CN109665517A - The preparation method and application of graphene nano material and modified graphene nano material - Google Patents
The preparation method and application of graphene nano material and modified graphene nano material Download PDFInfo
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- C01—INORGANIC CHEMISTRY
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
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- C01B32/186—Preparation by chemical vapour deposition [CVD]
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
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- C01B2204/02—Single layer graphene
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Abstract
The embodiment of the invention discloses the preparation methods and application of a kind of graphene nano material and modified graphene nano material, belong to graphene nano field of material technology.The preparation method of the graphene nano material the following steps are included: 1) catalyst aid, magnesia and deionized water complex reaction obtain slurry, the slurry obtains the magnesium oxide carrier rich in active material through mist projection granulating and drying and roasting；2) after the magnesium oxide carrier rich in active material is heated to 600-900 DEG C under atmosphere of inert gases, more carbon cracking gases are passed through, chemical vapour deposition reaction is carried out, obtains graphene nano material.When modified graphene nano material made from the graphene nano material of high single layer rate and high-specific surface area and silicate progress hydro-thermal reaction is added in concrete by the embodiment of the present invention, intensity, toughness, the performances such as water-fast of concrete can be obviously improved, there is vast potential for future development.
Description
Technical field
The present embodiments relate to graphene nano field of material technology, and in particular to a kind of graphene nano material and changes
The preparation method and application of property graphene nano material.
Background technique
With the industrialized deep development of society, normal concrete is as most widely used, most important traditional architecture material
One of material, yield and dosage are all promoted constantly.Normal concrete is by cement, coarse aggregate (rubble or cobble), thin bone
Expect (sand), additive and water mix, a kind of artificial stone made of hardened, wherein sand, stone play skeleton work in concrete
With inhibiting the contraction of cement, cement and water form cement slurry, the gap between filler aggregate.Due to the rigid mistake of normal concrete
Greatly, flexible insufficient, it is easy to crack, it is limited in the application in many fields, therefore to have become cement base compound for high performance concrete
Research hotspot in Material Field.
Nano material refers to that particle of the partial size between 1-100nm, nanoparticle are to be in cluster and macroscopic material boundary
Transitional region, be a kind of typical Mesoscopic structure, including metal, nonmetallic, organic and inorganic and biological etc. a variety of granular materials
Material.With the fine of substance, Electronic Structure and crystal structure change, and produce macroscopic material material and do not have
The excellent characteristics such as some small-size effects, quantum effect, surface and macroscopical tunnel-effect, to make superfines and conventional granulates
Material compares with a series of special physics, chemical property, it is thus possible to its added body is assigned in structure or function
The many performances for being different from traditional material of system.The strong of concrete can be increased substantially by developing novel concrete using nano material
Degree, workability and endurance quality.
Graphene is carbon atom with SP2Hybridized orbital is in the single layer two dimensional crystal that honeycomb lattice is arranged to make up, by carbon atom
It is formed by atomic size net with its covalent bond, is plane polycyclic aromatic hydrocarbons (PAH) atomic crystal, graphene has perfect two dimension brilliant
Body structure, its lattice are the hexagons surrounded by six carbon atoms, with a thickness of an atomic layer, are connected between carbon atom by σ key
It connects, combination sp2Hydridization, these σ keys impart the extremely excellent mechanical property of graphene and structural rigidity.Solely due to it
Special and perfect structure, so that graphene has the characteristics such as excellent electricity, mechanics, calorifics and optics.
In the prior art, graphene be mostly graphite oxide or removing graphite, by equipment machining accuracy and environmental pollution etc. because
Element influences, and the specific surface area and single layer rate of obtained graphene be not high, and there are inter-layer bonding force is weak and interlayer functional group
Difficult defect is filled, thus it is unobvious to the effect of concrete modifying enhancing.
In view of this, the present invention is specifically proposed.
Summary of the invention
For this purpose, the embodiment of the invention provides the preparation sides of a kind of graphene nano material and modified graphene nano material
Method and application have high single layer rate and high-specific surface area using graphene nano material made from chemical vapor deposition (CVD) method,
Modified graphene Application of micron made from hydro-thermal reaction further occurs with silicate when concrete, can be obviously improved mixed
Coagulate the performances such as native intensity, toughness, water-fast.
To achieve the goals above, the embodiment of the present invention uses following technical scheme:
In the first aspect of embodiments of the present invention, a kind of preparation method of graphene nano material is provided, is wrapped
Include following steps:
1) catalyst aid, magnesia and deionized water complex reaction obtain slurry, and the slurry is through mist projection granulating and drying
Roasting, obtain partial size be 10-100 μm, specific surface area 50-200m2The magnesium oxide carrier rich in active material of/g；
2) it after the magnesium oxide carrier rich in active material is heated to 600-900 DEG C under atmosphere of inert gases, is passed through
More carbon cracking gases carry out chemical vapor deposition (CVD) and react 0.5-3h, obtain graphene nano material.
Further, in step 1), catalyst aid and magnesia 1:50-100 in mass ratio, investment fill deionized water
In stirred autoclave, solid-liquid mass ratio 1:5-20 is warming up to 85-95 DEG C under normal pressure, and constant temperature complex reaction 4-6h is starched
Material.
Further, the catalyst aid be metal oxide or metal salt, the metal be selected from copper, chromium, ruthenium, nickel, aluminium,
Any one of palladium, zinc.
Further, the step 2) includes:
2.1) after fluidized-bed reactor carries out air-leakage test and qualification, inert gas replacement is carried out；
2.2) under the protection atmosphere of inert gas, the magnesia solid carrier investment fluidized bed that will be enriched in activating substance is anti-
Device is answered, and is warming up to 600-900 DEG C；
2.3) 600-900 DEG C at a temperature of, be continually fed into stage by stage by program through distributor be uniformly mixed indifferent gas
The gaseous mixture of body and more carbon cracking gases, wherein the volume ratio of inert gas and more carbon cracking gases is 1:0.1-10, gaseous mixture and richness
The mass ratio 1:0.5-5 of magnesium oxide carrier containing active material, the carbon atom of Pintsch process under the catalytic action of active material,
Again group forms the graphene nano material of single layer or few layer, when hydrogen content in tail gas to magnesium oxide carrier surface is deposited to
When less than 4%, stopping is passed through more carbon cracking gases, continues to be passed through inert gas；
2.4) be 1:10-20 in gas-solid ratio, under conditions of gas velocity is 10-30m/s, using inert gas by the single layer or
The graphene nano material of few layer is transported to intermediate bunker from fluidized-bed reactor, terminates single batch reaction；
2.5) continue according to 2.1), 2.2), 2.3), 2.4) the step of carry out next batch reaction.
Further, more carbon cracking gases are selected from methane, ethane, propane, normal butane, iso-butane, pentane, isoamyl
At least one of alkane, neopentane, ethylene, propylene, n-butene, isobutene.
In the second aspect of embodiments of the present invention, a kind of preparation side of modified graphene nano material is provided
Method, comprising the following steps: graphene nano material made from the preparation method of above-mentioned graphene nano material and silicate press matter
It measures and is filled in the stirred autoclave of deionized water than 1:3-4 investment, solid-liquid mass ratio 1:4-5 rises under the conditions of moderate-speed mixer
To 150-170 DEG C, reaction pressure control carries out hydro-thermal reaction 2-4h, can be prepared by modified graphene and receive temperature in 0.6-0.8MPa
Rice material.
Further, the silicate is selected from any one of sodium metasilicate, magnesium silicate, alumina silicate.
Further, it is 200-2000cp (25 DEG C), solid content 20- that the modified graphene nano material, which is viscosity,
30% slurry.
In the third aspect of embodiments of the present invention, provide a kind of by above-mentioned modified graphene nano material
Modified graphene nano material made from preparation method.
In the fourth aspect of embodiments of the present invention, above-mentioned modified graphene nano material is provided in concrete
Application in material.
The embodiment of the present invention has the advantages that
1, carrier, active metal, complex reaction condition is in optimized selection in the present invention, and it is high that catalytic activity is made
Carrier, under the high temperature conditions, the catalytic pyrolysis through active material makes carbon atom in magnesium oxide carrier surface in situ to more carbon cracking gases
Deposition generates the graphene nano material with high single layer rate and high-specific surface area.
2, hydro-thermal reaction occurs for graphene nano material and silicate, utilizes the two-dimensional network structure of graphene, Yi Jigao
Intensity, high tenacity, the characteristic of surface modificability and big specific surface area, it is filling-modified through silicate ion, form graphene
Hybridization network nucleus, modified graphene nano material obtained is added in concrete, and the silicate on nucleus is further
With the calcium binding in concrete, C-S-H gel is generated, realizes the calcium silicates lattice amplification of concrete, and then promotes coagulation
The performances such as the intensity, toughness of soil, water-fast, have vast potential for future development.
Detailed description of the invention
It, below will be to embodiment party in order to illustrate more clearly of embodiments of the present invention or technical solution in the prior art
Formula or attached drawing needed to be used in the description of the prior art are briefly described.It should be evident that the accompanying drawings in the following description is only
It is merely exemplary, it for those of ordinary skill in the art, without creative efforts, can also basis
The attached drawing of offer, which is extended, obtains other implementation attached drawings.
Fig. 1 is a kind of flow diagram of the preparation method of modified graphene nano material provided in an embodiment of the present invention.
Specific embodiment
Embodiments of the present invention are illustrated by particular specific embodiment below, those skilled in the art can be by this explanation
Content disclosed by book is understood other advantages and efficacy of the present invention easily, it is clear that described embodiment is the present invention one
Section Example, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not doing
Every other embodiment obtained under the premise of creative work out, shall fall within the protection scope of the present invention.
This part carries out general description to the material and test method that arrive used in present invention test.Although being
It realizes many materials used in the object of the invention and operating method is it is known in the art that still the present invention still uses up herein
It may detailed description.It will be apparent to those skilled in the art that within a context, if not specified, material therefor of the present invention and behaviour
It is well known in the art as method.
Below to the preparation method of the graphene nano material of the embodiment of the present invention and modified graphene nano material with answer
With being described in detail.
A kind of preparation method of graphene nano material, comprising the following steps:
1) catalyst aid, magnesia and deionized water complex reaction obtain slurry, and the slurry is through mist projection granulating and drying
Roasting, obtain partial size be 10-100 μm, specific surface area 50-200m2The magnesium oxide carrier rich in active material of/g.
In the present invention, catalyst aid is the oxide or salt of any one of metallic copper, chromium, ruthenium, nickel, aluminium, palladium, zinc, salt
Type include villaumite, nitrate, sulfate, hydrogen-oxygen salt dissolving etc..Preferably, catalyst aid includes copper oxide, three oxidations two
Chromium, ruthenium-oxide, nickel oxide, aluminum oxide, palladium oxide, zinc oxide, copper chloride, copper sulphate, Kocide SD, chromium chloride, nitric acid
Chromium, nitric acid ruthenium, nickel sulfate, nickel chloride, aluminum nitrate, aluminium hydroxide, palladium chloride, zinc chloride, zinc sulfate, zinc nitrate etc..
In the present invention, preferably magnesia is carrier, and magnesia under the high temperature conditions, easy-sintering and does not have high volcanic ash living
Property, in chemical vapour deposition reaction, the deposition of more carbon cracking gases is not influenced, while in the hydro-thermal reaction with silicate,
With water and CO2Subcarbonate or hydrogen-oxygen salt dissolving can be formed well, and aggregate can be good at by silicate ion polarity
Dispersion, does not influence the stability and uniformity of modified graphene nano material, and then do not influence its answering in concrete material
With.
In the present invention, catalyst aid (metal oxide or metal salt) carries out complex reaction first on magnesium oxide carrier,
It oxidizes metal object or metal salt is compounded on magnesium oxide carrier, specific surface small through mist projection granulating and drying and roasting formation partial size
The high magnesium oxide carrier rich in active material (presence in the form of metal complex) of product.In subsequent chemical vapour deposition reaction
In the process, metal complex is largely decomposed, the hydrogen reducing being further cracked to form at high temperature by more carbon cracking gases at
Active metal forms the catalyst carrier of active material (that is, active metal) high degree of dispersion.
Preferably, catalyst aid and magnesia 1:50-100 in mass ratio, investment fills being stirred to react for deionized water
In kettle, solid-liquid mass ratio 1:5-20 is warming up to 85-95 DEG C under normal pressure, and constant temperature complex reaction 4-6h obtains slurry, at this
Under part, the more economic progress of complex reaction, and the complexing amount of active metal is more.
Obtained slurry is quantitatively transported to mist projection granulating tower through metering pump, is centrifuged in high speed atomisation device and higher than 100 DEG C
Under environment, free water drying is carried out, obtained dry powder is transported to fluidized bed, carries out 450-550 DEG C of drying roast, finally
Obtain the magnesium oxide powder carrier rich in active material.
2) it after the magnesium oxide carrier rich in active material is heated to 600-900 DEG C under atmosphere of inert gases, is passed through
More carbon cracking gases carry out chemical vapor deposition (CVD) and react 0.5-3h, obtain graphene nano material, the specific steps are as follows:
2.1) after fluidized-bed reactor carries out air-leakage test and qualification, inert gas replacement is carried out；
2.2) under the protection atmosphere of inert gas (for example, nitrogen or argon gas), the magnesia that will be enriched in activating substance is carried
Body puts into fluidized-bed reactor, and is warming up to 600-900 DEG C；
2.3) 600-900 DEG C at a temperature of, be continually fed into stage by stage by program through distributor be uniformly mixed indifferent gas
The gaseous mixture of body and more carbon cracking gases, wherein the volume ratio of inert gas and more carbon cracking gases is 1:0.1-10, gaseous mixture and richness
The mass ratio 1:0.5-5 of magnesium oxide carrier containing active material, the carbon atom of Pintsch process under the catalytic action of active material,
Again group forms the graphene nano material of single layer or few layer, when hydrogen content in tail gas to magnesium oxide carrier surface is deposited to
When less than 4%, stopping is passed through more carbon cracking gases, continues to be passed through inert gas；
2.4) be 1:10-20 in gas-solid ratio, under conditions of gas velocity is 10-30m/s, using inert gas by the single layer or
The graphene nano material of few layer is transported to intermediate bunker from fluidized-bed reactor, terminates single batch reaction；
2.5) continue according to 2.1), 2.2), 2.3), 2.4) the step of carry out next batch reaction.
The present invention uses chemical vapour deposition technique, using magnesia as the deposition vehicle of graphene nano material, in inertia
Under atmosphere, more carbon cracking gases carry out Pintsch process catalysis under the action of catalyst (active metal), are formed monatomic
Carbon deposits on carrier, and the present invention is to catalyst carrier type, active metal, complex reaction condition and chemical vapor deposition
The process conditions of reaction, such as cracking temperature, gas-solid ratio are screened, and final graphene nano material obtained has excellent
High single layer rate and high-specific surface area.
In the present invention, more carbon cracking gases are selected from methane, ethane, propane, normal butane, iso-butane, pentane, isopentane, new
At least one of pentane, ethylene, propylene, n-butene and isobutene.
In the present invention, it is continually fed into more carbon cracking gases and inert gas stage by stage by program, just starts more when reaction
The amount that carbon cracking gas is passed through is more, after reacting a period of time, as active matter quality is reduced with magnesium oxide carrier surface
It deposited a part of graphene, so the demand of more carbon cracking gases is reduced, then reduce more carbon cracking gas intakes.
In the present invention, fluidized-bed reactor is vertical fluidised reactor.More carbon cracking reaction gas can be using segmentation preheating
Technique is added continuously in fluidized-bed reactor.
A kind of preparation method of modified graphene nano material, comprising the following steps:
Graphene nano material made from the above method fills stirring for deionized water with silicate 1:3-4 in mass ratio investment
It mixes in reaction kettle, solid-liquid mass ratio 1:4-5, under the conditions of moderate-speed mixer, is warming up to 150-170 DEG C, reaction pressure control exists
0.6-0.8MPa carries out hydro-thermal reaction 2-4h, can be prepared by modified graphene nano material, which is
Viscosity is 200-2000cp (25 DEG C), the slurry that solid content is 20-30%.
In the present invention, silicate is selected from any one of sodium metasilicate, magnesium silicate, alumina silicate.
In the present invention, graphene nano material has excellent high single layer rate and high-specific surface area, carries out with silicate
In hydro-thermal reaction modification procedure, silicate ion functional group filling rate is high, forms the hybridization network nucleus of graphene, and with
When concrete, calcium ion secondary hydration in the silicate and concrete on nucleus forms big graphene hybridization network
C-S-H gel nucleus reduces crackle caused by inside concrete tensile stress, last graphene since warm peak subtractive effect acts on
The interface area of nano material inhibits isolation, settlement action through the hydrated calcium silicate lattice condensation of concrete and aluminum magnesium silicate, improves
Interface cementitious material is bonded to what is gathered materials, is formed by curing homogeneous artificial stone, achievees the purpose that Material reinforcement and durable.
Simultaneously because the capillary gap in the micro- meso-hole structure and hydrated calcium silicate gel plugging cement stone of graphene, increases infiltration resistance
Power, greatly delayed by the immersion time of water penetration, also functioned to positive effect at water-fast, freeze proof aspect.
Concrete modifying is carried out, the actual interpolation amount of grapheme material of the invention only has ppm grades, that is, can reach and significantly change
The performances such as kind concrete strength, toughness, resistance to infiltration, heat exchange, therefore there is advantage at low cost.
The purpose of hydro-thermal reaction occurs for graphene nano material and silicate:
One, graphene nano material is after the functional group aquation of persilicate is compound, and graphene nano material is in the slurry
High degree of dispersion, soilless sticking object occur, and as additive be used for concrete when, form height with the calcium ion aquation in concrete
The calcium silicate crystals of intensity, silicate one end and graphene nano material carry out bond energy connection, the other end and calcium hydroxide aquation
Reaction generates hydrated calcium silicate crystal-[- C-SiO3 2--Ca-SiO3 2-- C-]-, so that the C-S-H gel of graphene hybridization network
Nucleus constantly amplifies, and plays the role of modified concrete.
Two, graphene nano material directly as additive application in concrete, other than influencing to blend the uniformity, by material
The hydrophobicity performance of material influences, and incorporation time greatly prolongs, and situation unmixed uniform and that concrete has been cured, Bu Nengman occurs
The process requirements of the subsequent concrete product of foot.
Three, the apparent density of graphene nano material is small, and the hybrid mode of concrete is largely open or semi-open
Formula, dust is unfriendly to working environment, will cause waste and influence worker occupational health health, by graphene nano material into
Capable modification is made slurry and can effectively solve the problem that the above problem.
Embodiment 1
The preparation method of the graphene nano material of the present embodiment the following steps are included:
1) copper sulphate and nickel chloride 1:2 in mass ratio, with magnesia 1:80 in mass ratio, investment fills stirring for deionized water
It mixes in reaction kettle, solid-liquid mass ratio 1:20, is warming up to 90 DEG C under normal pressure, constant temperature complex reaction 5h obtains slurry, the slurry
Through mist projection granulating and drying and roasting, obtain partial size be 30-50 μm, specific surface area 140-160m2/ g rich in active material
Magnesium oxide carrier；
2) it after the above-mentioned magnesium oxide carrier rich in active material is heated to 600 DEG C under atmosphere of inert gases, is passed through and includes
Methane, ethane, propane and normal butane more carbon cracking gases, carry out chemical vapor deposition (CVD) react 1.5h, obtain graphene and receive
Rice material.
It is tested through the methods of BET, SEM and TEM, the specific surface area of graphene nano material made from the present embodiment is
1600-1800m2/g。
Embodiment 2
The preparation method of the graphene nano material of the present embodiment the following steps are included:
1) zinc oxide, nitric acid ruthenium and magnesia 0.5:0.5:65 in mass ratio, investment fill being stirred to react for deionized water
In kettle, solid-liquid mass ratio 1:15 is warming up to 88 DEG C under normal pressure, and constant temperature complex reaction 6h obtains slurry, which is made by spraying
Grain and drying and roasting, obtain partial size be 80-100 μm, specific surface area 80-100m2The magnesia rich in active material of/g carries
Body；
2) it after the above-mentioned magnesium oxide carrier rich in active material is heated to 900 DEG C under atmosphere of inert gases, is passed through and includes
Methane, ethane, propane, propylene and n-butene more carbon cracking gases, carry out chemical vapor deposition (CVD) react 3h, obtain graphite
Alkene nano material.
It is tested through the methods of BET, SEM and TEM, the specific surface area of graphene nano material made from the present embodiment is
1300-1500m2/g。
Embodiment 3
The preparation method of the graphene nano material of the present embodiment the following steps are included:
1) zinc chloride, Kocide SD, aluminum nitrate and magnesia 0.2:0.4:0.4:92 in mass ratio, investment fill deionization
In the stirred autoclave of water, solid-liquid mass ratio 1:8 is warming up to 95 DEG C under normal pressure, and constant temperature complex reaction 4h obtains slurry, should
Slurry through mist projection granulating and drying and roasting, obtain partial size be 40-60 μm, specific surface area 120-150m2/ g's is rich in active matter
The magnesium oxide carrier of matter；
2) it after the above-mentioned magnesium oxide carrier rich in active material is heated to 800 DEG C under atmosphere of inert gases, is passed through and includes
Methane, ethane, propane, normal butane and iso-butane more carbon cracking gases, carry out chemical vapor deposition (CVD) react 2h, obtain stone
Black alkene nano material.
It is tested through the methods of BET, SEM and TEM, the specific surface area of graphene nano material made from the present embodiment is
1000-1200m2/g。
Embodiment 4
The preparation method of the modified graphene nano material of the present embodiment the following steps are included:
Graphene nano material made from embodiment 1 and sodium metasilicate 1:4 in mass ratio investment fill the stirring of deionized water
In reaction kettle, solid-liquid mass ratio 1:5 is warming up to 170 DEG C under the conditions of moderate-speed mixer, reaction pressure control in 0.8MPa, into
Row hydro-thermal reaction 4h can be prepared by the modified graphene nano material that viscosity is 1260cp, solid content is 22.6%.
Embodiment 5
The preparation method of the modified graphene nano material of the present embodiment the following steps are included:
Graphene nano material made from embodiment 2 fills stirring for deionized water with magnesium silicate 1:3.6 in mass ratio investment
It mixes in reaction kettle, solid-liquid mass ratio 1:4.5, under the conditions of moderate-speed mixer, is warming up to 150 DEG C, reaction pressure control exists
0.5MPa carries out hydro-thermal reaction 2h, can be prepared by the modified graphene nanometer material that viscosity is 1540cp, solid content is 25.8%
Material.
Embodiment 6
The preparation method of the modified graphene nano material of the present embodiment the following steps are included:
Graphene nano material made from embodiment 3 and alumina silicate 1:3 in mass ratio investment fill the stirring of deionized water
In reaction kettle, solid-liquid mass ratio 1:4 is warming up to 165 DEG C under the conditions of moderate-speed mixer, reaction pressure control in 0.7MPa, into
Row hydro-thermal reaction 3.5h can be prepared by the modified graphene nano material that viscosity is 1840cp, solid content is 28.5%.
Application examples
Application of the modified graphene nano material in steam-pressing aero-concrete.
It matches (mass ratio): 290 parts of lime, 370 parts of cement, 1160 parts of emery dust, 1080 parts of water, 2.5 parts of aluminium cream, modified stone
18 parts of black alkene nano material.
Blank group: modified graphene nano material is not mixed.
Contrast groups: with nano silica fume (being purchased from Beijing Deco Co., Ltd) replacement modified graphene nano material of equivalent.
It forms, get angry by mortar stirring, mold, High Temperature Curing, demoulding cutting, opening and inspecting the rings such as separation, the maintenance of 5d static state
Section, air entrained concrete test specimen made from the modified graphene nano material of embodiment 4-6, blank group and contrast groups, through intensity, is changed
The performance tests such as heat, test result are shown in Table 1.
Table 1
The result shows that: the modified graphene Application of micron of the embodiment of the present invention realizes 05 in steam-pressing aero-concrete
The purpose that grade intensity air entrained concrete heat exchange is 04 grade, the rank broken in steam-pressing aero-concrete GB15762-2008 standard refer to
Mark regulation meets the energy saving environmentally protective national policy requirement of lighting, high intensity, low heat exchange, therefore real through the invention
The addition of the modified graphene nano material of example is applied, is that the performance of steam-pressing aero-concrete improves, provides effectively application assistant
Card.
Modified graphene nano material provided by the invention is a kind of New Building Materials additive, intensity, it is water-fast, every
Heat etc. shows excellent performance, can be widely used for the infrastructure constructions field such as building, traffic, bridge, tunnel, mine,
It has broad application prospects.
Although above having used general explanation and specific embodiment, the present invention is described in detail, at this
On the basis of invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Therefore,
These modifications or improvements without departing from theon the basis of the spirit of the present invention are fallen within the scope of the claimed invention.
Claims (10)
1. a kind of preparation method of graphene nano material, which comprises the following steps:
1) catalyst aid, magnesia and deionized water complex reaction obtains slurry, the slurry through mist projection granulating and drying and roasting,
Obtain partial size be 10-100 μm, specific surface area 50-200m2The magnesium oxide carrier rich in active material of/g；
2) after the magnesium oxide carrier rich in active material is heated to 600-900 DEG C under atmosphere of inert gases, more carbon are passed through
Cracking gas carries out chemical vapor deposition (CVD) and reacts 0.5-3h, obtains graphene nano material.
2. the preparation method of graphene nano material according to claim 1, which is characterized in that in step 1), catalysis is helped
Agent and magnesia 1:50-100 in mass ratio, investment fill in the stirred autoclave of deionized water, solid-liquid mass ratio 1:5-20,
It is warming up to 85-95 DEG C under normal pressure, constant temperature complex reaction 4-6h obtains slurry.
3. the preparation method of graphene nano material according to claim 1, which is characterized in that the catalyst aid is gold
Belong to oxide or metal salt, the metal is selected from any one of copper, chromium, ruthenium, nickel, aluminium, palladium, zinc.
4. the preparation method of graphene nano material according to claim 1, which is characterized in that step 2) includes:
2.1) after fluidized-bed reactor carries out air-leakage test and qualification, inert gas replacement is carried out；
2.2) under the protection atmosphere of inert gas, it will be enriched in the magnesium oxide carrier investment fluidized-bed reactor of active material, and
It is warming up to 600-900 DEG C；
2.3) 600-900 DEG C at a temperature of, be continually fed into stage by stage by program through distributor be uniformly mixed inert gas and
The gaseous mixture of more carbon cracking gases, wherein the volume ratio of inert gas and more carbon cracking gases is 1:0.1-10, gaseous mixture with rich in living
The mass ratio 1:0.5-5 of the magnesium oxide carrier of property substance, the carbon atom of Pintsch process is under the catalytic action of active material, again
Group forms the graphene nano material of single layer or few layer, when hydrogen content is less than in tail gas to magnesium oxide carrier surface is deposited to
When 4%, stopping is passed through more carbon cracking gases, continues to be passed through inert gas；
It 2.4) is 1:10-20 in gas-solid ratio, under conditions of gas velocity is 10-30m/s, using inert gas by the single layer or few layer
Graphene nano material be transported to intermediate bunker from fluidized-bed reactor, terminate single batch reaction；
2.5) continue according to 2.1), 2.2), 2.3), 2.4) the step of carry out next batch reaction.
5. the preparation method of graphene nano material according to claim 1, which is characterized in that more carbon cracking gas choosings
From in methane, ethane, propane, normal butane, iso-butane, pentane, isopentane, neopentane, ethylene, propylene, n-butene, isobutene
At least one.
6. a kind of preparation method of modified graphene nano material, which comprises the following steps: claim 1-5 appoints
Graphene nano material made from one the method fills being stirred to react for deionized water with silicate 1:3-4 in mass ratio investment
In kettle, solid-liquid mass ratio 1:4-5 is warming up to 150-170 DEG C, reaction pressure is controlled in 0.6- under the conditions of moderate-speed mixer
0.8MPa carries out hydro-thermal reaction 2-4h, can be prepared by modified graphene nano material.
7. the preparation method of modified graphene nano material according to claim 6, which is characterized in that the silicate choosing
From any one of sodium metasilicate, magnesium silicate, alumina silicate.
8. the preparation method of modified graphene nano material according to claim 6, which is characterized in that the modified graphite
Alkene nano material is that viscosity is 200-2000cp (25 DEG C), the slurry that solid content is 20-30%.
9. a kind of modified graphene nano material as made from method as claimed in claim 6 to 8.
10. application of the modified graphene nano material as claimed in claim 9 in concrete material.
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| CN114180605A (en) * | 2021-12-31 | 2022-03-15 | 青海创信电子材料有限公司 | Preparation method of magnesium oxide particles |
| CN117886314A (en) * | 2023-12-27 | 2024-04-16 | 有研(广东)新材料技术研究院 | Graphitized carbon carrier with high specific surface area and preparation method thereof |
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| CN105967197B (en) * | 2016-05-10 | 2018-05-29 | 唐山建华科技发展有限责任公司 | A kind of water glass solution containing graphene and preparation method thereof |
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|---|---|---|---|---|
| CN114180605A (en) * | 2021-12-31 | 2022-03-15 | 青海创信电子材料有限公司 | Preparation method of magnesium oxide particles |
| CN114180605B (en) * | 2021-12-31 | 2024-02-06 | 青海创信电子材料有限公司 | Preparation method of magnesium oxide particles |
| CN117886314A (en) * | 2023-12-27 | 2024-04-16 | 有研(广东)新材料技术研究院 | Graphitized carbon carrier with high specific surface area and preparation method thereof |
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