CN108409229A - A kind of graphene is modified resistance-lowering material and preparation method thereof - Google Patents

A kind of graphene is modified resistance-lowering material and preparation method thereof Download PDF

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Publication number
CN108409229A
CN108409229A CN201810192105.XA CN201810192105A CN108409229A CN 108409229 A CN108409229 A CN 108409229A CN 201810192105 A CN201810192105 A CN 201810192105A CN 108409229 A CN108409229 A CN 108409229A
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China
Prior art keywords
graphene
resistance
cement
lowering material
bentonite
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CN201810192105.XA
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CN108409229B (en
Inventor
刘如铁
成凯
汪旭东
洪涛
刘正君
郭剑
林雪杨
陈洁
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Hunan Province Bodun Ray Technology Co Ltd
Central South University
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Hunan Province Bodun Ray Technology Co Ltd
Central South University
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • 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
    • 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
    • C04B2111/90Electrical properties
    • C04B2111/94Electrically conducting materials

Abstract

A kind of graphene of present invention offer is modified resistance-lowering material and preparation method thereof.It is made of the component proportion of following parts by weight:Cement 20~50, crystalline flake graphite 20~40, graphene 0.01~4, carbon fiber 1~10, zinc powder 1~10, dispersant 1~10, steel fibre 1~10, bentonite 10~30, the plaster of paris 0.5~2.Preparation method is:Graphene dispersing solution is made in the graphene, dispersant and water for choosing the formula first, then obtains the uniform suspension of graphene dispersion in case using, and bentonite and the plaster of paris are added in this suspension and stirred evenly by being ultrasonically treated;In addition cement and carbon fiber, steel fibre machinery are stirred, are added thereto after later mixing zinc powder with crystalline flake graphite, and be mixed evenly;Above two mixed liquor is merged and is uniformly mixed.Graphene modification resistance-lowering material resistivity is small, high mechanical properties, use scope is wide, antiseptic property is good, form of construction work is simple.

Description

A kind of graphene is modified resistance-lowering material and preparation method thereof
Technical field
The present invention relates to a kind of grounding resistance-reducing materials and preparation method thereof, belong to earth work Material Field.
Background technology
Skyscraper is easy to be struck by lightning in thunder and lightning weather, as the precautionary measures, it will usually earth protective device is set, Resistance-lowering material is exactly a kind of engineering material for reducing grounding electrode surrounding soil resistance in earth work protective device.
Early stage resistance-lowering material is mainly some metal salts or metal oxide, is ionized in water by these substances and generates band Electron ion is to make the electric conductivity of soil increase.This mode is inevitably easy to cause to corrode to wire ground electrode, and And resistance reducing effect is easily influenced by soil moisture and causes material stability poor.Therefore, with the development of resistance-lowering material, again It is added to some organic matters(Such as urinate aldehyde, amide, resin)The jello with tridimensional network is formed, to increase drop resistance The water suction moisture retention of material reduces the loss of electrolyte, but its corrosivity is stronger, and the organic matter that cannot degrade exist but also It is very big to the pollution of natural environment.Based on deficiency existing for chemical type resistance-lowering material, in recent years, people are for resistance-lowering material Research and development are concentrated mainly on non-electrolyte solid powder(Generally carbon materials)For conductive material, Silicates material is gelling The physical resistance-lowering material of object.This kind of resistance-lowering material directly plays the role of dropping resistance by the conductive powder of itself, not by the shadow of rainwater It rings, substantially alleviates the corrosion to wire ground electrode.Meanwhile conductive characteristic is not also by acid-alkali salt, high/low temperature, humidity institute Limit, is more easily satisfied arid, short of rain, extremely frigid zones the requirement of ground resistance stability.
Graphene is a kind of new material with good electric conductivity, thermal conductivity, high specific strength, bigger serface, is being permitted It is multi-field to have obtained good application effect.Patent document(CN105957577A)Disclose a kind of " earthy calcium-base bentonite Base friction reducer " has used grapheme material, the feed postition of wherein graphene to be and carbon fiber, aluminium powder, nickel powder, zinc powder and oxygen Changing calcium, addition is uniformly mixed jointly.π-π stackings effect due to graphene film interlayer and stronger van der Waals interaction, cause stone Black alkene is difficult to be uniformly dispersed in aqueous solution, is easy to reunite.Therefore, graphite is added using simple mode in above-mentioned patent Alkene cannot give full play to the advantage of graphene enhancing drop resistance it is difficult to which it is uniformly dispersed in resistance-lowering material.Meanwhile the patent In friction reducer add a large amount of electrolytic salts, be likely to encounter rainwater and be lost in, reduce resistance reducing effect.So far, although stone Black alkene is paid close attention in resistance-lowering material field, but can give full play to graphene advantage to greatly improve resistance-lowering material comprehensive The related report of energy is simultaneously few.
Invention content
The purpose of the present invention is the problems for graphene dispersion difference, using graphene dispersion technology into cement matrix Graphene is added, while adding conductive material, finally prepares that a kind of small resistivity, high mechanical properties, use scope be wide, anti-corrosion Performance is good, the simple resistance-lowering material of form of construction work.
Technical problem to be solved by the invention is to provide a kind of, and the graphene with good performance is modified drop resistance material Material and preparation method thereof.
A kind of graphene of the present invention is modified resistance-lowering material, it is made of the component proportion of following parts by weight:
Cement 20~50,
Crystalline flake graphite 20~40,
Graphene 0.01~4,
Carbon fiber 1~10,
Zinc powder 1~10,
Dispersant 1~10,
Steel fibre 1~10,
Bentonite 10~30,
The plaster of paris 0.5~2.
In the proportioning, cement chooses No. 425 cement of common silicate, and crystalline flake graphite chose 200 mesh powders, graphite It is 3-20 layers that alkene, which selects the number of plies, and for lamella size in the multi-layer graphene of 10-20um, it is 6-10mm, diameter that carbon fiber, which chooses length, For 7um;
In the proportioning, length of steel fiber 20-40mm, draw ratio 30-70 improve material power for improving electric conductivity Learn performance;Dispersant is neopelex or polyvinylpyrrolidone or sodium taurocholate;
In the proportioning, zinc powder chose the powder of 325 mesh, for preventing the surface corrosion of contact electrode, played cathodic protection Effect, and increase the electric conductivity of resistance-lowering material;Bentonite chooses sodium bentonite or calcium-base bentonite, and granularity is less than 300 mesh, with Increase the electric conductivity of this material in a wetted condition;The plaster of paris chooses granularity and is less than 300 mesh, the setting time for adjusting cement And increase strength of cement.
A kind of graphene as described above is modified the preparation method of resistance-lowering material, includes the following steps:
(1), it chooses and meets the graphene, dispersant and water of the ratio requirement and be made graphene dispersing solution, graphene and water ratio Example is 1:20-1:Between 30, dispersion liquid be ultrasonically treated 2 hours, and stir evenly;
(2), the bentonite for meeting the ratio requirement and the plaster of paris are added in mixed liquor made from step (1), machinery stirs It mixes 1 hour and reaches uniform state;
(3), the cement for meeting the ratio requirement and carbon fiber, steel fibre mechanical agitation are reached into uniform state in 1 hour, then It is added thereto to remix after the zinc powder for meeting the ratio requirement is mixed with crystalline flake graphite and reaches within 1 hour uniform state, and will The mixture obtained herein is all added in mixed slurry made from step (2), and stirring reaches uniform state in 1 hour;
(4), by slurry agitation made from step (3) it is uniform after pour into mold, obtain the stone after standing solidification in 24 hours Black alkene is modified resistance-lowering material.
A kind of graphene of the present invention is modified resistance-lowering material and preparation method thereof, and advantage has:
The present invention uses graphene dispersion technology, by graphene uniform is added in resistance-lowering material, physical resistance-lowering material one As can add cement as gelling object, and graphene has template effect to the formation of hydrated cementitious crystalline product, can promote water Mud hydrated product forms regular nano-sized crystal body, to dramatically increase cement matrix intensity, toughness, electric conductivity, corrosion-resistant The comprehensive performances such as property;On the other hand, the graphene of incorporation can be attached to the surface of the hydrated calcium silicate in cement, be filled into water Change in the micron order pore between product, effectively improves the consistency of material.Based on above-mentioned advantage, evenly dispersed a small amount of stone Black alkene can improve the comprehensive performance of resistance-lowering material in the present invention.Meanwhile the present invention is a kind of solid modules material, is not made Use electrolyte as conductive constituent element, compared with traditional resistance-lowering material, material of the invention have intensity is high, resistance is small, it is pollution-free, Simple to install, Applicable temperature range are wide, and to the free from corrosion advantage of grounding electrode.
Specific implementation mode
For the present invention is better described, it is easy to understand technical scheme of the present invention, below further specifically to the present invention Bright but following embodiment is only the simple example of the present invention, does not represent or limit the scope of the present invention, this Invention protection domain is subject to claims.
Embodiment 1:
The first step:3% graphene is chosen, 5% sodium taurocholate, which is poured into water, is prepared into graphene dispersing solution, the ratio of graphene and water Example is 1:25, and carry out ultrasonic agitation 2 hours.
Second step:It is small that 20% sodium bentonite bentonite and 1% plaster of paris are added to stirring 1 in graphene dispersing solution When reach uniform state.
Third walks:27% cement is mixed with 7% carbon fiber and 7% steel fibre, mechanical agitation is added thereto after 1 hour 25% graphite and 5% zinc powder, which remix 1 hour, reaches uniform state, is mixed again with the material that second step obtains later, and stir It mixes 1 hour and reaches uniform state.
4th step:Slurry obtained is poured into mold, 24 hours is stood and obtains graphene after its solidification and be modified and drop resistance Module material.
Embodiment 2:
The first step:4% graphene is chosen, 3% neopelex, which is poured into water, is prepared into graphene dispersing solution, graphite The ratio of alkene and water is 1:20, and carry out ultrasonic agitation 2 hours.
Second step:The plaster of paris of 20% sodium bentonite and 0.5% is added to stir 1 hour in graphene dispersing solution and is reached To uniform state.
Third walks:34% cement is mixed with 5% carbon fiber and 7% steel fibre, mechanical agitation is added thereto after 1 hour 20% graphite and 6.5% zinc powder, which remix 1 hour, reaches uniform state, is mixed again with the material that second step obtains later, and Stirring reaches uniform state in 1 hour.
4th step:Slurry obtained is poured into mold, 24 hours is stood and obtains graphene after its solidification and be modified and drop resistance Module material.
Embodiment 3:
The first step:1% graphene is chosen, being poured into water for 5% polyvinylpyrrolidone is prepared into graphene dispersing solution, graphene Ratio with water is 1:30, and carry out ultrasonic agitation 2 hours.
Second step:The plaster of paris of 20% sodium bentonite and 1% is added to stir 1 hour in graphene dispersing solution and is reached Uniform state.
Third walks:30% cement is mixed with 5% carbon fiber and 7% steel fibre, mechanical agitation is added thereto after 1 hour 24% graphite and 7% zinc powder, which remix 1 hour, reaches uniform state, is mixed again with the material that second step obtains later, and stir It mixes 1 hour and reaches uniform state.
4th step:Slurry obtained is poured into mold, 24 hours is stood and obtains graphene after its solidification and be modified and drop resistance Module material.
Embodiment 4:
The first step:3% graphene is chosen, 4.5% sodium taurocholate, which is poured into water, is prepared into graphene dispersing solution, graphene and water Ratio is 1:20, and carry out ultrasonic agitation 2 hours.
Second step:The plaster of paris of 19% sodium bentonite and 1.5% is added to stir 1 hour in graphene dispersing solution and is reached To uniform state.
Third walks:30% cement is mixed with 5% carbon fiber and 7% steel fibre, mechanical agitation is added thereto after 1 hour 25% graphite and 5% zinc powder, which remix 1 hour, reaches uniform state, is mixed again with the material that second step obtains later, and stir It mixes 1 hour and reaches uniform state.
4th step:Slurry obtained is poured into mold, 24 hours is stood and obtains graphene after its solidification and be modified and drop resistance Module material.
Embodiment 5:
The first step:2.5% graphene is chosen, 5% neopelex, which is poured into water, is prepared into graphene dispersing solution, stone The ratio of black alkene and water is 1:25, and carry out ultrasonic agitation 2 hours.
Second step:The plaster of paris of 25% calcium-base bentonite and 1.5% is added to stir 1 hour in graphene dispersing solution and is reached To uniform state.
Third walks:29% cement is mixed with 5% carbon fiber and 5% steel fibre, mechanical agitation is added thereto after 1 hour 20% graphite and 7% zinc powder, which remix 1 hour, reaches uniform state, is mixed again with the material that second step obtains later, and stir It mixes 1 hour and reaches uniform state.
4th step:Slurry obtained is poured into mold, 24 hours is stood and obtains graphene after its solidification and be modified and drop resistance Module material.
In order to illustrate in the present invention graphene addition and dispersion technology can actually promote the performance of resistance-lowering material, this hair It is bright also to have devised the experiment of two comparative examples and be compared.
Comparative example 1:
The first step:It is mixed and stirred for the plaster of paris of 20% sodium bentonite and 1% to reach uniform state in 1 hour.
Second step:35% cement is mixed with 7% carbon fiber and 7% steel fibre, mechanical agitation is added thereto after 1 hour 25% graphite and 5% zinc powder mix and reach uniform state in 1 hour, mixs again with the material that the first step obtains later, and stirring 1 Hour reaches uniform state.Later plus water, the 40%-60% that water weight matches total weight according to above-mentioned resistance-lowering material are separately added.
Third walks:Slurry obtained is poured into mold, 24 hours is stood and obtains graphene after its solidification and be modified and drop resistance Module material.
Comparative example 2:
The first step:It is mixed and stirred for 20% sodium bentonite and 1% plaster of paris, 3% graphene to reach uniform shape in 1 hour State.
Second step:32% cement is mixed with 7% carbon fiber and 7% steel fibre, mechanical agitation is added thereto after 1 hour 25% graphite and 5% zinc powder mix and reach uniform state in 1 hour, mixs again with the material that the first step obtains later, and stirring 1 Hour reaches uniform state.Later plus water, the 40%-60% that water weight matches total weight according to above-mentioned resistance-lowering material are separately added.
Third walks:Slurry obtained is poured into mold, 24 hours is stood and obtains graphene after its solidification and be modified and drop resistance Module material.
Measure the basic performance such as table 1 and table 2 of material obtained by embodiment 1-5 and comparative example 1-2.Wherein, comparative example 1 graphene is not added, and comparative example 2 is added graphene and does not use dispersion technology.Performance test is all made of survey well known in the art Trial work section carries out.As can be seen that compared with the resistance-lowering material performance for being not added with graphene, by graphene uniform using dispersion technology Resistivity can be significantly decreased by being added in resistance-lowering material, improve the strength of materials, and reduce the corrosion to being grounded metallic object Rate, energy with good stability, and lower resistivity can be still kept at low temperature.If only addition graphene is without making With dispersion technology, since graphene dispersion is uneven, the properties of improvement unobvious, resistance-lowering material are significantly lower than this hair The bright resistance-lowering material.
Table 1, basic performance situation
Table 2, temperature characterisitic experiment
The preferred embodiment of the present invention has been described above in detail, still, the tool during present invention is not limited to the embodiments described above Body details can carry out a variety of simple variants, these letters to technical scheme of the present invention within the scope of the technical concept of the present invention Monotropic type all belongs to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention equally should be considered as technical proposal scope disclosed in this invention.

Claims (5)

1. a kind of graphene is modified resistance-lowering material, which is characterized in that it is made of the component proportion of following parts by weight:
Cement 20~50,
Crystalline flake graphite 20~40,
Graphene 0.01~4,
Carbon fiber 1~10,
Zinc powder 1~10,
Dispersant 1~10,
Steel fibre 1~10,
Bentonite 10~30,
The plaster of paris 0.5~2.
2. a kind of graphene according to claim 1 is modified resistance-lowering material, which is characterized in that in the proportioning, cement No. 425 cement of common silicate are chosen, crystalline flake graphite chose 200 mesh powders, and it is 3-20 layers that graphene, which selects the number of plies, piece For layer size in the multi-layer graphene of 10-20um, it is 6-10mm, a diameter of 7um that carbon fiber, which chooses length,.
3. a kind of graphene according to claim 1 is modified resistance-lowering material, which is characterized in that in the proportioning, steel is fine Dimension length is 20-40mm, draw ratio 30-70 improves material mechanical performance for improving electric conductivity;Dispersant is dodecane Base benzene sulfonic acid sodium salt or polyvinylpyrrolidone or sodium taurocholate.
4. a kind of graphene according to claim 1 is modified resistance-lowering material, which is characterized in that in the proportioning, zinc powder The powder for choosing 325 mesh plays the role of cathodic protection, and increase resistance-lowering material for preventing the surface corrosion of contact electrode Electric conductivity;Bentonite chooses sodium bentonite or calcium-base bentonite, and granularity is less than 300 mesh, to increase this material in wet condition Under electric conductivity;The plaster of paris chooses granularity and is less than 300 mesh, and the setting time for adjusting cement simultaneously increases strength of cement.
5. a kind of graphene such as Claims 1-4 any one of them is modified the preparation method of resistance-lowering material, feature exists In comprising following step:
(1), it chooses and meets the graphene, dispersant and water of the ratio requirement and be made graphene dispersing solution, graphene and water ratio Example is 1:20-1:Between 30, dispersion liquid be ultrasonically treated 2 hours, and stir evenly;
(2), the bentonite for meeting the ratio requirement and the plaster of paris are added in mixed liquor made from step (1), machinery stirs It mixes 1 hour and reaches uniform state;
(3), the cement for meeting the ratio requirement and carbon fiber, steel fibre mechanical agitation are reached into uniform state in 1 hour, then It is added thereto to remix after the zinc powder for meeting the ratio requirement is mixed with crystalline flake graphite and reaches within 1 hour uniform state, and will The mixture obtained herein is all added in mixed slurry made from step (2), and stirring reaches uniform state in 1 hour;
(4), by slurry agitation made from step (3) it is uniform after pour into mold, obtain the stone after standing solidification in 24 hours Black alkene is modified resistance-lowering material.
CN201810192105.XA 2018-03-08 2018-03-08 Modified resistance-lowering material of a kind of graphene and preparation method thereof Expired - Fee Related CN108409229B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110137704A (en) * 2019-05-30 2019-08-16 武汉明心电力科技有限公司 A kind of novel power transmission overhead line structures earthing pole material
CN112624725A (en) * 2019-10-09 2021-04-09 中国科学院宁波材料技术与工程研究所 Conductive concrete composition capable of being rapidly cured and formed, preparation method and application thereof
CN112688093A (en) * 2020-12-24 2021-04-20 湖北省雷博盾科技有限公司 Graphene modified grounding resistance-reducing module and processing method
CN113517082A (en) * 2021-04-09 2021-10-19 湖南省雷博盾科技有限公司 Resistance reducing liquid for grounding and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1472750A (en) * 2002-08-01 2004-02-04 寇承平 Physical grounding resistance reducing agent
CN105957577A (en) * 2016-05-05 2016-09-21 国网江西省电力科学研究院 Grounding calcium bentonite-based resistance-reducing agent
CN106064907A (en) * 2016-06-05 2016-11-02 南昌航空大学 A kind of sulfonated polyaniline modification Na-bentonite soil matrix friction reducer

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1472750A (en) * 2002-08-01 2004-02-04 寇承平 Physical grounding resistance reducing agent
CN105957577A (en) * 2016-05-05 2016-09-21 国网江西省电力科学研究院 Grounding calcium bentonite-based resistance-reducing agent
CN106064907A (en) * 2016-06-05 2016-11-02 南昌航空大学 A kind of sulfonated polyaniline modification Na-bentonite soil matrix friction reducer

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110137704A (en) * 2019-05-30 2019-08-16 武汉明心电力科技有限公司 A kind of novel power transmission overhead line structures earthing pole material
CN112624725A (en) * 2019-10-09 2021-04-09 中国科学院宁波材料技术与工程研究所 Conductive concrete composition capable of being rapidly cured and formed, preparation method and application thereof
CN112688093A (en) * 2020-12-24 2021-04-20 湖北省雷博盾科技有限公司 Graphene modified grounding resistance-reducing module and processing method
CN112688093B (en) * 2020-12-24 2021-08-17 湖北省雷博盾科技有限公司 Graphene modified grounding resistance-reducing module and processing method
CN113517082A (en) * 2021-04-09 2021-10-19 湖南省雷博盾科技有限公司 Resistance reducing liquid for grounding and preparation method thereof

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