preservative film, form removal after maintenance, graphene concrete obtained afterwards.
Embodiment 2
A kind of preparation process of graphene concrete of the present invention, step are as follows:
1) prepared by lignosulfonates:5g industrial lignins are weighed, add in 100mL water and the stirring of 0.5g sodium hydroxides;Add Heat adjusts pH to 5 to 55 DEG C, adds in hydrogen peroxide 2mL and the 0.7g ferrous sulfate that concentration is 33% and reacts 2h, adjusts pH to 7; It is continuously heating to 80 DEG C and adjusts pH to 9, add in 1g ferric trichlorides, react 1.5h;95 DEG C are continuously heating to, adds in the sulfurous of 5g Sour sodium;To the reaction was complete, then stop stirring and heating, and be cooled to room temperature, spray drying obtains lignosulfonates.
2) weigh by weight, raw material:Strength of cement is that grade is 220 parts of 42.5 Portland cement, sea sand 220 Part, ballast grain sizes size is 330 parts of 10~20mm rubbles, and 40 parts of silica flour, I grade of its specific surface area is more than 400cm2/ g, density are 2.6~2.8g/cm345 parts of flyash, 5 parts of graphene, 6 parts of graphene oxide, 2.5 parts of magnesium powder, 12 parts of polypropylene fibre, carbon are fine 15 parts of dimension, 1 part of ethylene glycol, 100 parts of water, 18 parts of lignosulfonates made from step 1).
3) lignosulfonates and water weighed step 2) mix graphite complete to dissolving, to be weighed in addition step 2) Alkene and graphene oxide, ultrasonic disperse are stirred at room temperature to it and are completely dissolved, and obtain mixture solution.
4) after the cement that weighs step 2), sea sand, rubble elder generation mixing, under stirring, then the mixing by step 3) Object solution is poured slowly into mixer, continues to stir evenly, and it is fine to add in silica flour, flyash, magnesium powder, polypropylene that step 2) weighs Dimension, carbon fiber, ethylene glycol stir in concrete mixer, obtain graphene concrete mix;
5) it is concrete prefabricated, pour:Graphene concrete mix made from step 4) is delivered in mold, fills slurry It smoothes out and is covered with preservative film, form removal after maintenance, graphene concrete obtained afterwards.
Embodiment 3
A kind of preparation process of graphene concrete of the present invention, step are as follows:
1) prepared by lignin sulfonic acid saline solution:5g industrial lignins are weighed, 100mL water is added in and 0.4g sodium hydroxides stirs It mixes;50 DEG C are heated to, adjusts pH to 4, hydrogen peroxide 1.5mL and the 0.6g ferrous sulfate that concentration is 30% is added in and reacts 1.5h, Adjust pH to 6.5;It is continuously heating to 75 DEG C and adjusts pH to 8.5, add in ferric trichloride 0.8g, react 1.2h;It is continuously heating to 90 DEG C, add in the sodium sulfite of 3g.To the reaction was complete, then stop stirring and heating, and be cooled to room temperature, spray drying, obtain wooden Plain sulfonate.
2) weigh by weight, raw material:Intensity is that grade is 180 parts of 42.5 Portland cement, 180 parts of sea sand, grain Footpath size be 250 parts of 20~25mm rubbles, 20 parts of silica flour, I grade, its specific surface area be more than 400cm2/ g, density for 2.6~ 2.8g/cm320 parts of flyash, 3 parts of graphene, 4 parts of graphene oxide, 1.5 parts of magnesium powder, 5 parts of polypropylene fibre, 8 parts of carbon fiber, 0.6 part of ethylene glycol, 60 parts of water, 8 parts of lignosulfonates made from step 1).
3) after the lignosulfonates and water mixed dissolution that weigh step 2) are complete, the graphite weighed in step 2) is added in Alkene and graphene oxide, ultrasonic disperse are stirred at room temperature to it and are completely dissolved, and obtain mixture solution.
4) after the cement that weighs step 2), sea sand, rubble elder generation mixing, under stirring, then will step 3) it is obtained Mixture solution is poured slowly into mixer, continues to stir evenly, add in step 2) weigh silica flour, flyash, magnesium powder, poly- third Alkene fiber, carbon fiber, ethylene glycol stir in concrete mixer, obtain graphene concrete mix;
5) it is concrete prefabricated, pour:Graphene concrete mix made from step 4) is delivered in mold, fills slurry It smoothes out and is covered with preservative film, form removal after maintenance, graphene concrete obtained afterwards.
Embodiment 4
A kind of preparation process of graphene concrete of the present invention, step are as follows:
1) prepared by lignin sulfonic acid saline solution:5g industrial lignins are weighed, 100mL water is added in and 0.3g sodium hydroxides stirs It mixes, is heated to 48 DEG C, adjust pH to 4, add in hydrogen peroxide 2mL and the 0.6g ferrous sulfate that concentration is 30% and react 2h, adjust PH to 7;It is continuously heating to 76 DEG C and adjusts pH to 9, add in 0.9g ferric trichlorides, react 1.3h;92 DEG C are continuously heating to, is added in The sodium sulfite of 4g until the reaction was complete, then stops stirring and heating, and is cooled to room temperature, and spray drying obtains lignosulfonates.
2) weigh by weight, raw material:Intensity is that grade is 200 parts of 42.5 Portland cement, and 200 parts of sea sand is broken Stone particle size be 5~10mm50% and particle size be 20~25mm50% mix 300 parts, 30 parts of silica flour, I grade, its compare table Area is more than 400cm2/ g, density are 2.6~2.8g/cm340 parts of flyash, 4 parts of graphene, 5 parts of graphene oxide, polypropylene 10 parts of fiber, 12 parts of carbon fiber, 2.0 parts of magnesium powder, 0.9 part of ethylene glycol, 80 parts of water, lignosulfonates 15 made from step 1) Part.
3) lignosulfonates and water weighed step 2) are mixed to dissolving completely, add in the stone weighed in step 2) Black alkene and graphene oxide, ultrasonic disperse are stirred at room temperature to it and are completely dissolved, and obtain mixture solution.
4) after the cement that weighs step 2), sea sand, rubble elder generation mixing, under stirring, then will step 2) it is obtained Mixture solution is poured slowly into mixer, continues to stir evenly, and it is fine to add in silica flour, flyash, polypropylene that step 2) weighs Dimension, carbon fiber, magnesium powder, ethylene glycol stir in concrete mixer, obtain graphene concrete mix;
5) it is concrete prefabricated, pour:Graphene concrete mix made from step 4) is delivered in mold, fills slurry It smoothes out and is covered with preservative film, form removal after maintenance, graphene concrete obtained afterwards.
Embodiment 5
A kind of preparation process of graphene concrete of the present invention, step are as follows:
1) prepared by lignin sulfonic acid saline solution:5g industrial lignins are weighed, 100mL water is added in and 0.3g sodium hydroxides stirs It mixes, is heated to 52 DEG C, adjust pH to 4, add in hydrogen peroxide 2mL and the 0.6g ferrous sulfate that concentration is 30% and react 1.5h, adjust Save pH to 6;It is continuously heating to 78 DEG C and adjusts pH to 8, add in 0.8g ferric trichlorides, react 1.4h;92 DEG C are continuously heating to, is added Enter the sodium sulfite of 5g, until the reaction was complete, then stop stirring and heating, and be cooled to room temperature, spray drying obtains lignin sulfonic acid Salt.
2) weigh by weight, raw material:Intensity is that grade is 190 parts of 42.5 Portland cement, and 190 parts of sea sand is broken Stone particle size is 5~10mm30%, particle size is 10~20mm35% and particle size is 10~20mm35% mixing 270 Part, 25 parts of silica flour, I grade, its specific surface area be more than 400cm2/ g, density are 2.6~2.8g/cm330 parts of flyash, graphene 3.5 Part, 4.5 parts of graphene oxide, 7 parts of polypropylene fibre, 10 parts of carbon fiber, 1.8 parts of magnesium powder, 0.8 part of ethylene glycol, 70 parts of water, step 1) 12 parts of lignosulfonates made from.
3) lignosulfonates and water weighed step 2) are mixed to dissolving completely, add in the stone weighed in step 2) Black alkene and graphene oxide, ultrasonic disperse are stirred at room temperature to it and are completely dissolved, and obtain mixture solution.
4) after the cement that weighs step 2), sea sand, rubble elder generation mixing, under stirring, then will step 3) it is obtained Mixture solution is poured slowly into mixer, continues to stir evenly, and it is fine to add in silica flour, flyash, polypropylene that step 2) weighs Dimension, carbon fiber, magnesium powder, ethylene glycol stir in concrete mixer, obtain graphene concrete mix;
5) it is concrete prefabricated, pour:Graphene concrete mix made from step 4) is delivered in mold, fills slurry It smoothes out and is covered with preservative film, form removal after maintenance, graphene concrete obtained afterwards.
Comparative example 1
A kind of preparation process of graphene concrete, step are as follows:
1) weigh by weight, raw material:Intensity is that grade is 190 parts of 42.5 Portland cement, and 190 parts of sea sand is broken Stone particle size is 5~10mm30%, particle size is 10~20mm35% and particle size is 10~20mm35% mixing 270 Part, 25 parts of silica flour, I grade, its specific surface area be more than 400cm2/ g, density are 2.6~2.8g/cm330 parts of flyash, graphene 3.5 Part, 4.5 parts of graphene oxide, 7 parts of polypropylene fibre, 10 parts of carbon fiber, 1.8 parts of magnesium powder, 0.8 part of ethylene glycol, 70 parts of water.
2) preparation of cement mortar:Step 1) is taken to weigh 70 parts of water, adds in graphene and graphene oxide, ultrasonic disperse, room Temperature stirring is completely dissolved to it, obtains mixture solution.
3) after the cement that weighs step 1), sea sand, rubble elder generation mixing, under stirring, then will step 2) it is obtained Mixture solution is poured slowly into mixer, continues to stir evenly, and is eventually adding silica flour, flyash, poly- third that step 1) weighs Alkene fiber, carbon fiber, magnesium powder, ethylene glycol stir in concrete mixer, obtain graphene concrete mix;
4) it is concrete prefabricated, pour:Graphene concrete mix made from step 3) is delivered in mold, fills slurry It smoothes out and is covered with preservative film, form removal after maintenance, graphene concrete obtained afterwards.
Comparative example 2
A kind of preparation process of concrete, step are as follows:
1) prepared by lignin sulfonic acid saline solution:5g industrial lignins are weighed, 100mL water is added in and 0.3g sodium hydroxides stirs It mixes, is heated to 52 DEG C, adjust pH to 4, add in hydrogen peroxide 2mL and the 0.6g ferrous sulfate that concentration is 30% and react 1.5h, adjust Save pH to 6;It is continuously heating to 78 DEG C and adjusts pH to 8, add in 0.8g ferric trichlorides, react 1.4h;92 DEG C are continuously heating to, is added Enter the sodium sulfite of 5g, until the reaction was complete, then stop stirring and heating, and be cooled to room temperature, spray drying obtains lignin sulfonic acid Salt.
2) weigh by weight, raw material:Intensity be grade be 190 parts of 42.5 Portland cement, it is 190 parts of sea sand, broken Stone particle size is 5~10mm30%, particle size is 10~20mm35% and particle size is 10~20mm35% mixing 270 Part, 25 parts of silica flour, I grade, its specific surface area be more than 400cm2/ g, density are 2.6~2.8g/cm330 parts of flyash, polypropylene are fine 7 parts of dimension, 10 parts of carbon fiber, 1.8 parts of magnesium powder, 0.8 part of ethylene glycol, 70 parts of water, 12 parts of lignosulfonates made from step 1).
3) after the lignosulfonates and water mixed dissolution that weigh step 2) are complete, ultrasonic disperse is stirred at room temperature to it It is completely dissolved, obtains mixture solution.
4) after the cement that weighs step 2), sea sand, rubble elder generation mixing, under stirring, then will step 3) it is obtained Mixture solution is poured slowly into mixer, continues to stir evenly, and is eventually adding silica flour, flyash, poly- third that step 2) weighs Alkene fiber, carbon fiber, magnesium powder, ethylene glycol stir in concrete mixer, obtain concrete mix;
5) it is concrete prefabricated, pour:Concrete mix made from step 4) is delivered in mold, is smoothed out after filling slurry And it is covered with preservative film, form removal after maintenance, concrete obtained.
Only as described above, is only specific embodiments of the present invention, when cannot limit the model implemented of the present invention with this It encloses, such as lignosulfonates or commercially available lignosulfonates in above-described embodiment 1~5.
The performance of the graphene concrete further illustrated the present invention below by performance test results.
(1) tested material:Concrete is as quilt made from graphene concrete made from Examples 1 to 5 and comparative example 1~2 Detect sample;
(2) experimental method:According to GB/T50081-2002《Standard for test methods of mechanical properties of ordinary concrete》、 GB50010-2010《Code for design of concrete structures》Standard, GB23439-2009《Cement expansive material》Standard, GB6566 《Radioactive material nucleic》Standard, GB748《Sulfate resisting Portland cement》Standard requirement, JTJ275《Harbour engineering is mixed Xtah Crude Clay structure anticorrosion technique specification》Standard and GB50119《Technical code for application of admixture in concrete》It is every to detect it for standard Performance the results are shown in Table 1.
1 concrete properties testing result of table
Concrete performance of the present invention is as a result, the electric flux of graphene concrete, coagulation made from Examples 1 to 5 after testing The freeze proof grade of soil, compression strength, resistant to corrosion coefficient, early stage cracking resistance, water resistant infiltration grade are each with the concrete of comparative example 1~2 Item performance has conspicuousness raising;Wherein concrete formulation does not add in lignin compared with Examples 1 to 5 formula in comparative example 1 Sulfonic acid saline solution, concrete formulation does not add in graphene and graphene oxide compared with Examples 1 to 5 formula in comparative example 2, In the graphene concrete formulation for absolutely proving the present invention, the lignosulfonates of addition, graphene oxide, graphene three association Same-action promotes Behavior of Hardened Cement Paste to form crystal structure small, that shape is unified, forming concrete, arrangement is fine and close, and shape is neat Acicular crystals reduces micro pore volume, effectively reduces cracks, add the compaction rate of concrete, reduce its electric conductivity Can, further enhance its water resistant infiltration grade and resistant to corrosion coefficient.
The electric flux of graphene concrete, concrete antifreezing grade, compression strength, resistant to corrosion system made from Examples 1 to 5 Number, early stage cracking resistance, water resistant infiltration grade, meet GB23439-2009《Cement expansive material》Standard, GB6566《Construction material Radionuclide》Standard, GB748《Sulfate resisting Portland cement》Standard requirement, JTJ275《Concrete for marine works structure is prevented Corrosion technology specification》Standard and GB50119《Technical code for application of admixture in concrete》The requirement of standard concrete items technology, Middle embodiment 5 has excellent anti-erosion, cracking resistance and impermeability, improves concrete structure durability.
Only as described above, is only specific embodiments of the present invention, when cannot limit the model implemented of the present invention with this It encloses, all equivalent changes and modifications done according to scope of the present invention patent, should all belong to the covering scope of the present invention.

Claims (9)

1. a kind of graphene concrete, which is characterized in that by weight, raw material is made of following components:Cement 150~ 220 parts, 150~220 parts of sea sand, 225~330 parts of rubble, 5~18 parts of lignosulfonates, 40~100 parts of water, silica flour 10~ 40 parts, 15~45 parts of flyash, 2~5 parts of graphene, 3~6 parts of graphene oxide, 1~2.5 part of magnesium powder, polypropylene fibre 2~ 12 parts, 5~15 parts of carbon fiber, 0.5~1 part of ethylene glycol.
2. a kind of graphene concrete according to claim 1, which is characterized in that by weight, the raw material by with Lower component is formed:180~200 parts of cement, 180~200 parts of sea sand, 250~300 parts of rubble, 8~15 parts of lignosulfonates, 60~80 parts of water, 20~30 parts of silica flour, 20~40 parts of flyash, 3~4 parts of graphene, 4~5 parts of graphene oxide, magnesium powder 1.5 ~2.0 parts, 5~10 parts of polypropylene fibre, 8~12 parts of carbon fiber, 0.6~0.9 part of ethylene glycol.
3. a kind of graphene concrete according to claim 2, which is characterized in that by weight, the raw material by with Lower component is formed:190 parts of cement, 190 parts of sea sand, 270 parts of rubble, 12 parts of lignosulfonates, 70 parts of water, 25 parts of silica flour, powder 30 parts of coal ash, 3.5 parts of graphene, 4.5 parts of graphene oxide, 1.8 parts of magnesium powder, 7 parts of polypropylene fibre, 10 parts of carbon fiber, second two 0.8 part of alcohol.
4. according to a kind of graphene concrete described in claims 1 to 3 any of which one, which is characterized in that the cement Strength grade is 42.5 Portland cements.
5. according to a kind of graphene concrete described in claims 1 to 3 any of which one, which is characterized in that the fine coal Ash is I grade of flyash, and specific surface area is more than 400cm2/ g, density are 2.6~2.8g/cm3
6. according to a kind of graphene concrete described in claims 1 to 3 any of which one, which is characterized in that the rubble Particle size is 5~10mm, 10~20mm and 20~25mm any of which or several.
7. according to a kind of preparation process of graphene concrete described in claim 1~6 any of which one, feature exists In step is as follows:
1) number weighs raw material according to the required weight:Cement, sea sand, rubble, lignosulfonates, water, silica flour, flyash, graphite Alkene, graphene oxide, magnesium powder, polypropylene fibre, carbon fiber, ethylene glycol;
2) after step 1) being weighed lignosulfonates and water mixed dissolution, graphene and oxidation stone that step 1) weighs are added respectively Black alkene, ultrasonic disperse are stirred at room temperature to it and are completely dissolved, and obtain mixture solution;
3) cement, sea sand, the rubble weighed step 1) is first added in mixer after mixing, under stirring, then by step 2) mixture solution is poured slowly into mixer made from, continues to stir evenly, and is eventually adding silica flour, fine coal that step 1) weighs Ash, magnesium powder, polypropylene fibre, carbon fiber, ethylene glycol stirring, obtain graphene concrete mix;
4) it is concrete prefabricated, pour.
A kind of 8. preparation process of graphene concrete according to claim 7, which is characterized in that the lignin sulfonic acid The preparation method of salt is:Weigh industrial lignin, add in water and sodium hydroxide stirring, be heated to 45~55 DEG C, adjust pH to 3~ 5, concentration is added to be more than 27% 1~2mL of hydrogen peroxide and ferrous sulfate 1~2h of reaction, adjusts pH to 6~7;It is continuously heating to 70~ 80 DEG C and pH to 8~9 is adjusted, add ferric trichloride, react 1~1.5h;85~95 DEG C are continuously heating to, adds sodium sulfite, until anti- Stirring and heating then should be stopped completely, and be cooled to room temperature, spray drying obtains lignosulfonates.
A kind of 9. preparation process of graphene concrete according to claim 8, which is characterized in that the industrial wood The weight ratio that element, water and sodium hydroxide add in is 1 ︰, 20 ︰ 0.04~0.1;The industrial lignin, ferrous sulfate, ferric trichloride Weight ratio with the addition of sodium sulfite is 5 ︰, 0.5~0.7 ︰, 0.5~1 ︰ 1~5.
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CN109053095A (en) * 2018-10-23 2018-12-21 含山县领创新材料科技有限公司 A kind of enhanced frost-resistant concrete of modified graphene
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CN116143474A (en) * 2023-02-16 2023-05-23 深圳大学 Cement-based composite slurry and preparation method thereof
CN116143474B (en) * 2023-02-16 2023-12-08 深圳大学 Cement-based composite slurry and preparation method thereof

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