CN110498634A

CN110498634A - A kind of graphene aqueous dispersions, graphene concrete and preparation method thereof

Info

Publication number: CN110498634A
Application number: CN201910711794.5A
Authority: CN
Inventors: 周铭; 李虓; 董健苗; 梁培森; 曹嘉威; 王留阳; 刘振钊; 李亮川; 陈鑫
Original assignee: Guangxi Qing Lu New Material Science And Technology Co Ltd; Liuzhou Qinglu Lubricant Co Ltd; Guangxi University of Science and Technology
Current assignee: Guangxi Qinglu Biotechnology Co.,Ltd.; GUANGXI QINGLU NEW MATERIAL TECHNOLOGY Co.,Ltd.; Guangxi University of Science and Technology
Priority date: 2019-08-02
Filing date: 2019-08-02
Publication date: 2019-11-26
Anticipated expiration: 2039-08-02
Also published as: CN110498634B

Abstract

The present invention provides a kind of graphene aqueous dispersions, graphene concrete and preparation method thereof, the graphene aqueous dispersions, it is made of the raw material for including following mass percent: graphene or graphene oxide 1-5%, neopelex 0.5%-2%, polyvinylpyrrolidone 0.5%-2%, remaining is water.Preparation method includes the following steps: precentagewise takes graphene or graphene oxide, neopelex, polyvinylpyrrolidone and water, be sufficiently mixed dispersion after to get.The present invention is intended to provide a kind of graphene aqueous dispersions and preparation method thereof, and the preparation method of the graphene concrete of the graphene aqueous dispersions is utilized, this graphene aqueous dispersions can improve the settlement issues of graphene in aqueous medium, the uniform and stable dispersion for realizing graphene in cement concrete, can be made the graphene concrete of quality and function admirable.

Description

A kind of graphene aqueous dispersions, graphene concrete and preparation method thereof

Technical field

The invention belongs to field of fine chemical, and in particular to a kind of graphene aqueous dispersions and preparation method thereof, and utilize The preparation method of the graphene concrete of the graphene aqueous dispersions.

Background technique

Cement concrete because of the advantage that its is cheap, overall performance is good etc., become at present most extensively, most cheap building Engineering material and special engineered material.But the durability of cement concrete is insufficient over time easily destroys, with Social economy and construction level it is increasingly developed, more stringent requirements are proposed for diversification and special property to concrete, passes The cement of system can not adapt to the requirement under special operation condition.In recent years, numerous studies have shown that in concrete add nanometer material It is greatly improved because the advantages such as its partial size is small, surface energy height, large specific surface area can effectively improve the microstructure of concrete in material Mechanical property, thermal property, electric conductivity, durability and corrosion resistance etc..

However, be added in cement concrete in nano material, although the part of properties of concrete can be improved, also band Come the side effect that can not ignore.For example, SiO₂Nano particle can be obviously improved the Sulphate-resistant property of concrete, while also make to mix Coagulate the early strength decline of soil；Nano-TiO₂With good catalytic performance, exhaust emission can especially be catalytically decomposed, but prolong Concrete final setting time is grown；CaCO₃Nano material greatly improves the mechanical property of concrete, but concrete occurs Later strength retraction problem；Nanometer AI₂O₃Material can improve the pore structure of concrete well, and CNT can significantly improve concrete Mechanical property, can be used as the additive of special concrete construction material, but CNT, AI₂O₃Preparation cost is high.Graphene (GN) as newfound two-dimension nano materials in recent years, there are the performances such as excellent mechanics, electricity, calorifics, be to promote cement One of best nano materials of performances such as agent on crack resistance of concrete folding, resistance to compression, conduction.But graphene itself neither oleophylic nor hydrophilic Performance, the added material as concrete easily occur sedimentation, agglomeration traits, it is necessary to decentralized processing is made to its surface, realize The uniform and stable dispersion of graphene in concrete.

Summary of the invention

The present invention is intended to provide a kind of graphene aqueous dispersions and preparation method thereof, and the graphene moisture is utilized The preparation method of the graphene concrete of dispersion liquid, this graphene aqueous dispersions can improve the sedimentation of graphene in aqueous medium Problem realizes the uniform and stable dispersion of graphene in cement concrete, the graphene coagulation of quality and function admirable can be made Soil.

To achieve the above object, technical scheme is as follows:

The graphene aqueous dispersions are made: graphene or graphite oxide of the raw material for including following mass percent Alkene 1-5%, neopelex 0.5%-2%, the polycarboxylic acids diminishing of polyvinylpyrrolidone 0.5%-2%, 0-10% Agent, remaining is water.

The graphene aqueous dispersions are made: graphene or graphite oxide of the raw material for including following mass percent Alkene 1-5%, neopelex 0.5%-2%, polyvinylpyrrolidone 0.5%-2%, polycarboxylate water-reducer 2- 10%, remaining is water.

The oxygen content of the graphene is 0.5-50%.

The graphene aqueous dispersions, preparation method includes the following steps:

Precentagewise takes graphene or graphene oxide, neopelex, polyvinylpyrrolidone and water, sufficiently Mixing dispersion after, be made the preliminary dispersion liquid of graphene, be added polycarboxylate water-reducer, be sufficiently mixed dispersion after to get.

The mixing point of the graphene or graphene oxide, neopelex, polyvinylpyrrolidone and water Method is dissipated, using one of ultrasound, homogeneous, grinding or more than one combination；Polycarboxylate water-reducer mixing dispersion is added Method be one of ultrasound, homogeneous, grinding or more than one combination.

The mixing point of the graphene or graphene oxide, neopelex, polyvinylpyrrolidone and water Dissipate method are as follows: at 60 ± 2.5 DEG C, constant temperature stirs 1 hour or more, it then carries out ultrasonic treatment 8 hours or more；Polycarboxylic acids is added The method of water-reducing agent mixing dispersion is one of ultrasound, homogeneous, grinding or more than one combination.

The preparation method of the graphene oxide the following steps are included:

The concentrated sulfuric acid for taking 200-500 parts by weight is cooled to 0 DEG C, and then under 0 DEG C of environment, the nitre of 4-10 parts by weight is added The crystalline flake graphite of sour sodium and 5-20 parts by weight stirs 10-60 minutes, is added slowly with stirring the permanganic acid of 30-80 parts by weight Potassium continues to be uniformly mixed, and uniformly mixed system is transferred quickly in 30-40 DEG C of water-bath or oil bath, constant temperature stirring 1-4 hours, the water of 200-800 parts by weight is added, then moves into reaction system rapidly in 90-100 DEG C of oil bath pan, constant temperature stirs It mixes 0.5-2 hours, is then stirred for that the hydrogen peroxide of 50-200 parts by weight is added under state, continues to stir, until solution is in shallow When yellow, water dilution, stirring, isolated solid is added, is added water into solid, stirring and washing separates solid, repeats to adding Dispersion after entering water is neutrality, separation take solid to get.

The preparation method of the preliminary dispersion liquid of the graphene the following steps are included:

The concentrated sulfuric acid for taking 200-500 parts by weight is cooled to 0 DEG C, and then under 0 DEG C of environment, the nitre of 4-10 parts by weight is added The crystalline flake graphite of sour sodium and 5-20 parts by weight stirs 10-60 minutes, is added slowly with stirring the permanganic acid of 30-80 parts by weight Potassium continues to be uniformly mixed, and uniformly mixed system is transferred quickly in 30-40 DEG C of water-bath or oil bath, constant temperature stirring 1-4 hours, the water of 200-800 parts by weight is added, then moves into reaction system rapidly in 90-100 DEG C of oil bath pan, constant temperature stirs It mixes 0.5-2 hours, is then stirred for that the hydrogen peroxide of 50-200 parts by weight is added under state, continues to stir, until solution is in shallow When yellow, water dilution, stirring, isolated solid is added；

The water of 50-150 parts by weight is added into solid, stirring and washing separates solid, repeats to the dispersion after addition water System is neutrality；

The quality of graphene oxide is in terms of the quality for the crystalline flake graphite being initially added, using the quality of this graphene oxide as base Neopelex, polyvinylpyrrolidone are added into aqueous dispersion, and supplements and adds water for standard, are sufficiently mixed dispersion, Polycarboxylate water-reducer is added, after being sufficiently mixed dispersion, aqueous dispersion is obtained, so that graphene oxide in the aqueous dispersion Mass percentage content is 1-5%, and neopelex mass percentage content is 0.5%-2%, polyvinylpyrrolidine Ketone mass percentage content is 0.5%-2%, the polycarboxylate water-reducer of 0-10%.

In the graphene aqueous dispersions, the partial size of graphene or graphene oxide are as follows:: D50=5 μm~140 μm.

A kind of preparation method of graphene concrete, applies above-mentioned graphene aqueous dispersions, comprising the following steps:

Graphene aqueous dispersions are taken, polycarboxylate water-reducer, water and cement is added；

Then ultrasound 10-30min, adds normal sand, stirring be made into cement mortar to get；

Or without ultrasound, be directly added into normal sand, stirring be made into cement mortar to get；

Wherein, graphene or graphene oxide are 0.003%~0.08% relative to the mass fraction of cement；Polycarboxylic acids subtracts Aqua is 0.1-0.9% relative to the mass fraction of cement.

The invention has the benefit that

Inventor has found by numerous studies, using anionic surfactant sodium dodecylbenzene sulfonate (SDBS) and non- Ionic surface active agent polyvinylpyrrolidone (PVP) combination is used as dispersing agent, the graphene aqueous dispersions prepared, mixed There are very outstanding uniform and stable disperse properties in solidifying soil, can effectively substitute expensive CNT, AI₂O₃Etc. the prior arts dispersion Agent material.

The present invention uses anionic surfactant and anionic surfactant matched combined with heterocycle structure to make For dispersing agent, more stable π-π interaction can be formed with graphene, while alkane long-chain passes through negative electron exchange adsorption On the surface of graphene, overcome the Van der Waals force between graphene sheet layer, form steric hindrance and electrostatic steric effect overcomes graphite The agglomeration traits of alkene, and the hydrophilic group on heterocycle can improve the hydrophily at graphene interface, and pass through electrostatic repulsion forces and sky Between steric hindrance realize the uniform and stable dispersion of graphene in concrete, the sedimentation so as to improve graphene in cement concrete asks Topic.

Moreover, inventor also found after study, using concrete made of this graphene aqueous dispersions, have very Outstanding flexural strength after the present dispersions system of a small amount of graphene is added, can reach flexural strength and promote 10% or more Excellent technical effect after the present dispersions system of small amounts graphene is added, can reach flexural strength and promote 27% or more Excellent technical effect.Also, dispersion liquid of the invention, is directly added into cement paste, also can preferably promote cement paste The flexural strength and compression strength of part is made.

The preferred ultrasound removing expanded graphite of the present invention prepares graphene aqueous liquid dispersion, inventor has found that relatively In other dispersion means, ultrasound can increase the hydrophily of graphene, promote its stable dispersion in cement concrete.

The present invention use graphene oxide aqueous dispersions scheme, using graphene surface oxygen-containing group and aoxidizing The oxygen-containing group generated in journey can form more hydrogen bond mating reactions with dispersing agent, can preferably improve stone in aqueous medium The settlement issues of black alkene realize the uniform and stable dispersion of graphene in cement concrete.

Graphene dispersing solution of the invention has following three advantages significantly: 1) increasing adjoining graphite alkene piece interlamellar spacing, have Help solve the dispersion of graphene；2) node is provided for the absorption of dispersing agent on the surface of graphene, passes through electrostatic repulsion Power and space bit resistance offset the Van der Waals force of graphene film interlayer, solve the agglomeration traits of graphene；3) compare other stones The graphene defect of black alkene preparation method, program preparation is less, and the oxygen-containing group of graphene surface improves its interface Hydrophily.

Detailed description of the invention

Fig. 1 ultrasonic disperse (left side), mechanical stirring (right side) stand 0 point of comparison diagram；

Fig. 2 ultrasonic disperse (left side), mechanical stirring (right side) stand 10 points of comparison diagrams；

Fig. 3 test specimen illustraton of model；

Fig. 4 cement mortar tryout figure；

The examination body figure that Fig. 5 is removed；

First and second batch of graphene oxide 7d glue sand flexural strength analysis chart of Fig. 6；

First and second batch of graphene oxide 7d glue sand Compressive Strength Analysis figure of Fig. 7；

First and second batch of graphene oxide 7d cement paste flexural strength analysis chart of Fig. 8；

First and second batch of graphene oxide 7d cement paste Compressive Strength Analysis figure of Fig. 9.

Specific embodiment

The present invention is described in detail combined with specific embodiments below.

Embodiment 1

The graphene aqueous dispersions are made: graphene 1%, dodecane of the raw material for including following mass percent Base benzene sulfonic acid sodium salt 0.5%, polyvinylpyrrolidone 0.5%, remaining is water.

The oxygen content of the graphene is 0.5%.

Precentagewise takes graphene, neopelex, polyvinylpyrrolidone and water, is dispersed using ultrasonic mixing Afterwards to get.

In the graphene aqueous dispersions, the partial size of graphene are as follows: D50=5-60 μm.

Apply above-mentioned graphene aqueous dispersions, the method for preparing graphene concrete, comprising the following steps:

Graphene aqueous dispersions are taken, polycarboxylate water-reducer, 190kg water and 310kg cement, ultrasonic 10min is added and adds 710kg normal sand, stirring be made into cement mortar to get；Wherein, graphene is 0.003% relative to the mass fraction of cement；It is poly- Carboxylic acid water reducer is 0.1% relative to the mass fraction of cement.

It is as needed using unit, increase the other materials such as coarse aggregate by mix Design, is made after agitated Concrete.

Embodiment 2

The graphene aqueous dispersions, which is characterized in that be made of the raw material for including following mass percent: graphene 5%, neopelex 2%, polyvinylpyrrolidone 2%, remaining is water.

The oxygen content of the graphene is 50%.

Precentagewise takes graphene, neopelex, polyvinylpyrrolidone and water, is mixed and is dispersed using homogeneous Afterwards to get.

In the graphene aqueous dispersions, the partial size of graphene are as follows:: D50=100-140 μm.

Graphene aqueous dispersions are taken, polycarboxylate water-reducer, 200kg water and 320kg cement is added, after being stirred, then plus Enter 810kg normal sand, stirring be made into cement mortar to get；

Wherein, graphene is 0.08% relative to the mass fraction of cement；Quality of the polycarboxylate water-reducer relative to cement Score is 1%.

Embodiment 3

The graphene aqueous dispersions, which is characterized in that be made of the raw material for including following mass percent: graphene 3%, neopelex 1%, polyvinylpyrrolidone 1.2%, remaining is water.

The oxygen content of the graphene is 10%.

Precentagewise takes graphene, neopelex, polyvinylpyrrolidone and water, is dispersed using ground and mixed Afterwards to get.

In the graphene aqueous dispersions, the partial size of graphene are as follows:: D50=50-100 μm.

Graphene aqueous dispersions are taken, polycarboxylate water-reducer, 150kg water and 330kg cement, ultrasonic 30min is added and adds 680kg normal sand, stirring be made into cement mortar to get；

Wherein, graphene is 0.08% relative to the mass fraction of cement；Quality of the polycarboxylate water-reducer relative to cement Score is 0.9%.

Embodiment 4

The oxygen content of the graphene is 30%.

Precentagewise takes graphene, neopelex, polyvinylpyrrolidone and water, permanent at 60 ± 2.5 DEG C Temperature stirring 1 hour or more, then carry out ultrasonic treatment 8 hours or more to get.

In the graphene aqueous dispersions, the partial size of graphene are as follows:: D50=60-110 μm.

Graphene aqueous dispersions are taken, polycarboxylate water-reducer, 140kg water and 430kg cement, ultrasonic 20min is added and adds 640kg normal sand, stirring be made into cement mortar to get；

Wherein, graphene oxide is 0.02% relative to the mass fraction of cement；Polycarboxylate water-reducer is relative to cement Mass fraction is 0.3%.

Embodiment 5

The graphene aqueous dispersions are made of the raw material for including following mass percent: graphene oxide 1%, and ten Dialkyl benzene sulfonic acids sodium 0.5%, polyvinylpyrrolidone 0.5%, remaining is water.

Precentagewise takes graphene oxide, neopelex, polyvinylpyrrolidone and water, using ultrasonic mixing After dispersion to get.

The preparation method of the graphene oxide the following steps are included:

The concentrated sulfuric acid for taking 200kg is cooled to 0 DEG C, and then under 0 DEG C of environment, the sodium nitrate of 4kg and the scale of 5kg is added Graphite stirs 10-60 minutes, is added slowly with stirring the potassium permanganate of 30kg, continues to be uniformly mixed, will be uniformly mixed System be transferred quickly in 30 DEG C of water-bath or oil bath, constant temperature stir 1 hour, the water of 200kg is added, then by reaction system It moving into rapidly in 90 DEG C of oil bath pan, constant temperature stirs 0.5 hour, it is then stirred for that the hydrogen peroxide of 50kg is added under state, after Continuous stirring water is added into solid, stirring is clearly until water dilution, stirring, isolated solid is added when solution is in light yellow Wash, separate solid, repeat to be added water after dispersion for neutrality, separation take solid to get.

In the graphene aqueous dispersions, the partial size of graphene oxide are as follows:: D50=5-40 μm.

Graphene aqueous dispersions are taken, polycarboxylate water-reducer, 190kg water and 430kg cement, ultrasonic 10min is added and adds 645kg normal sand, stirring be made into cement mortar to get；

Wherein, graphene oxide is 0.003% relative to the mass fraction of cement；Polycarboxylate water-reducer is relative to cement Mass fraction is 0.1%.

Embodiment 6

The graphene aqueous dispersions are made of the raw material for including following mass percent: graphene oxide 5%, and ten Dialkyl benzene sulfonic acids sodium 2%, polyvinylpyrrolidone 2%, remaining is water.

The preparation method of the graphene oxide the following steps are included:

The concentrated sulfuric acid for taking 500kg is cooled to 0 DEG C, and then under 0 DEG C of environment, the sodium nitrate of 10kg and the squama of 20kg is added Piece graphite stirs 60 minutes, is added slowly with stirring the potassium permanganate of 80kg, continues to be uniformly mixed, will be uniformly mixed System be transferred quickly in 40 DEG C of water-bath or oil bath, constant temperature stir 4 hours, the water of 800kg is added, then by reaction system It moving into rapidly in 100 DEG C of oil bath pan, constant temperature stirs 2 hours, it is then stirred for that the hydrogen peroxide of 200kg is added under state, after Continuous stirring water is added into solid, stirring is clearly until water dilution, stirring, isolated solid is added when solution is in light yellow Wash, separate solid, repeat to be added water after dispersion for neutrality, separation take solid to get.

In the graphene aqueous dispersions, the partial size of graphene oxide are as follows:: D50=100 μm -140 μm.

Graphene aqueous dispersions are taken, polycarboxylate water-reducer, 200kg water and 572kg cement, ultrasonic 30min is added and adds 480kg normal sand, stirring be made into cement mortar to get；

Wherein, graphene oxide is 0.08% relative to the mass fraction of cement；Polycarboxylate water-reducer is relative to cement Mass fraction is 0.9%.

Embodiment 7

The graphene aqueous dispersions are made of the raw material for including following mass percent: graphene oxide 3%, and ten Dialkyl benzene sulfonic acids sodium 1.1, polyvinylpyrrolidone 0.8%, remaining is water.

The preparation method of the graphene oxide the following steps are included:

The concentrated sulfuric acid for taking 300kg is cooled to 0 DEG C, and then under 0 DEG C of environment, the sodium nitrate of 6kg and the scale of 10kg is added Graphite stirs 30 minutes, is added slowly with stirring the potassium permanganate of 50kg, continues to be uniformly mixed, by what is be uniformly mixed System is transferred quickly in 35 DEG C of water-bath or oil bath, and constant temperature stirs 2 hours, and the water of 400kg is added, then that reaction system is fast Speed moves into 95 DEG C of oil bath pan, and constant temperature stirs 1 hour, is then stirred for that the hydrogen peroxide of 100kg is added under state, continues to stir It mixes, when solution is in light yellow, water dilution, stirring, isolated solid is added, water is added into solid, stirring and washing is divided From solid, repeat to be added water after dispersion for neutrality, separation take solid to get.

In the graphene aqueous dispersions, the partial size of graphene oxide are as follows:: D50=80 μm -120 μm.

Graphene aqueous dispersions are taken, polycarboxylate water-reducer, 180kg water and 360kg cement, ultrasonic 20min is added and adds 660kg normal sand, stirring be made into cement mortar to get；

Wherein, graphene oxide is 0.01% relative to the mass fraction of cement；Polycarboxylate water-reducer is relative to cement Mass fraction is 0.4%.

Embodiment 8

The graphene aqueous dispersions are made of the raw material for including following mass percent: graphene oxide 4%, and ten Dialkyl benzene sulfonic acids sodium 1.5, polyvinylpyrrolidone 0.9%, remaining is water.

Precentagewise takes graphene oxide, neopelex, polyvinylpyrrolidone and water, at 60 ± 2.5 DEG C Under, constant temperature stirs 1 hour or more, then carry out ultrasonic treatment 8 hours or more to get.

The preparation method of the graphene oxide the following steps are included:

The concentrated sulfuric acid for taking 400kg is cooled to 0 DEG C, and then under 0 DEG C of environment, the sodium nitrate of 6kg and the scale of 15kg is added Graphite stirs 40 minutes, is added slowly with stirring the potassium permanganate of 60kg, continues to be uniformly mixed, by what is be uniformly mixed System is transferred quickly in 38 DEG C of water-bath or oil bath, and constant temperature stirs 3 hours, and the water of 600kg is added, then that reaction system is fast Speed moves into 98 DEG C of oil bath pan, and constant temperature stirs 1.5 hours, is then stirred for that the hydrogen peroxide of 150kg is added under state, continues Stirring, until solution in it is light yellow when, water dilution, stirring, isolated solid is added, is added water into solid, stirring and washing, Separate solid, repeat to be added water after dispersion for neutrality, separation take solid to get.

In the graphene aqueous dispersions, the partial size of graphene oxide are as follows:: D50=60 μm -110 μm.

Using above-mentioned graphene aqueous dispersions, the method for preparing graphene concrete, comprising the following steps:

Graphene aqueous dispersions are taken, polycarboxylate water-reducer, 192kg water and 300kg cement is added, is uniformly mixed, adds 735kg normal sand, stirring be made into cement mortar to get；

Wherein, crystalline flake graphite is 0.008% relative to the mass fraction of cement；Matter of the polycarboxylate water-reducer relative to cement Measuring score is 0.6%.

Embodiment 9

Graphene oxide aqueous dispersions preparation method the following steps are included:

The concentrated sulfuric acid for taking 200kg is cooled to 0 DEG C, and then under 0 DEG C of environment, the sodium nitrate of 4kg and the scale of 5kg is added Graphite stirs 10 minutes, is added slowly with stirring the potassium permanganate of 30kg, continues to be uniformly mixed, by what is be uniformly mixed System is transferred quickly in 30 DEG C of water-bath or oil bath, and constant temperature stirs 1 hour, and the water of 200kg is added, then that reaction system is fast Speed moves into 90 DEG C of oil bath pan, and constant temperature stirs 0.5 hour, is then stirred for that the hydrogen peroxide of 50kg is added under state, continues Stirring, until water dilution, stirring, isolated solid is added when solution is in light yellow；The water of 80kg is added into solid, stirs Cleaning is mixed, solid is separated, repeats to the dispersion after addition water to be neutrality；Squama of the quality of graphene oxide to be initially added Neopelex is added into aqueous dispersion on the basis of the quality of this graphene oxide for the quality meter of piece graphite, Polyvinylpyrrolidone, and supplement plus water, ultrasound prepares aqueous dispersion so that in the aqueous dispersion graphene oxide matter Measuring degree is 1%, and neopelex mass percentage content is 0.5%, polyvinylpyrrolidone quality hundred Dividing than content is 0.5%.

In the graphene aqueous dispersions, the partial size of graphene oxide are as follows:: D50=5 μm -40 μm.

Graphene aqueous dispersions are taken, polycarboxylate water-reducer, 170kg water and 240kg cement, ultrasonic 10min is added and adds 880kg normal sand, stirring be made into cement mortar to get；

Wherein, crystalline flake graphite is 0.003% relative to the mass fraction of cement；Matter of the polycarboxylate water-reducer relative to cement Measuring score is 0.1.

Embodiment 10

The concentrated sulfuric acid for taking 500kg is cooled to 0 DEG C, and then under 0 DEG C of environment, the sodium nitrate of 10kg and the squama of 20kg is added Piece graphite stirs 60 minutes, is added slowly with stirring the potassium permanganate of 80kg, continues to be uniformly mixed, will be uniformly mixed System be transferred quickly in 40 DEG C of water-bath or oil bath, constant temperature stir 4 hours, the water of 800kg is added, then by reaction system It moving into rapidly in 100 DEG C of oil bath pan, constant temperature stirs 2 hours, it is then stirred for that the hydrogen peroxide of 200kg is added under state, after Continuous stirring, until water dilution, stirring, isolated solid is added when solution is in light yellow；The water of 60kg is added into solid, Stirring and washing separates solid, repeatedly, until the dispersion being added after water is neutrality；The weight of graphene oxide is with most Dodecane is added into aqueous dispersion on the basis of the weight of this graphene oxide for the poidometer for the crystalline flake graphite being just added Base benzene sulfonic acid sodium salt, polyvinylpyrrolidone, and supplement and add water, homogeneous prepares aqueous dispersion, so that oxygen in the aqueous dispersion The mass percentage content of graphite alkene is 5%, and neopelex mass percentage content is 2%, polyvinyl pyrrole Alkanone mass percentage content is 2%.

In the graphene aqueous dispersions, the partial size of graphene oxide are as follows:: D50=110 μm -140 μm.

Graphene aqueous dispersions are taken, polycarboxylate water-reducer, 205kg water and 370kg cement, ultrasonic 30min is added and adds 720kg normal sand, stirring be made into cement mortar to get；

Wherein, crystalline flake graphite is 0.08% relative to the mass fraction of cement；Matter of the polycarboxylate water-reducer relative to cement Measuring score is 0.9%.

Embodiment 11

The graphene aqueous dispersions are made of the raw material for including following mass percent: graphene oxide 4%, and ten Dialkyl benzene sulfonic acids sodium 0.9%, polyvinylpyrrolidone 1.7%, remaining is water.

The concentrated sulfuric acid for taking 280kg is cooled to 0 DEG C, and then under 0 DEG C of environment, the sodium nitrate of 8kg and the scale of 12kg is added Graphite stirs 35 minutes, is added slowly with stirring the potassium permanganate of 60kg, continues to be uniformly mixed, by what is be uniformly mixed System is transferred quickly in 35 DEG C of water-bath or oil bath, and constant temperature stirs 3 hours, and the water of 700kg is added, then that reaction system is fast Speed moves into 97 DEG C of oil bath pan, and constant temperature stirs 1.2 hours, is then stirred for that the hydrogen peroxide of 110kg is added under state, continues Stirring, until water dilution, stirring, isolated solid is added when solution is in light yellow；The water of 90kg is added into solid, stirs Cleaning is mixed, solid is separated, repeats to the dispersion after addition water to be neutrality；Squama of the weight of graphene oxide to be initially added Neopelex is added into aqueous dispersion on the basis of the weight of this graphene oxide for the poidometer of piece graphite, Polyvinylpyrrolidone, and supplement plus water, grinding prepares aqueous dispersion so that in the aqueous dispersion graphene oxide matter Measuring degree is 2%, and neopelex mass percentage content is 1.7%, polyvinylpyrrolidone quality hundred Dividing than content is 0.7%.

In the graphene aqueous dispersions, the partial size of graphene oxide are as follows:: D50=80 μm -130 μm.

Graphene aqueous dispersions are taken, polycarboxylate water-reducer, 195kg water and 429kg cement, ultrasonic 23min is added and adds 640kg normal sand, stirring be made into cement mortar to get；

Wherein, crystalline flake graphite is 0.01% relative to the mass fraction of cement；Matter of the polycarboxylate water-reducer relative to cement Measuring score is 0.8%.

Embodiment 12

The graphene aqueous dispersions are made of the raw material for including following mass percent: graphene oxide 2%, and ten Dialkyl benzene sulfonic acids sodium 1.5%, polyvinylpyrrolidone 0.5%, remaining is water.

The concentrated sulfuric acid for taking 250kg is cooled to 0 DEG C, and then under 0 DEG C of environment, the sodium nitrate of 5kg and the scale of 8kg is added Graphite stirs 20 minutes, is added slowly with stirring the potassium permanganate of 40kg, continues to be uniformly mixed, by what is be uniformly mixed System is transferred quickly in 32 DEG C of water-bath or oil bath, and constant temperature stirs 1.5 hours, the water of 300kg is added, then by reaction system It moving into rapidly in 92 DEG C of oil bath pan, constant temperature stirs 0.8 hour, it is then stirred for that the hydrogen peroxide of 90kg is added under state, after Continuous stirring, until water dilution, stirring, isolated solid is added when solution is in light yellow；It is added 130kg's into solid Water, stirring and washing separate solid, repeat to the dispersion after addition water to be neutrality；The weight of graphene oxide is initially to add Detergent alkylate is added into aqueous dispersion on the basis of the weight of this graphene oxide for the poidometer of the crystalline flake graphite entered Sodium sulfonate, polyvinylpyrrolidone, and supplement and add water, aqueous dispersion is prepared using ultrasound, so that oxygen in the aqueous dispersion The mass percentage content of graphite alkene is 3%, and neopelex mass percentage content is 0.8%, polyethylene pyrrole Pyrrolidone mass percentage content is 0.8%.

In the graphene aqueous dispersions, the partial size of graphene oxide are as follows: D50=50 μm -120 μm.

Apply above-mentioned graphene aqueous dispersions, the method for preparing graphene mortar, concrete, comprising the following steps:

Graphene aqueous dispersions are taken, polycarboxylate water-reducer, 205kg water and 320kg cement is added, is uniformly mixed, adds 760kg normal sand, stirring be made into cement mortar to get；Wherein, crystalline flake graphite is relative to the mass fraction of cement 0.009%；Polycarboxylate water-reducer is 0.2% relative to the mass fraction of cement.

Embodiment 13

The graphene aqueous dispersions are made: graphene 1%, dodecane of the raw material for including following mass percent Base benzene sulfonic acid sodium salt 0.5%, polyvinylpyrrolidone 0.5%, polycarboxylate water-reducer 2%, remaining is water.

The oxygen content of the graphene is 0.5%.

Precentagewise takes graphene, neopelex, polyvinylpyrrolidone and water, is dispersed using ultrasonic mixing Afterwards, be added polycarboxylate water-reducer, be added polycarboxylate water-reducer, after being dispersed using ultrasonic mixing to get.

Embodiment 14

The graphene aqueous dispersions, which is characterized in that be made of the raw material for including following mass percent: graphene 5%, neopelex 2%, polyvinylpyrrolidone 2%, polycarboxylate water-reducer 10%, remaining is water.

The oxygen content of the graphene is 50%.

Precentagewise takes graphene, neopelex, polyvinylpyrrolidone and water, is mixed and is dispersed using homogeneous Afterwards, be added carboxylic acid water reducer, using homogeneous mixing dispersion after to get.

Embodiment 15

The graphene aqueous dispersions, which is characterized in that be made of the raw material for including following mass percent: graphene 3%, neopelex 1%, polyvinylpyrrolidone 1.2%, polycarboxylate water-reducer 5%, remaining is water.

The oxygen content of the graphene is 10%.

Precentagewise takes graphene, neopelex, polyvinylpyrrolidone and water, is dispersed using ground and mixed Afterwards, be added polycarboxylate water-reducer, then ground mixing disperse after to get.

Embodiment 16

The graphene aqueous dispersions, which is characterized in that be made of the raw material for including following mass percent: graphene 3%, neopelex 1%, polycarboxylate water-reducer 8%, remaining is water.

The oxygen content of the graphene is 30%.

Precentagewise takes graphene, neopelex, polyvinylpyrrolidone and water, permanent at 60 ± 2.5 DEG C It temperature stirring 1 hour or more, then carries out ultrasonic treatment 8 hours or more, polycarboxylate water-reducer is then added, then through ultrasonic mixing point Dissipate after to get.

Embodiment 17

The graphene aqueous dispersions are made of the raw material for including following mass percent: graphene oxide 1%, and ten Dialkyl benzene sulfonic acids sodium 0.5%, polyvinylpyrrolidone 0.5%, polycarboxylate water-reducer 2%, remaining is water.

Precentagewise takes graphene oxide, neopelex, polyvinylpyrrolidone and water, using ultrasonic mixing After dispersion, polycarboxylate water-reducer is then added, after being dispersed using ultrasonic mixing to get.

The preparation method of the graphene oxide the following steps are included:

Embodiment 18

The graphene aqueous dispersions are made of the raw material for including following mass percent: graphene oxide 5%, and ten Dialkyl benzene sulfonic acids sodium 2%, polyvinylpyrrolidone 2%, polycarboxylate water-reducer 10%, remaining is water.

Precentagewise takes graphene oxide, neopelex, polyvinylpyrrolidone and water, using ground and mixed After dispersion, be added polycarboxylate water-reducer, after being dispersed using ground and mixed to get.

The preparation method of the graphene oxide the following steps are included:

Embodiment 19

The graphene aqueous dispersions are made of the raw material for including following mass percent: graphene oxide 3%, and ten Dialkyl benzene sulfonic acids sodium 1.1, polyvinylpyrrolidone 0.8%, polycarboxylate water-reducer 4%, remaining is water.

Precentagewise takes graphene oxide, neopelex, polyvinylpyrrolidone and water, is mixed using homogeneous After dispersion, polycarboxylate water-reducer is then added, using homogeneous mixing dispersion after to get.

The preparation method of the graphene oxide the following steps are included:

Embodiment 20

The graphene aqueous dispersions are made of the raw material for including following mass percent: graphene oxide 4%, and ten Dialkyl benzene sulfonic acids sodium 1.5, polyvinylpyrrolidone 0.9%, polycarboxylate water-reducer 6%, remaining is water.

Precentagewise takes graphene oxide, neopelex, polyvinylpyrrolidone and water, at 60 ± 2.5 DEG C Under, constant temperature stirs 1 hour or more, it then carries out ultrasonic treatment 8 hours or more, polycarboxylate water-reducer is then added, then through ultrasound Dispersion to get.

The preparation method of the graphene oxide the following steps are included:

Using above-mentioned graphene aqueous dispersions, the method for preparing graphene mortar, concrete, comprising the following steps:

Embodiment 21

The concentrated sulfuric acid for taking 200kg is cooled to 0 DEG C, and then under 0 DEG C of environment, the sodium nitrate of 4kg and the scale of 5kg is added Graphite stirs 10 minutes, is added slowly with stirring the potassium permanganate of 30kg, continues to be uniformly mixed, by what is be uniformly mixed System is transferred quickly in 30 DEG C of water-bath or oil bath, and constant temperature stirs 1 hour, and the water of 200kg is added, then that reaction system is fast Speed moves into 90 DEG C of oil bath pan, and constant temperature stirs 0.5 hour, is then stirred for that the hydrogen peroxide of 50kg is added under state, continues Stirring, until water dilution, stirring, isolated solid is added when solution is in light yellow；The water of 80kg is added into solid, stirs Cleaning is mixed, solid is separated, repeats to the dispersion after addition water to be neutrality；Squama of the quality of graphene oxide to be initially added Neopelex is added into aqueous dispersion on the basis of the quality of this graphene oxide for the quality meter of piece graphite, Polyvinylpyrrolidone, and supplement and add water, it is sufficiently mixed dispersion, polycarboxylate water-reducer is then added, is sufficiently mixed dispersion, is prepared Aqueous dispersion, so that the mass percentage content of graphene oxide is 1% in the aqueous dispersion, neopelex Mass percentage content is 0.5%, and polyvinylpyrrolidone mass percentage content is 0.5%, the quality of polycarboxylate water-reducer Degree is 2%.

Embodiment 22

The concentrated sulfuric acid for taking 500kg is cooled to 0 DEG C, and then under 0 DEG C of environment, the sodium nitrate of 10kg and the squama of 20kg is added Piece graphite stirs 60 minutes, is added slowly with stirring the potassium permanganate of 80kg, continues to be uniformly mixed, will be uniformly mixed System be transferred quickly in 40 DEG C of water-bath or oil bath, constant temperature stir 4 hours, the water of 800kg is added, then by reaction system It moving into rapidly in 100 DEG C of oil bath pan, constant temperature stirs 2 hours, it is then stirred for that the hydrogen peroxide of 200kg is added under state, after Continuous stirring, until water dilution, stirring, isolated solid is added when solution is in light yellow；The water of 60kg is added into solid, Stirring and washing separates solid, repeatedly, until the dispersion being added after water is neutrality；The weight of graphene oxide is with most Dodecane is added into aqueous dispersion on the basis of the weight of this graphene oxide for the poidometer for the crystalline flake graphite being just added Base benzene sulfonic acid sodium salt, polyvinylpyrrolidone, and supplement and add water, it is sufficiently mixed dispersion, polycarboxylate water-reducer is then added, it is sufficiently mixed Dispersion is closed, aqueous dispersion is prepared, so that the mass percentage content of graphene oxide is 5%, 12 in the aqueous dispersion Sodium alkyl benzene sulfonate mass percentage content is 2%, and polyvinylpyrrolidone mass percentage content is 2%, polycarboxylic acids diminishing Agent mass percentage content is 10%.

Embodiment 23

The graphene aqueous dispersions are made of the raw material for including following mass percent: graphene oxide 4%, and ten Dialkyl benzene sulfonic acids sodium 0.9%, polyvinylpyrrolidone 1.7%, it is water that polycarboxylate water-reducer 3%, which is remaining,.

The concentrated sulfuric acid for taking 280kg is cooled to 0 DEG C, and then under 0 DEG C of environment, the sodium nitrate of 8kg and the scale of 12kg is added Graphite stirs 35 minutes, is added slowly with stirring the potassium permanganate of 60kg, continues to be uniformly mixed, by what is be uniformly mixed System is transferred quickly in 35 DEG C of water-bath or oil bath, and constant temperature stirs 3 hours, and the water of 700kg is added, then that reaction system is fast Speed moves into 97 DEG C of oil bath pan, and constant temperature stirs 1.2 hours, is then stirred for that the hydrogen peroxide of 110kg is added under state, continues Stirring, until water dilution, stirring, isolated solid is added when solution is in light yellow；The water of 90kg is added into solid, stirs Cleaning is mixed, solid is separated, repeats to the dispersion after addition water to be neutrality；Squama of the weight of graphene oxide to be initially added Neopelex is added into aqueous dispersion on the basis of the weight of this graphene oxide for the poidometer of piece graphite, Polyvinylpyrrolidone, and supplement plus water, grinding prepares aqueous dispersion so that in the aqueous dispersion graphene oxide matter Measuring degree is 2%, and neopelex mass percentage content is 1.7%, polyvinylpyrrolidone quality hundred Dividing than content is 0.7%, and polycarboxylate water-reducer mass percentage content is 3%.

Embodiment 24

The graphene aqueous dispersions are made of the raw material for including following mass percent: graphene oxide 2%, and ten Dialkyl benzene sulfonic acids sodium 1.5%, polyvinylpyrrolidone 0.5%, polycarboxylate water-reducer 9%, remaining is water.

The concentrated sulfuric acid for taking 250kg is cooled to 0 DEG C, and then under 0 DEG C of environment, the sodium nitrate of 5kg and the scale of 8kg is added Graphite stirs 20 minutes, is added slowly with stirring the potassium permanganate of 40kg, continues to be uniformly mixed, by what is be uniformly mixed System is transferred quickly in 32 DEG C of water-bath or oil bath, and constant temperature stirs 1.5 hours, the water of 300kg is added, then by reaction system It moving into rapidly in 92 DEG C of oil bath pan, constant temperature stirs 0.8 hour, it is then stirred for that the hydrogen peroxide of 90kg is added under state, after Continuous stirring, until water dilution, stirring, isolated solid is added when solution is in light yellow；It is added 130kg's into solid Water, stirring and washing separate solid, repeat to the dispersion after addition water to be neutrality；The weight of graphene oxide is initially to add Detergent alkylate is added into aqueous dispersion on the basis of the weight of this graphene oxide for the poidometer of the crystalline flake graphite entered Sodium sulfonate, polyvinylpyrrolidone, and supplement and add water, aqueous dispersion is prepared using ultrasound, so that oxygen in the aqueous dispersion The mass percentage content of graphite alkene is 3%, and neopelex mass percentage content is 0.8%, polyethylene pyrrole Pyrrolidone mass percentage content is 0.8%, and polycarboxylate water-reducer mass percentage content is 9%.

Experimental example 1

Graphene oxide dispersing method comparative experiments in concrete

1, test material: 1. ordinary portland cements are bought from Guangxi Yu Feng Co., Ltd, model: P.O42.5；2. oxygen Graphite alkene using Hummers be prepared into come；3. polycarboxylate water-reducer is bought from Suzhou Fu Ke technical concern Co., Ltd.

2, dispersing agent；Polycarboxylate water-reducer is used in this test and carries out distributed test, has seen whether significantly to divide Layer phenomenon.

3, specific test procedure；It takes 1wt% graphene oxide solution 0.3g to be diluted in 500ml distilled water, is separately added into 0.1g polycarboxylate water-reducer；Then 2g cement is weighed, is slowly added in graphene oxide dispersion (carry out machinery respectively to stir Mix dispersion and ultrasonic wave disperse 15 minutes), whether there is obviously observation dispersion liquid after standing 0 point, 10 points and 30 points after mixing evenly Lamination.

4, experimental result is shown in Fig. 1 and Fig. 2: Fig. 1 ultrasonic disperse (left side), mechanical stirring (right side) stand 0 point of comparison diagram, and Fig. 2 is super Sound disperses (left side), mechanical stirring (right side) stands 10 points of comparison diagrams.

By Fig. 1 and Fig. 2 as it can be seen that generating particle agglomeration phenomenon after mechanical stirring hydrated product standing, dispersion effect is poor； Hydrated product dispersion is more uniform after excusing from death dispersion, and hydrated product particle refines, and does not generate agglomeration, dispersion effect is very Well.And the two light transmission discovery by the naked eye, mechanical stirring translucency is good, and ultrasonic disperse translucency is poor, it was demonstrated that ultrasound Dispersion hydrated product disperses more uniform in the sample, and it is heavy to be that mechanical stirring generates with the dispersion results obtained after mechanical stirring It forms sediment and is significantly more than ultrasonic disperse.Therefore, the preferred ultrasound of the present invention is used as dispersing method.

Experimental example 2

Effect on Mechanical Properties of the graphene oxide to cement mortar

1, the production of test specimen

Graphite oxide is carried out according to the relevant regulations in GB/T17671-1999 Test method for strength of hydraulic cement mortar (ISO method) The production of alkene cement mortar examination.

It tests and carries out two batches altogether, in each batch, only change graphene dispersing solution dosage in test, the dosage of material is shown in Table 1 and 2.

First batch experiment: application is graphene.The proportion of glue sand production is with the amount of a cement with three parts of standards Then sand adds moiety water (its ratio of mud is 0.5), be then added in polycarboxylate water-reducer (PCs) and embodiment 15 prepared by method Graphene dispersing solution (GO solution), wherein graphene dispersing solution dosage is calculated with the quality of the graphene wherein contained, point Not Wei cement quality 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, the GO solution usage occurred in table 1 is it The quality of contained graphene.In addition, wherein have one group as a control group, not graphene-doped dispersion liquid.

Second lot experiment: application is graphene oxide.The proportion of glue sand production is with the amount of a cement with three parts Then normal sand adds moiety water (its ratio of mud is 0.38), method in polycarboxylate water-reducer (PCs) and embodiment 23 is then added Prepared graphene dispersing solution (GO solution), wherein graphene dispersing solution dosage is with the matter of the graphene oxide wherein contained It measures to calculate, respectively 0.01%, 0.02%, 0.03%, 0.04%, the 0.05% of cement quality, the GO solution occurred in table 2 Dosage be the quality of the graphene oxide contained by it in addition, wherein have one group as a control group, not graphene-doped dispersion Liquid.

Test test block is having a size of 40mm × 40mm × 160mm, and one group of 3 test block, maintenance was to 7 days in standard curing room Age can carry out mechanical property test.Flexural strength test is carried out first, using the result average value that tests out as the group Test result, be averaged again when having positive and negative beyond average value 10% in three intensity values, after should rejecting strong as anti-folding Spend test result；Cubic compressive strength test is carried out, again with the average value table of 6 compression strength on one group of three prism Show, as in 6 measured values, exceeds positive and negative the 10% of average value as soon as having, this should be rejected as a result, measuring with remaining 5 The average value of value indicates result.If in remaining 5 measured values, having exceeded the positive and negative of this 5 average values there are one value 10%, then test calcellation.

First graphene cement mortar material utilization amount unit of table 1: g

Number	Cement	Normal sand	Water	GO dispersion liquid	PCs
						1	450	1350	225	0	0.9
2	450	1350	225	0.045	0.9
						4	450	1350	225	0.09	0.9
4	450	1350	225	0.135	0.9
						5	450	1350	225	0.18	0.9
6	450	1350	225	0.225	0.9

2 second batch graphene oxide cement mortar material utilization amount unit of table: g

Number	Cement	Normal sand	Water	PCs	GO dispersion liquid
						1	450	1350	171	0.9	0
2	450	1350	171	0.9	0.045
						4	450	1350	171	0.9	0.09
4	450	1350	171	0.9	0.135
						5	450	1350	171	0.9	0.18
6	450	1350	171	0.9	0.225

2, test material and appliance device

Test material: 1. ordinary portland cements, Guangxi Yu Feng Co., Ltd, model: P.O 42.5；2. China ISO is marked Quasi- sand, Xiamen Aisiou Standard Sand Co., Ltd；3. high-efficiency water-reducing agent of poly-carboxylic acid, Suzhou Fu Ke technical concern Co., Ltd；4. Tap water.

Testing equipment: 1. planetary cement mortar mixer (lSO-679) model JJ-5, upper sea route are limited up to laboratory apparatus Company；2. assay balance, model JA5003N, Shanghai Precision Scientific Apparatus Co., Ltd；3. supersonic wave cleaning machine, model: JP- 100plus, Jie Meng cleaning equipment Co., Ltd；4. mortar fluidity jumping table, model: HB.92-SLY-10, Beijing Zhuo Chuan electronics Science and Technology Ltd.；5. glue sand plain bumper, model: ZS -15, Cangzhou Huayang testing machine Manufacturing Co., Ltd；6.40mm×40mm × 160mm test piece mould；7. curing box；8. glass beaker；9. universal testing machine, model: WAW-300, Jinan day occasion science and technology have Limit company.

3, the operating procedure of cement gel sand test blocks

(1) die trial is dismantled, template applies a certain amount of butter with the place that base contacts arrive, and the effect of butter is conveniently to tear open Mould.It has to closely assemble when die-filling, closely assembly can prevent slurry leakage slurry.After the assembly is completed in die trial Inner wall in coat a thin layer of machine oil, apply machine oil and played the role of preferably being demoulded after shaping cement block, still Excessive machine oil cannot be brushed.Test specimen illustraton of model is shown in Fig. 3

(2) die trial that will be assembled is clamped on the center of glue sand plain bumper.

(3) according to the amount in table 1, table 2.It is weighed, amount can fill each die trial, each die trial available three Item molding examination body.

(4) production cement mortar test specimen uses planetary glue sand agitator, weighs up corresponding amount according to quantity and pours into planet In formula glue sand agitated kettle, it is subsequently installed on loom.Booting is stirred, and the process of stirring is automatically, when stirring end loom can be certainly Dynamic to stop, the glue sand being sticked on blade is scraped using scoop after stopping and completely removes agitated kettle by loom.

(5) when having stirred a kind of material each time, the blade of agitated kettle, blender will be wiped clean with wet cloth, The production of next group of material can just be carried out.

(6) cement mortar being stirred is poured into inside forming die trial, opens plain bumper, cement mortar passes through vibration meeting Complete model of die trial filling is flowed into, can automatically be stopped after plain bumper vibration (120 scholar 5) s.

(7) die trial is removed after plain bumper parking, is placed on the cement mortar that some horizontal place comes out height using scraper It strikes off.And then it finishes writing and is marked outside the die trial of number notice.Cement mortar tryout is shown in Fig. 4

(8) demoulding is taken out after 24 scholar 3h.The damage that should be noted that examination body in demoulding, hardening slow cement can be with Extend striking time, but to record the time of demoulding.The examination body removed is shown in Fig. 5.

4, the maintenance of cement gel sand test blocks

(1) it should be put at once in curing box and conserve after trying body demoulding, trying between body and examination body will there are certain gaps.

(2) curing time for passing through 7 days takes out examination body and first tests flexural strength, then uses every section of material after fractureing again The test of compression strength is carried out again.

5, the measurement of bending and compressive strength

A, flexural strength measures

Examination body is taken out in curing box, has cloth to wipe completely examination body, while also the fixture of test is wiped completely.So Examination body to be tested is installed in fixture afterwards.

This test is lever-type Intensity of Breaking Tester, and lever is needed to adjust to the position of balance when test It sets.

The speed loaded when operation is (50 scholar 10) N/s, just stops load until disconnecting, writes down current power.

It is calculated according to the power tested, formula is

By flexural strength is calculated.

By test result is calculated, acquired results answer round numbers average value.Same group of test result is more than average value 10% when, remove corresponding value and average again, obtained average value is exactly the result that flexural strength is tested.

B, the measurement of compression strength

The two pieces of examination bodies obtained after the test of bending test carry out compressive strength test.Intensity test is by force institute Examination body to be tested is wiped clean and is installed with resistance to compression fixture.

The examination body that will be installed, side contact positioning surface as compression face, bottom surface.Clamp central will be directed at the center of pressing plate.

Pressure loading with the rate uniform of (2400 scholar 200) N/s loading stops loading until destroying.Record load Power is simultaneously calculated, calculation formula

6, cement mortar anti-folding and anti-pressing strength test results and analysis

First graphene concrete analysis: test result is shown in Fig. 6, and by trying the production of body, it is anti-that anti-folding is carried out after maintenance The test of Compressive Strength has obtained anti-folding, the compression strength intensity in graphene-doped 0.01% amount and has improved about 10%.Separately Outside, inventor has also carried out the experiment of more large dosage, finds the resistance to compression of cement gel sand test blocks after graphene volume has crossed 0.01% Folding intensity starts gradually to decline, and is not The more the better this illustrates volume.

Second batch graphene oxide concrete analysis: test result is shown in Fig. 7, by trying the production of body, is resisted after maintenance The test for rolling over compression strength has obtained flexural strength intensity when mixing the amount of graphene oxide 0.03% and has improved 28%, Compression strength intensity when mixing the amount of graphene oxide 0.03% improves 10%, mixes the amount of graphene oxide 0.05% When intensity improve 20%.

Experimental example 3

Effect on Mechanical Properties of the graphene oxide to cement paste

1, the production of test specimen

The ratio of mud of this experiment net slurry is 0.29, is divided into two batches and is tested,

The experiment of first batch cement paste: application is graphene.Using graphene prepared by method in embodiment 16 Dispersion liquid (GO solution), wherein graphene dispersing solution dosage is calculated with the quality of the graphene wherein contained, is respectively deleted Except the 0.01% of quality, 0.02%, 0.03%, 0.04%, 0.05%, the GO solution usage occurred in table 3 is contained by it Graphene quality.In addition, wherein have one group as a control group, not graphene-doped dispersion liquid.

The experiment of second lot cement paste: application is graphene oxide.Using stone prepared by method in embodiment 20 Black alkene dispersion liquid (GO solution), wherein graphene dispersing solution dosage is calculated with the quality of the graphene oxide wherein contained, point Not Wei cement quality 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, the GO solution usage occurred in table 4 is it The quality of contained graphene oxide.In addition, wherein have one group as a control group, not graphene-doped dispersion liquid.

Each specific dosage of ingredient is shown in Table 3, table 4.The amount of material is calculated according to die trial 40mm × 40mm × 160mm Come, a die trial is made three test specimens and tested as cement mortar.

First graphene concrete paste specimen material mixture ratio unit of table 3: g

Number	Cement	Water	PCs	GO dispersion liquid
					1	1415	410	2.83	0
2	1415	410	2.264	0.1415
					3	1415	410	1.698	0.283
4	1415	410	1.012	0.4525
					5	1415	410	0.566	0.566
6	1415	410	0	0.7075

4 second batch graphene oxide concrete paste specimen material mixture ratio unit of table: g

Number	Cement	Water	PCs	GO dispersion liquid
					1	1415	410	2.83	0
2	1415	410	2.83	0.1415
					3	1415	410	2.83	0.283
4	1415	410	2.83	0.4525
					5	1415	410	2.83	0.566
6	1415	410	2.83	0.7075

2, test material and appliance device

Using to material have: Guangxi Yu Feng Co., Ltd production 42.5 ordinary portland cement of P.O；Suzhou is not gram The high-efficiency water-reducing agent of poly-carboxylic acid of technical concern Co., Ltd production；Tap water.

Testing equipment；1. experimental instruments and equipment limited is analysed by planetary net slurry blender, model NJ-160B, Hebei section；2. electricity Sub- balance, model JA5003N, Shanghai Precision Scientific Apparatus Co., Ltd；3. supersonic wave cleaning machine, model: JP-100plus, it is clean Cleaning equipment Co., Ltd, alliance；4.40mm × 40mm × 160mm test piece mould；5. curing box；6. universal testing machine, model: WAW-300, Jinan Tian Chen Science and Technology Ltd.；7. glass beaker；8. glass paddle.

3, the operating procedure that cement paste examination system is made

(1) die trial is dismantled, template applies a certain amount of butter with the place that base contacts arrive, and the effect of butter is conveniently to tear open Mould.It has to closely assemble when die-filling, closely assembly can prevent slurry leakage slurry.After the assembly is completed in die trial Inner wall in coat a thin layer of machine oil, apply machine oil and played the role of preferably being demoulded after shaping cement block, still Excessive machine oil cannot be brushed.

(2) according to the amount in table 3, table 4.It is weighed, amount can fill each die trial, each die trial available three Item molding examination body.

(3) production cement mortar test specimen uses planetary glue sand agitator, weighs up corresponding amount according to quantity and pours into planetary glue In sand agitated kettle, it is subsequently installed on loom.Booting stirring, the process of stirring are automatically, to stop automatically when stirring terminates loom Under, the glue sand being sticked on blade is scraped using scoop after stopping and completely removes agitated kettle by loom.

(4) when having stirred a kind of material each time, the blade of agitated kettle, blender will be wiped clean with wet cloth, The production of next group of material can just be carried out.

(5) cement mortar being stirred is poured into inside forming die trial, is placed on some horizontal place using scraper high Cement mortar out strikes off.And then it finishes writing and is marked outside the die trial of number notice.

(6) demoulding is taken out after 24 scholar 3h.The damage that should be noted that test examination body in demoulding, hardens slow cement Striking time can be extended, but to record the time of demoulding.

4, the maintenance of cement paste examination body

(2) time conserved is 7 days.

(3) try body curing time to when will examination body taken out from curing box, first carry out flexural strength test, resist After folding intensity is finished, then the test of compression strength is carried out with every section of material after fractureing again.

5, the measurement of bending and compressive strength

A, flexural strength measures

It is calculated according to the power tested, formula is

By flexural strength is calculated.

B, the measurement of compression strength

6, cement paste bending and compressive strength test result and analysis

First graphene cement paste pressure-proof and snap-resistent intensive analysis: test result is shown in that Fig. 8, graphene cement paste try body By the test of pressure-proof and snap-resistent mechanical property, according to the line chart that data are done be known that graphene volume 0.01%~ The bending and compressive strength improved when 0.02% be it is highest, increment reaches 20% or more.Know by the analysis of test data It is to have good effect to cement mechanical property that road graphene, which is added in cement base,.

Second batch graphene oxide cement paste pressure-proof and snap-resistent intensive analysis: test result is shown in Fig. 9, graphene oxide cement Net slurry tries test of the body Jing Guo pressure-proof and snap-resistent intensity, and the volume for being known that graphene oxide according to the line chart that data are done is Bending and compressive strength is highest when 0.01%~0.02%, and increment reaches 20% or more.By point of test data It is to have good effect to cement mechanical property that analysis, which knows that graphene oxide is added in cement base,.

Experimental example 4

Effect on Mechanical Properties of the graphene oxide to cement mortar

1, the production of test specimen

It tests and carries out two batches altogether, in each batch, only change graphene dispersing solution dosage in test, the dosage of material is shown in Table 5 and 6.

First batch test: application is graphene.The proportion of glue sand production is with the amount of a cement with three parts of standards Then sand adds moiety water (its ratio of mud is 0.5), graphene dispersing solution prepared by method (is free of in GO solution and embodiment 3 Polycarboxylate water-reducer), wherein graphene dispersing solution dosage is calculated with the quality of the graphene wherein contained, respectively cement 0.01%, 0.02%, 0.03%, 0.04%, the 0.05% of quality, the GO solution usage occurred in table 1 is contained by it The quality of graphene.In addition, wherein have one group as a control group, not graphene-doped dispersion liquid.

Second lot experiment: application is graphene oxide.The proportion of glue sand production is with the amount of a cement with three parts Then normal sand adds moiety water (its ratio of mud is 0.5), graphene dispersing solution prepared by method in GO solution and embodiment 5 (be free of polycarboxylate water-reducer), wherein graphene dispersing solution dosage is calculated with the quality of the graphene oxide wherein contained, point Not Wei cement quality 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, the GO solution usage occurred in table 2 is it The quality of contained graphene oxide in addition, wherein have one group as a control group, not graphene-doped dispersion liquid.

First graphene cement mortar material utilization amount unit of table 5: g

Number	Cement	Normal sand	Water	GO dispersion liquid
					1	450	1350	225	0
2	450	1350	225	0.045
					4	450	1350	225	0.09
4	450	1350	225	0.135
					5	450	1350	225	0.18
6	450	1350	225	0.225

6 second batch graphene oxide cement mortar material utilization amount unit of table: g

Number	Cement	Normal sand	Water	GO dispersion liquid
					1	450	1350	171	0
2	450	1350	171	0.045
					4	450	1350	171	0.09
4	450	1350	171	0.135
					5	450	1350	171	0.18
6	450	1350	171	0.225

2, test material and appliance device

Test material: 1. ordinary portland cements, Guangxi Yu Feng Co., Ltd, model: P.O 42.5；2. China ISO is marked Quasi- sand, Xiamen Aisiou Standard Sand Co., Ltd；3. tap water.

3, the operating procedure of cement gel sand test blocks

(3) according to the amount in table 5, table 6.It is weighed, amount can fill each die trial, each die trial available three Item molding examination body.

(8) demoulding is taken out after 24 scholar 3h.The damage that should be noted that examination body in demoulding, hardening slow cement can be with Extend striking time, but to record the time of demoulding.

4, the maintenance of cement gel sand test blocks

5, the measurement of bending and compressive strength

A, flexural strength measures

It is calculated according to the power tested, formula is

By flexural strength is calculated.

B, the measurement of compression strength

6, cement mortar anti-folding and anti-pressing strength test results

7 cement mortar pressure-proof and snap-resistent intensity summary sheet of table

Experimental example 5

Effect on Mechanical Properties of the graphene oxide to cement paste

1, the production of test specimen

The ratio of mud of this test net slurry is 0.29, is divided into two batches and is tested,

The experiment of first batch cement paste: application is graphene.Using graphene prepared by method in embodiment 4 point Dispersion liquid (the non-addition polymerization carboxylic acid water reducer of GO solution), wherein graphene dispersing solution dosage is come with the quality of the graphene wherein contained It calculates, respectively 0.01%, 0.02%, 0.03%, 0.04%, the 0.05% of cement quality, the GO solution usage occurred in table 3 It is the quality of the graphene contained by it.In addition, wherein have one group as a control group, not graphene-doped dispersion liquid.

The experiment of second lot cement paste: application is graphene oxide.Using graphite prepared by method in embodiment 6 Alkene dispersion liquid (the non-addition polymerization carboxylic acid water reducer of GO solution), wherein graphene oxide of the graphene dispersing solution dosage wherein to contain Quality calculate, respectively 0.01%, 0.02%, 0.03%, 0.04%, the 0.05% of cement quality, the GO occurred in table 4 Solution usage is the quality of the graphene oxide contained by it.In addition, wherein have one group as a control group, it is not graphene-doped Dispersion liquid.

Each specific dosage of ingredient is shown in Table 8, table 9.The amount of material is calculated according to die trial 40mm × 40mm × 160mm Come, a die trial is made three test specimens and tested as cement mortar.

First graphene concrete paste specimen material mixture ratio unit of table 8: g

9 second batch graphene oxide concrete paste specimen material mixture ratio unit of table: g

Number	Cement	Water	GO dispersion liquid
				1	1415	410	0
2	1415	410	0.1415
				3	1415	410	0.283
4	1415	410	0.4525
				5	1415	410	0.566
6	1415	410	0.7075

2, test material and appliance device

Using to material have: Guangxi Yu Feng Co., Ltd production 42.5 ordinary portland cement of P.O；Tap water.

3, the operating procedure that cement paste examination system is made

(2) according to the amount in table 5, table 6.It is weighed, amount can fill each die trial, each die trial available three Item molding examination body.

4, the maintenance of cement paste examination body

(2) time conserved is 7 days.

5, the measurement of bending and compressive strength

A, flexural strength measures

It is calculated according to the power tested, formula is

By flexural strength is calculated.

B, the measurement of compression strength

6, cement paste bending and compressive strength test result:

10. cement paste bending and compressive strength summary sheet of table

Claims

1. a kind of graphene aqueous dispersions, which is characterized in that be made of the raw material for including following mass percent: graphene or oxygen Graphite alkene 1-5%, neopelex 0.5%-2%, the polycarboxylic acids diminishing of polyvinylpyrrolidone 0.5%-2%, 0-10% Agent, remaining is water.

2. graphene aqueous dispersions as described in claim 1, which is characterized in that by the raw material system including following mass percent At: graphene or graphene oxide 1-5%, neopelex 0.5%-2%, polyvinylpyrrolidone 0.5%-2%, poly- carboxylic Sour water-reducing agent 2-10%, remaining is water.

3. graphene aqueous dispersions as claimed in claim 1 or 2, it is characterised in that: the oxygen content of the graphene is 0.5-50%。

4. graphene aqueous dispersions as claimed in claim 1 or 2, which is characterized in that preparation method includes the following steps:

Precentagewise takes graphene or graphene oxide, neopelex, polyvinylpyrrolidone and water, is sufficiently mixed After dispersion, be made the preliminary dispersion liquid of graphene, be added polycarboxylate water-reducer, be sufficiently mixed dispersion after to get.

5. graphene aqueous dispersions as claimed in claim 1 or 2, it is characterised in that:

The mixing dispersion side of the graphene or graphene oxide, neopelex, polyvinylpyrrolidone and water Method, using one of ultrasound, homogeneous, grinding or more than one combination；The side of polycarboxylate water-reducer mixing dispersion is added Method is one of ultrasound, homogeneous, grinding or more than one combination.

6. graphene aqueous dispersions as claimed in claim 1 or 2, it is characterised in that: the graphene or graphene oxide, The mixing dispersing method of neopelex, polyvinylpyrrolidone and water are as follows: at 60 ± 2.5 DEG C, constant temperature stirring 1 is small When more than, then carry out ultrasonic treatment 8 hours or more；The method that polycarboxylate water-reducer mixing dispersion is added is ultrasound, homogeneous, grinds One of mill or more than one combination.

7. graphene aqueous dispersions as claimed in claim 1 or 2, which is characterized in that the preparation method of graphene oxide includes Following steps:

The concentrated sulfuric acid for taking 200-500 parts by weight is cooled to 0 DEG C, and then under 0 DEG C of environment, the sodium nitrate of 4-10 parts by weight is added With the crystalline flake graphite of 5-20 parts by weight, stirs 10-60 minutes, be added slowly with stirring the potassium permanganate of 30-80 parts by weight, after It is continuous to be uniformly mixed, uniformly mixed system is transferred quickly in 30-40 DEG C of water-bath or oil bath, it is small that constant temperature stirs 1-4 When, the water of 200-800 parts by weight is added, then moves into reaction system rapidly in 90-100 DEG C of oil bath pan, constant temperature stirring It 0.5-2 hours, is then stirred for that the hydrogen peroxide of 50-200 parts by weight is added under state, continues to stir, until solution is in pale yellow When color, water dilution, stirring, isolated solid is added, water is added into solid, stirring and washing separates solid, repeats to addition Dispersion after water is neutrality, separation take solid to get.

8. graphene aqueous dispersions as claimed in claim 4, when using graphene oxide, which is characterized in that preparation method The following steps are included:

The concentrated sulfuric acid for taking 200-500 parts by weight is cooled to 0 DEG C, and then under 0 DEG C of environment, the sodium nitrate of 4-10 parts by weight is added With the crystalline flake graphite of 5-20 parts by weight, stirs 10-60 minutes, be added slowly with stirring the potassium permanganate of 30-80 parts by weight, after It is continuous to be uniformly mixed, uniformly mixed system is transferred quickly in 30-40 DEG C of water-bath or oil bath, it is small that constant temperature stirs 1-4 When, the water of 200-800 parts by weight is added, then moves into reaction system rapidly in 90-100 DEG C of oil bath pan, constant temperature stirring It 0.5-2 hours, is then stirred for that the hydrogen peroxide of 50-200 parts by weight is added under state, continues to stir, until solution is in pale yellow When color, water dilution, stirring, isolated solid is added；

Into solid be added 50-150 parts by weight water, stirring and washing, separate solid, repeat to be added water after dispersion be It is neutral；

The quality of graphene oxide is in terms of the quality for the crystalline flake graphite being initially added, on the basis of the quality of this graphene oxide, Neopelex, polyvinylpyrrolidone are added into aqueous dispersion, and supplements and adds water, is sufficiently mixed dispersion, adds Enter polycarboxylate water-reducer, after being sufficiently mixed dispersion, obtain aqueous dispersion so that in the aqueous dispersion graphene oxide matter Amount degree is 1-5%, and neopelex mass percentage content is 0.5%-2%, polyvinylpyrrolidone quality Degree is 0.5%-2%, the polycarboxylate water-reducer of 0-10%.

9. graphene aqueous dispersions as claimed in claim 1 or 2, it is characterised in that: in the graphene aqueous dispersions, stone The partial size of black alkene or graphene oxide are as follows:: D50=5 μm ~ 140 μm.

10. a kind of preparation method of graphene concrete applies the graphene aqueous dispersions as described in power 1-9 any one, Characterized by comprising the following steps:

Wherein, graphene or graphene oxide are 0.003% ~ 0.08% relative to the mass fraction of cement；Polycarboxylate water-reducer phase Mass fraction for cement is 0.1-0.9%.