CN106315573B - The preparation method of modified graphene and its cement composite material - Google Patents
The preparation method of modified graphene and its cement composite material Download PDFInfo
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- CN106315573B CN106315573B CN201610707671.0A CN201610707671A CN106315573B CN 106315573 B CN106315573 B CN 106315573B CN 201610707671 A CN201610707671 A CN 201610707671A CN 106315573 B CN106315573 B CN 106315573B
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- modified graphene
- graphene
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- silicate
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 239000004568 cement Substances 0.000 title claims abstract description 104
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002131 composite material Substances 0.000 title claims description 36
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 63
- 238000003756 stirring Methods 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000010438 heat treatment Methods 0.000 claims abstract description 33
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 23
- JHXCINJSAAFBDH-UHFFFAOYSA-N [Ca].O[Si](O)(O)O Chemical compound [Ca].O[Si](O)(O)O JHXCINJSAAFBDH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 60
- 239000007788 liquid Substances 0.000 claims description 25
- 239000011575 calcium Substances 0.000 claims description 23
- 238000009938 salting Methods 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 20
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 19
- 229910052791 calcium Inorganic materials 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- 239000004111 Potassium silicate Substances 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000391 magnesium silicate Substances 0.000 claims description 3
- 235000019792 magnesium silicate Nutrition 0.000 claims description 3
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 3
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 3
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 235000012241 calcium silicate Nutrition 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 8
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 abstract description 7
- 239000000920 calcium hydroxide Substances 0.000 abstract description 7
- 229910001861 calcium hydroxide Inorganic materials 0.000 abstract description 7
- 238000006703 hydration reaction Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 230000036571 hydration Effects 0.000 abstract description 4
- 230000006911 nucleation Effects 0.000 abstract description 3
- 238000010899 nucleation Methods 0.000 abstract description 3
- 239000002002 slurry Substances 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000012423 maintenance Methods 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 239000011083 cement mortar Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 229910052602 gypsum Inorganic materials 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- 229910021534 tricalcium silicate Inorganic materials 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229910000171 calcio olivine Inorganic materials 0.000 description 1
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 235000019976 tricalcium silicate Nutrition 0.000 description 1
Classifications
-
- 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
-
- 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
- C04B20/10—Coating or impregnating
- C04B20/1055—Coating or impregnating with inorganic materials
- C04B20/1074—Silicates, e.g. glass
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- 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
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The present invention provides a kind of preparation methods of modified graphene, comprising: A) graphene oxide water solution, soluble calcium salt are mixed with silicate, heating is reacted under stirring conditions, obtains the modified graphene that surface growth has silicic acid calcium nano.Compared with prior art, the present invention generates cement main component silicic acid calcium nano in surface of graphene oxide and obtains modified graphene, after the modified graphene and cement mixing, nanometer calcium silicates can play nucleation in cement hydration process, and then promote the generation of hydrated product calcium silicates in cement, growth, the generation for reducing nuisance calcium hydroxide and acicular substance, improves the intensity of cement；And the modified graphene can effectively solve reunion present in existing graphene addition manner, disperse the problems such as being not thorough.
Description
Technical field
The invention belongs to technical field of composite materials more particularly to the systems of a kind of modified graphene and its cement composite material
Preparation Method.
Background technique
The cement construction material most wide as usage amount maximum, the performance improvement for studying cement have very great meaning.
It theoretically analyzes, cement is in dry state mainly by tricalcium silicate (C3S, Ca3SiO5), dicalcium silicate (C2S, Ca2SiO4), aluminic acid
Tricalcium (C3A, Ca3Al2O6) and a small amount of hydrosulphate (sylvite, sodium salt), gypsum (CaSO4·2H2O it) forms.In cement water
During change, C3A reacts to form entringite with gypsum therein first；Entringite continues and C3A reaction is converted into single sulfur type aquation
Aluminum sulfate (Afm)；C3S and C2S occurs hydration reaction and forms calcium hydroxide (CH) and calcium silicates (C-S-H) gel.These lenticulars
Product and gel and unhydrated cement granules together form cement slurry, intensity and brittleness tool to cement-base composite material
There is conclusive effect.Wherein calcium hydroxide and other spicules are the key factors for influencing strength of cement, how to reduce its life
At most important.
With the maturation of graphene preparation, chemical modification and dispersion technology, the composite material based on graphene is ground in recent years
Study carefully and makes much progress.Since there are graphene the performances such as excellent electricity, mechanics, calorifics to make the composite material based on graphene past
It is past that there are many excellent characteristics, thus graphene composite material has been a great concern.According to the literature, there is more scholar
Currently it is dedicated to the research of graphene/cement.But dispersion and graphene of the graphene in cement how are solved in cement water
Change in the process how with the intact Complex Problem of hydrated product, become current hot spot urgently to be solved.
It is current mainly to use three kinds of addition manners in the research of graphene/cement composite material: directly to mix, be added
Mixing, the modified mixing of graphene after dispersing agent.The mode directly mixed can not solve graphene agglomeration traits；Dispersion is added
Although agent mode can improve dispersion effect to a certain extent, currently still without preferable dispersion, and the addition of dispersing agent
For the later period, the influence of hydrated cementitious effect be can not be ignored；The modified mode of graphene can promote graphene to divide in aqueous solution
It dissipates, but it still can generate certain influence to later period hydrated cementitious effect.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of modified graphene and its cement composite material
Preparation method, the modified graphene of this method preparation can promote the hydration reaction of cement, improves the intensity of composite material.
The present invention provides a kind of preparation methods of modified graphene, comprising:
A) graphene oxide water solution, soluble calcium salt are mixed with silicate, heating carries out anti-under stirring conditions
It answers, obtains the modified graphene that surface growth has silicic acid calcium nano.
Preferably, the step A) specifically:
A1 the pH value of graphene oxide water solution) is adjusted to faintly acid or neutrality, then under conditions of heating stirring
Solubility calcium salting liquid is added；
A2) under conditions of heating stirring, silicate solutions are added into step A1) in obtained reaction solution, then stirring
Under conditions of heat and reacted, obtain the modified graphene that surface growth has silicic acid calcium nano.
Preferably, the step A1) specifically:
After graphene oxide water solution is ultrasonically treated, then its pH value is adjusted to 5~7, then in heating stirring
Under conditions of be added solubility calcium salting liquid.
Preferably, the mass concentration of graphene oxide is 0.01%~5% in the graphene oxide water solution；
Soluble calcium salt in the solubility calcium salting liquid is CaCl2And/or Ca (NO3)2；The soluble calcium salt is molten
The mass concentration of soluble calcium salt is 0.1%~20% in liquid；
Silicate in the silicate solutions is one of sodium metasilicate, potassium silicate and magnesium silicate or a variety of；The silicon
The mass concentration of silicate is 0.1%~20% in acid salt solution.
Preferably, the step A1) in heating stirring, step A2) in heating stirring and the revolving speed of stirring each independently
For 150~500rpm；
The speed that the solubility calcium salting liquid is added is 1~200ml/min；
The speed that the silicate solutions are added is 1~200ml/min.
Preferably, the step A1) in heating stirring temperature be 20 DEG C~80 DEG C；Step A2) in heating stirring temperature
Degree is 20 DEG C~100 DEG C；The temperature of the reaction is 50 DEG C~120 DEG C；The time of the reaction is more than or equal to for 24 hours.
Preferably, soluble calcium salt and graphene oxide in graphene oxide water solution in the solubility calcium salting liquid
Mass ratio is 0.1 ‰ -10%；The molar ratio of soluble calcium salt and silicate in silicate solutions in the solubility calcium salting liquid
For 1:(0.9~1.2).
The present invention also provides a kind of modified graphene/cement composite materials, including modified graphene and cement.
The present invention also provides a kind of preparation methods of modified graphene/cement composite material, comprising:
B1 modified graphene is mixed with water), obtains modified graphite aqueous solution；
B2) by the modified graphite aqueous solution and cement mixing, modified graphene/cement composite material is obtained.
Preferably, the mass concentration of modified graphene is 0.05%~20% in the modified graphite aqueous solution；It is described
The quality of modified graphite aqueous solution is the 0.01%~5% of cement quality.
The present invention provides a kind of preparation methods of modified graphene, comprising: A) by graphene oxide water solution, solubility
Calcium salt is mixed with silicate, and heating is reacted under stirring conditions, and obtaining surface growth has changing for silicic acid calcium nano
Property graphene.Compared with prior art, the present invention generates cement main component silicic acid calcium nano in surface of graphene oxide
Modified graphene is obtained, after the modified graphene and cement mixing, nanometer calcium silicates can play crystalline substance in cement hydration process
Core effect, and then promote the generation of hydrated product calcium silicates in cement, growth, reduce nuisance calcium hydroxide and acicular substance
It generates, improves the intensity of cement；And the modified graphene can effectively solve present in existing graphene addition manner reunion,
The problems such as dispersion is not thorough.
The experimental results showed that modified graphene/cement composite material prepared by the present invention can make the fold resistance of cement paste
25% can be improved, compression strength improves 21%.
Attached drawing invention
Fig. 1 is the stereoscan photograph of graphene oxide used in the embodiment of the present invention 1；
Fig. 2 is the stereoscan photograph of modified graphene obtained in the embodiment of the present invention 1；
Fig. 3 is the stereoscan photograph of the traditional cements net slurry after conserving 7 days in the embodiment of the present invention 1；
Fig. 4 is modified graphene/cement composite material stereoscan photograph after conserving 7 days in the embodiment of the present invention 1；
Fig. 5 is the stereoscan photograph of the traditional cements net slurry after conserving 14 days in the embodiment of the present invention 1；
Fig. 6 is that modified graphene/cement composite material scanning electron microscope after conserving 14 days in the embodiment of the present invention 1 is shone
Piece.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
The present invention provides a kind of preparation methods of modified graphene, comprising: A) by graphene oxide water solution, solubility
Calcium salt is mixed with silicate, and heating is reacted under stirring conditions, obtains modified graphene.
Wherein, the present invention is not particularly limited the source of all raw materials, is commercially available.
In the present invention, it is preferred to first be ultrasonically treated graphene oxide water solution, it is at good dispersed
State；Wherein, the mass concentration of graphene oxide is preferably 0.01%~5% in the graphene oxide water solution, more preferably
0.1%~4%, it is further preferably 0.1%~3%, is further preferably 0.1%~2%, most preferably 0.5%~2%；In the present invention
In some embodiments provided, the mass concentration of graphene oxide is preferably 0.5% in the graphene oxide water solution；At this
It invents in some embodiments provided, the mass concentration of graphene oxide is preferably 0.1% in the graphene oxide water solution；
In other embodiments provided by the invention, the mass concentration of graphene oxide is preferably in the graphene oxide water solution
2%；Graphene oxide in the graphene oxide water solution is graphene oxide well known to those skilled in the art, and
Without special limitation, the graphene oxide of preferred monolithic rate (within 5 layers) 90% or more in the present invention；The graphene oxide is excellent
Gating oxidization-reduction mode obtains；The temperature of the ultrasound is preferably 40 DEG C~80 DEG C, and more preferably 40 DEG C~60 DEG C, then it is excellent
It is selected as 40 DEG C~50 DEG C, most preferably 40 DEG C~45 DEG C；The time of the ultrasound is preferably 10~60min, more preferably 20~
50min is further preferably 30~50min.
After ultrasonic treatment, its pH value is preferably adjusted to faintly acid or neutrality, its pH value is more preferably adjusted to 5~7, then
It is preferred that its pH value is adjusted to 5.5~6.5；In the present invention, it is preferred to adjust pH value using aqueous slkali；The aqueous slkali is ability
Aqueous slkali known to field technique personnel, has no special limitation, in the present invention preferably ammonium hydroxide, sodium hydrate aqueous solution with
One of potassium hydroxide aqueous solution is a variety of.
After adjusting pH value, solubility calcium salting liquid is added under conditions of heating stirring；The temperature of the heating stirring is excellent
20 DEG C~80 DEG C are selected as, it is further preferably 50 DEG C~65 DEG C that more preferably 40 DEG C~80 DEG C, which be further preferably 45 DEG C~70 DEG C, optimal
It is selected as 50 DEG C~60 DEG C；In some embodiments provided by the invention, the temperature of the heating stirring is preferably 50 DEG C；In this hair
In some embodiments of bright offer, the temperature of the heating stirring is preferably 55 DEG C；In other embodiments provided by the invention
In, the temperature of the heating stirring is preferably 60 DEG C；The revolving speed of the heating stirring is preferably 150~500rpm, more preferably
200~500rpm is further preferably 300~500rpm, most preferably 300~400rpm；It is solvable in the solubility calcium salting liquid
Property calcium salt be soluble calcium salt well known to those skilled in the art, have no special limitation, preferably chlorination in the present invention
Calcium (CaCl2) and/or calcium nitrate (Ca (NO3)2)；Soluble calcium salt and graphene oxide are water-soluble in the solubility calcium salting liquid
The mass ratio of graphene oxide preferably 0.1 ‰~10%, more preferably 0.5%~5% in liquid are further preferably 2%~3%, most
Preferably 1%~2%；The mass concentration of soluble calcium salt is preferably 0.1%~50% in the solubility calcium salting liquid, more excellent
It is selected as 0.1%~20%, is further preferably 5%~20%, is further preferably 8%~15%, most preferably 8%~10%；It is described can
Dissolubility calcium salt soln preferably uses constant pressure funnel to be added；The addition speed of the solubility calcium salting liquid is preferably 1~
200ml/min, more preferably 20~150ml/min are further preferably 50~150ml/min, most preferably 50~100ml/min.
After adding solubility calcium salting liquid, under conditions of heating stirring, silicate solutions are added；The heating stirring
Temperature is preferably 20 DEG C~100 DEG C, more preferably 30 DEG C~100 DEG C, is further preferably 35 DEG C~80 DEG C, is further preferably 35 DEG C~60
DEG C, most preferably 35 DEG C~50 DEG C；In some embodiments provided by the invention, the temperature of the heating stirring is preferably 35
℃；In other embodiments provided by the invention, the temperature of the heating stirring is preferably 45 DEG C；The heating stirring turns
Speed is preferably 150~500rpm, more preferably 200~500rpm, is further preferably 300~500rpm, most preferably 300~
400rpm；Silicate in the silicate solutions is silicate well known to those skilled in the art, has no special limit
It makes, is preferably one of sodium metasilicate, potassium silicate and magnesium silicate or a variety of in the present invention；In the silicate solutions silicate with
The molar ratio of soluble calcium salt is preferably 1:(0.9~1.2 in solubility calcium salting liquid), more preferably 1:(1~1.1), optimal
It is selected as 1:1；The mass concentration of silicate is preferably 0.1%~50% in the silicate solutions, more preferably 0.1%~
20%, it is further preferably 2%~20%, most preferably 5%~20%；The silicate solutions are preferably added using constant pressure funnel
Enter；The addition speed of the silicate solutions is preferably 1~200ml/min, more preferably 20~150ml/min, further preferably for
40~100ml/min, most preferably 50~80ml/min；In some embodiments provided by the invention, the silicate solutions
Addition speed be preferably 50ml/min.
After silicate solutions have been added, then heating is reacted under stirring conditions；The speed of the stirring is preferred
It is further preferably 200~300rpm for 150~500rpm, more preferably 200~400rpm, most preferably 200~250rpm；Institute
The temperature for stating reaction is preferably 50 DEG C~120 DEG C, and more preferably 60 DEG C~100 DEG C, be further preferably 60 DEG C~90 DEG C, most preferably
60 DEG C~80 DEG C；The time of the reaction is preferably greater than to be equal to for 24 hours, and more preferably 24~60h is further preferably 24~50h, most
Preferably 24~48h；In some embodiments provided by the invention, the temperature of the reaction is preferably 80 DEG C, the reaction
Time is preferably for 24 hours；In some embodiments provided by the invention, the temperature of the reaction is preferably 70 DEG C, the reaction
Time is preferably 36h；In other embodiments provided by the invention, the temperature of the reaction is preferably 60 DEG C, the reaction
Time be preferably 48h.
After reaction, it is preferably washed with water, removes salting liquid, obtain the modification that surface growth has silicic acid calcium nano
Graphene.
The present invention generates cement main component silicic acid calcium nano in surface of graphene oxide and obtains modified graphene, should
After modified graphene and cement mixing, nanometer calcium silicates can play nucleation in cement hydration process, and then promote water
The generation, growth of hydrated product calcium silicates, reduce the generation of nuisance calcium hydroxide and acicular substance, improve the strong of cement in mud
Degree；And the modified graphene can effectively solve reunion present in existing graphene addition manner, disperse the problems such as being not thorough.
The present invention also provides a kind of modified graphene/cement composite materials, including above-mentioned modified graphene and cement；Its
In, the cement is cement well known to those skilled in the art, have no special limitation, preferably 32.5 in the present invention,
One of 32.5R, 42.5,42.5R, high alumina cement and sulphate aluminium cement are a variety of.
The present invention also provides a kind of preparation methods of above-mentioned modified graphene/cement composite material, including B1) it will be above-mentioned
Modified graphene is mixed with water, obtains modified graphite aqueous solution；B2) by the modified graphite aqueous solution and cement mixing,
Obtain modified graphene/cement composite material.
In the present invention, modified graphene concentration of polymer solution is preferably 0.05%~20%, more preferably 0.1%~
10%, most preferably 0.5%~5%；The quality of modified graphene solution is preferably the 0.01%~5% of cement quality, more excellent
It is selected as 0.05%~3%, most preferably 0.1%~2%；The cement is cement well known to those skilled in the art, and
Without special limitation, in the present invention in preferably 32.5,32.5R, 42.5,42.5R, high alumina cement and sulphate aluminium cement one
Kind is a variety of.Modified graphene is added during cement mixing in a manner of aqueous solution, and whipping procedure is according to national standards
It can.Stirring terminates, and obtains modified graphene/cement composite material, is put into mold and conserves.
The present invention generates cement main component silicic acid calcium nano in surface of graphene oxide and obtains modified graphene, should
After modified graphene and cement mixing, nanometer calcium silicates can play nucleation in cement hydration process, and then promote water
The generation of hydrated product calcium silicates in mud reduces the generation of nuisance calcium hydroxide and acicular substance, improves the intensity of cement；And
And the modified graphene can effectively solve reunion present in existing graphene addition manner, disperse the problems such as being not thorough.
In order to further illustrate the present invention, with reference to embodiments to a kind of modified graphene provided by the invention and its water
The preparation method of mud composite material is described in detail.
Reagent used in following embodiment is commercially available.
Embodiment 1
1.1 take 1000g graphene oxide water solution, and content 0.5% is ultrasonically treated at 40 DEG C, ultrasonic 30min, surpass
Acoustic frequency 50Hz；
1.2 are added 5% NaOH solution, adjust pH value of solution to 5.7；
1.3 use constant pressure funnel to be slowly added to 10%CaCl with the speed of 50ml/min2Solution 100ml, and control
60 DEG C of experimental temperature, revolving speed 300rpm；
1.4 use constant pressure funnel be slowly added to the speed of 50ml/min with calcium ion same molar 10%
Na2SiO3Solution controls 35 DEG C of experimental temperature, revolving speed 300rpm；
1.5 are warming up to 80 DEG C, are persistently stirred 24 hours with 200rpm revolving speed；
1.6 wash with water solution obtained in 1.5, remove salting liquid to get modified graphite aqueous solution.It is dissolved in
The aqueous solution that mass concentration is 2% is made into water；
1.7 are added in 42.5R cement according to 1% adding proportion that modified graphene Mass Solution is cement quality,
Modified graphene cement paste is prepared, carries out Morphology analysis after maintenance.And it synchronizes and prepares traditional cements net slurry (i.e. without changing
The cement paste of property graphene), it is compared and analyzed with it.
Graphene oxide used in embodiment 1 is analyzed using scanning electron microscope, obtains its scanning electron microscope
Photo, as shown in Figure 1.
Modified graphene obtained in embodiment 1 is analyzed using scanning electron microscope, obtains its scanning electron microscope
Photo, as shown in Figure 2.
It is net to modified graphene/cement composite material cement after being conserved in embodiment 1 using scanning electron microscope
Slurry is analyzed with traditional cements net slurry, obtains its stereoscan photograph, as shown in Fig. 3~Fig. 6, after wherein Fig. 3 is maintenance 7 days
Traditional cements net slurry stereoscan photograph；Fig. 4 is that modified graphene/cement composite material cement after conserving 7 days is net
The stereoscan photograph of slurry；Fig. 5 is the stereoscan photograph of the traditional cements net slurry after conserving 14 days；After Fig. 6 is maintenance 14 days
Modified graphene/cement composite material cement paste stereoscan photograph.
By Fig. 3~Fig. 6 it is found that Microcosmic Comparative Analysis finds that there are more needles for traditional cements net slurry section after maintenance 7 days
Shape substance, this will produce bigger effect strength of cement, and modified graphene/cement composite material cement paste section is needle-shaped
Substance is obviously less, combines more closely between substance.14 day datas are conserved, as a result unanimously.Illustrate that modified graphene/cement is multiple
Condensation material can effectively change the microstructure of hydrolysis product of cement.
Embodiment 2
2.1 take 2500g graphene oxide water solution, and content 0.1% is ultrasonically treated at 40 DEG C, ultrasonic 30min, surpass
Acoustic frequency 50Hz；
2.2 are added 1% ammonia spirit, adjust pH value of solution to 6.2；
2.3 use constant pressure funnel to be slowly added to 10%CaCl with the speed of 100ml/min2Solution 80ml, and control
50 DEG C of experimental temperature, revolving speed 400rpm；
2.4 use constant pressure funnel be slowly added to the speed of 50ml/min with calcium ion same molar 10%
Na2SiO3Solution controls 45 DEG C of experimental temperature, revolving speed 400rpm；
2.5 are warming up to 70 DEG C, are persistently stirred 36 hours with 250rpm revolving speed；
2.6 wash with water solution obtained in 2.5, remove salting liquid to get modified graphite aqueous solution.It is dissolved in
The aqueous solution that mass concentration is 1% is made into water；
2.7 are added in 42.5R cement according to 0.5% adding proportion that modified graphene solution is cement quality, make
Standby modified graphene cement paste prepares 40*40*160mm cement mortar according to the proportion of standard cement mortar, carries out after maintenance
Performance test.And synchronize and prepare traditional cements net slurry, it is compared and analyzed with it.Microscopic appearance result and embodiment 1 are consistent.
Macro-mechanical property is shown in Table 1, and data are analyzed from table 1, and modified graphene/cement composite material mechanical property obtains
To largely being promoted, the change with microscopic appearance coincide.
The fracture resistance of cement paste analyzes result in 1 embodiment 2 of table
Embodiment 3
3.1 take 1000g graphene oxide water solution, and content 2% is ultrasonically treated at 45 DEG C, ultrasonic 50min, surpass
Acoustic frequency 50Hz；
3.2 are added 2% KOH solution, adjust pH value of solution to 6.2；
3.3 use constant pressure funnel to be slowly added to 8%CaCl with the speed of 50ml/min2Solution 150ml, and control reality
55 DEG C of temperature are tested, revolving speed 300rpm；
3.4 use constant pressure funnel be slowly added to the speed of 50ml/min with calcium ion same molar 8%
Na2SiO3Solution controls 35 DEG C of experimental temperature, revolving speed 300rpm；
3.5 are warming up to 60 DEG C, are persistently stirred 48 hours with 200rpm revolving speed；
3.6 wash with water solution obtained in 3.5, remove salting liquid to get modified graphite aqueous solution.It is dissolved in
The aqueous solution that mass concentration is 0.5% is made into water；
3.7 are added in 42.5 cement according to 2% adding proportion that modified graphene solution is cement quality, according to mark
The proportion of quasi- cement mortar prepares 40*40*160mm cement mortar, is tested for the property after maintenance.And it synchronizes and prepares traditional cements
Net slurry is compared and analyzed with it, and the performance test data of the two is shown in Table 2.
The compressive property of cement paste analyzes result in 2 embodiment 3 of table
Claims (9)
1. a kind of modified graphene/cement composite material, which is characterized in that including modified graphene and cement；
The modified graphene is prepared in accordance with the following methods:
A) graphene oxide water solution, soluble calcium salt are mixed with silicate, heating is reacted under stirring conditions, is obtained
The modified graphene for having silicic acid calcium nano is grown to surface.
2. modified graphene/cement composite material according to claim 1, which is characterized in that the step A) specifically:
A1 the pH value of graphene oxide water solution) is adjusted to faintly acid or neutrality, is then added under conditions of heating stirring
Solubility calcium salting liquid；
A2) under conditions of heating stirring, silicate solutions are added into step A1) in obtained reaction solution, then in the item of stirring
Heating is reacted under part, obtains the modified graphene that surface growth has silicic acid calcium nano.
3. modified graphene/cement composite material according to claim 2, which is characterized in that the step A1) it is specific
Are as follows:
After graphene oxide water solution is ultrasonically treated, then its pH value is adjusted to 5~7, then in the item of heating stirring
Solubility calcium salting liquid is added under part.
4. modified graphene/cement composite material according to claim 2, which is characterized in that the graphene oxide water
The mass concentration of graphene oxide is 0.01%~5% in solution；
Soluble calcium salt in the solubility calcium salting liquid is CaCl2And/or Ca (NO3)2；In the solubility calcium salting liquid
The mass concentration of soluble calcium salt is 0.1%~20%；
Silicate in the silicate solutions is one of sodium metasilicate, potassium silicate and magnesium silicate or a variety of；The silicate
The mass concentration of silicate is 0.1%~20% in solution.
5. modified graphene/cement composite material according to claim 2, which is characterized in that the step A1) in heating
Stirring, step A2) in heating stirring and the revolving speed of stirring be each independently 150~500rpm；
The speed that the solubility calcium salting liquid is added is 1~200ml/min；
The speed that the silicate solutions are added is 1~200ml/min.
6. modified graphene/cement composite material according to claim 2, which is characterized in that the step A1) in heating
The temperature of stirring is 20 DEG C~80 DEG C；Step A2) in heating stirring temperature be 20 DEG C~100 DEG C；The temperature of the reaction is
50 DEG C~120 DEG C；The time of the reaction is more than or equal to for 24 hours.
7. modified graphene/cement composite material according to claim 2, which is characterized in that the soluble calcium salt is molten
The mass ratio of soluble calcium salt and graphene oxide in graphene oxide water solution is 0.1 ‰~10% in liquid；The solubility
The molar ratio of soluble calcium salt and silicate in silicate solutions is 1:(0.9~1.2 in calcium salt soln).
8. a kind of preparation method of modified graphene/cement composite material characterized by comprising
B1 modified graphene is mixed with water), obtains modified graphite aqueous solution；
B2) by the modified graphite aqueous solution and cement mixing, modified graphene/cement composite material is obtained；
The modified graphene is prepared in accordance with the following methods:
A) graphene oxide water solution, soluble calcium salt are mixed with silicate, heating is reacted under stirring conditions, is obtained
The modified graphene for having silicic acid calcium nano is grown to surface.
9. preparation method according to claim 8, which is characterized in that modified graphene in the modified graphite aqueous solution
Mass concentration be 0.05%~20%；The quality of the modified graphite aqueous solution is the 0.01%~5% of cement quality.
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| CN106830858A (en) * | 2017-03-17 | 2017-06-13 | 青岛瑞利特新材料科技有限公司 | A kind of modified graphene complex cement Self-leveling closed material |
| CN108609918A (en) * | 2018-03-26 | 2018-10-02 | 青岛瑞利特新材料科技有限公司 | Graphene is except aldehyde diatom plate and preparation method thereof |
| CN110016379A (en) * | 2018-12-12 | 2019-07-16 | 山西大同大学 | A kind of modified graphene lubricating oil and preparation method thereof |
| CN109824292A (en) * | 2019-03-26 | 2019-05-31 | 菲大装配式建筑工程(重庆)有限责任公司 | A kind of graphene-based composite material and preparation method, application |
| CN110790528B (en) * | 2019-11-28 | 2022-02-11 | 北京服装学院 | Preparation method and application of micro-nano crystal nucleus composite material |
| CN110981298B (en) * | 2019-11-28 | 2021-03-30 | 浙江大学 | Graphene oxide-nano mineral enhanced geopolymer material and preparation method thereof |
| CN112479625B (en) * | 2020-11-06 | 2022-04-12 | 安徽工业大学 | Preparation method of graphene modified cement and product thereof |
| CN112794318B (en) * | 2021-01-28 | 2023-06-27 | 中国科学院生态环境研究中心 | Pipeline lining based on three-dimensional graphene material and preparation method and application thereof |
| CN114441573B (en) * | 2021-12-29 | 2023-07-28 | 广西科技大学 | Novel scanning electron microscope sample preparation method convenient for observing morphology of graphene-regulated cement hydration crystals |
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