CN106315573A - Preparation method of modified graphene and cement composite material thereof - Google Patents
Preparation method of modified graphene and cement composite material thereof Download PDFInfo
- Publication number
- CN106315573A CN106315573A CN201610707671.0A CN201610707671A CN106315573A CN 106315573 A CN106315573 A CN 106315573A CN 201610707671 A CN201610707671 A CN 201610707671A CN 106315573 A CN106315573 A CN 106315573A
- Authority
- CN
- China
- Prior art keywords
- cement
- graphene
- silicate
- preparation
- modified graphene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
Abstract
The invention provides a preparation method of modified graphene. The preparation method comprises the following steps: A) mixing a graphene oxide aqueous solution, soluble calcium salt and silicate, and heating and carrying out reaction under stirring conditions, so that the modified graphene with calcium silicate nanoparticles grown on the surface is obtained. Compared with the prior art, the preparation method has the advantages that a cement main component, namely calcium silicate nanoparticles, is generated on the surface of graphene oxide, so that the modified graphene is obtained; after the modified graphene is mixed with cement, nano calcium silicate can serve as a crystal nucleus in a cement hydration process, further generation and growth of a hydration product, namely calcium silicate, in the cement are promoted, fewer harmful substances such as calcium hydroxide and needle-like substances are generated, and the cement strength is improved; and meanwhile, the modified graphene can be used for effectively solving the problems of agglomeration, not thorough dispersion and the like of an existing graphene addition manner.
Description
Technical field
The invention belongs to technical field of composite materials, particularly relate to the system of a kind of modified graphene and cement composite material thereof
Preparation Method.
Background technology
Cement has the most great meaning as usage amount the widest maximum construction material, the performance improvement of research cement.
Analyze theoretically, cement when dry state mainly by tricalcium silicate (C3S, Ca3SiO5), dicalcium silicate (C2S, Ca2SiO4), aluminic acid
DFP (C3A, Ca3Al2O6) and a small amount of hydrosulphate (potassium salt, sodium salt), Gypsum Fibrosum (CaSO4·2H2O) composition.At cement water
During change, C3First A forms entringite with Gypsum Fibrosum therein reaction；Entringite continues and C3A reaction is converted into single sulfur type aquation
Aluminum sulfate (Afm)；C3S and C2S occurs hydration reaction to form calcium hydroxide (CH) and calcium silicates (C-S-H) gel.These lenticulars
Product together form cement slurry with gel and unhydrated cement granules, intensity and the fragility tool to cement-base composite material
There is conclusive effect.Wherein calcium hydroxide and other spicules are the key factors affecting strength of cement, how to reduce it raw
Become most important.
Along with Graphene prepare, chemical modification and the maturation of dispersion technology, composite based on Graphene grinds in recent years
Study carefully and make much progress.Having the performances such as the electricity of excellence, mechanics, calorifics due to Graphene makes composite based on Graphene past
Toward having many excellent characteristics, thus graphene composite material has been a great concern.According to the literature, there is more scholar
Currently it is devoted to the research of Graphene/cement.But how to solve Graphene dispersion in cement, and Graphene is at cement water
Complex Problem the most intact with hydrated product during change, becomes the current focus be badly in need of and solving.
In the research of Graphene/cement composite material, three kinds of addition manners of current main employing: directly mix, add
Mixing, the modified mixing of Graphene after dispersant.Directly the mode of mixing can not solve Graphene agglomeration traits；Add dispersion
Although agent mode can improve dispersion effect to a certain extent, but does not currently still have preferable dispersion, and the interpolation of dispersant
For the later stage, the impact of hydrated cementitious effect can not be ignored；The mode of Graphene modification can promote that Graphene divides in aqueous
Dissipate, but it still can produce certain impact to later stage hydrated cementitious effect.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of modified graphene and cement composite material thereof
Preparation method, modified graphene prepared by the method can promote the hydration reaction of cement, improves the intensity of composite.
The invention provides the preparation method of a kind of modified graphene, including:
A) graphene oxide water solution, soluble calcium salt being mixed with silicate, under conditions of stirring, heating carries out anti-
Should, obtaining superficial growth has the modified graphene of calcium silicates nano-particle.
Preferably, described step A) particularly as follows:
A1) pH value of graphene oxide water solution is regulated to faintly acid or neutrality, then under conditions of heated and stirred
Add solubility calcium saline solution；
A2) under conditions of heated and stirred, silicate solutions is added to step A1) in the reactant liquor that obtains, then in stirring
Under conditions of heat and react, obtaining superficial growth has the modified graphene of calcium silicates nano-particle.
Preferably, described step A1) particularly as follows:
After graphene oxide water solution is carried out supersound process, then its pH value is regulated to 5～7, then in heated and stirred
Under conditions of add solubility calcium saline solution.
Preferably, in described graphene oxide water solution, the mass concentration of graphene oxide is 0.01%～5%；
Soluble calcium salt in described solubility calcium saline solution is CaCl2And/or Ca (NO3)2；Described soluble calcium salt is molten
In liquid, the mass concentration of soluble calcium salt is 0.1%～20%；
Silicate in described silicate solutions is sodium silicate, potassium silicate and one or more in magnesium silicate；Described silicon
In acid salt solution, the mass concentration of silicate is 0.1%～20%.
Preferably, described step A1) in heated and stirred, step A2) in heated and stirred and stirring rotating speed independently of one another
It is 150～500rpm；
The speed that described solubility calcium saline solution adds is 1～200ml/min；
The speed that described silicate solutions adds is 1～200ml/min.
Preferably, described step A1) in the temperature of heated and stirred be 20 DEG C～80 DEG C；Step A2) in the temperature of heated and stirred
Degree is 20 DEG C～100 DEG C；The temperature of described reaction is 50 DEG C～120 DEG C；The time of described reaction is more than or equal to 24h.
Preferably, soluble calcium salt and graphene oxide in graphene oxide water solution in described solubility calcium saline solution
Mass ratio is 0.1 ‰-10%；Soluble calcium salt and the mol ratio of silicate in silicate solutions in described solubility calcium saline solution
For 1:(0.9～1.2).
Present invention also offers a kind of modified graphene/cement composite material, including modified graphene and cement.
Present invention also offers the preparation method of a kind of modified graphene/cement composite material, including:
B1) modified graphene is mixed with water, obtain modified graphite aqueous solution；
B2) by described modified graphite aqueous solution and cement mixing, modified graphene/cement composite material is obtained.
Preferably, in described modified graphite aqueous solution, the mass concentration of modified graphene is 0.05%～20%；Described
The quality of modified graphite aqueous solution is the 0.01%～5% of cement quality.
The invention provides the preparation method of a kind of modified graphene, including: A) by graphene oxide water solution, solubility
Calcium salt mixes with silicate, heats and react under conditions of stirring, and obtaining superficial growth has changing of calcium silicates nano-particle
Property Graphene.Compared with prior art, the present invention generates cement main component calcium silicates nano-particle in surface of graphene oxide
Obtaining modified graphene, after this modified graphene and cement mixing, nanometer calcium silicates can play crystalline substance in cement hydration process
The generation of hydrated product calcium silicates, growth in core effect, and then promotion cement, minimizing nuisance calcium hydroxide and acicular substance
Generate, improve the intensity of cement；And this modified graphene can effectively solve to reunite present in existing Graphene addition manner,
Disperse the problems such as the most thorough.
Test result indicate that, modified graphene/cement composite material prepared by the present invention can make the fold resistance of cement paste
Can improve 25%, comprcssive strength improves 21%.
Accompanying drawing is invented
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 the modified graphene obtained in the embodiment of the present invention 1；
Fig. 3 is the stereoscan photograph that in the embodiment of the present invention 1, traditional cements after maintenance 7 days is starched only；
Fig. 4 is the stereoscan photograph of the modified graphene/cement composite material in the embodiment of the present invention 1 after maintenance 7 days；
Fig. 5 is the stereoscan photograph that in the embodiment of the present invention 1, traditional cements after maintenance 14 days is starched only；
Fig. 6 is that the scanning electron microscope of the modified graphene/cement composite material in the embodiment of the present invention 1 after maintenance 14 days shines
Sheet.
Detailed description of the invention
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described,
Obviously, described embodiment is only a part of embodiment of the present invention rather than whole embodiments.Based in the present invention
Embodiment, the every other embodiment that those of ordinary skill in the art are obtained under not making creative work premise, all
Belong to the scope of protection of the invention.
The invention provides the preparation method of a kind of modified graphene, including: A) by graphene oxide water solution, solubility
Calcium salt mixes with silicate, heats and reacts, obtain modified graphene under conditions of stirring.
Wherein, the source of all raw materials is not particularly limited by the present invention, for commercially available.
In the present invention, it is preferred to first graphene oxide water solution is carried out supersound process so that it is be in good dispersed
State；Wherein, in described graphene oxide water solution, the mass concentration of graphene oxide is preferably 0.01%～5%, 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, in described graphene oxide water solution, the mass concentration of graphene oxide is preferably 0.5%；At this
In some embodiments that invention provides, in described graphene oxide water solution, the mass concentration of graphene oxide is preferably 0.1%；
In other embodiments that the present invention provides, in described graphene oxide water solution, the mass concentration of graphene oxide is preferably
2%；The graphene oxide that graphene oxide in described graphene oxide water solution is well known to those skilled in the art, and
Without special restriction, the graphene oxide of preferred monolithic rate (within 5 layers) more than 90% in the present invention；Described graphene oxide is excellent
Gating oxidization-reduction mode obtains；Described ultrasonic temperature is preferably 40 DEG C～80 DEG C, more preferably 40 DEG C～60 DEG C, more excellent
Elect 40 DEG C～50 DEG C as, most preferably 40 DEG C～45 DEG C；The described ultrasonic time be preferably 10～60min, more preferably 20～
50min, is further preferably 30～50min.
After supersound process, preferably its pH value is regulated to faintly acid or neutrality, more preferably its pH value is regulated to 5～7, then
Preferably its pH value is regulated to 5.5～6.5；In the present invention, it is preferred to use aqueous slkali regulation pH value；Described aqueous slkali is ability
Aqueous slkali known to field technique personnel, there is no special restriction, in the present invention be preferably ammonia, sodium hydrate aqueous solution with
One or more in potassium hydroxide aqueous solution.
After regulation pH value, under conditions of heated and stirred, add solubility calcium saline solution；The temperature of described heated and stirred is excellent
Electing 20 DEG C～80 DEG C as, more preferably 40 DEG C～80 DEG C, be further preferably 45 DEG C～70 DEG C, is further preferably 50 DEG C～65 DEG C, optimum
Elect 50 DEG C～60 DEG C as；In some embodiments that the present invention provides, the temperature of described heated and stirred is preferably 50 DEG C；At this
In some embodiments of bright offer, the temperature of described heated and stirred is preferably 55 DEG C；In other embodiments that the present invention provides
In, the temperature of described heated and stirred is preferably 60 DEG C；The rotating speed of described heated and stirred is preferably 150～500rpm, more preferably
200～500rpm, it is further preferably 300～500rpm, most preferably 300～400rpm；Solvable in described solubility calcium saline solution
Property the soluble calcium salt that is well known to those skilled in the art of calcium salt, there is no special restriction, the present invention be preferably chlorination
Calcium (CaCl2) and/or calcium nitrate (Ca (NO3)2)；In described solubility calcium saline solution, soluble calcium salt is water-soluble with graphene oxide
The mass ratio of graphene oxide preferably 0.1 ‰～10% in liquid, more preferably 0.5%～5%, be further preferably 2%～3%,
It is preferably 1%～2%；In described solubility calcium saline solution, the mass concentration of soluble calcium salt is preferably 0.1%～50%, more excellent
Elect 0.1%～20% as, be further preferably 5%～20%, be further preferably 8%～15%, most preferably 8%～10%；Described can
Soluble calcium saline solution preferably employs constant pressure funnel and adds；The addition speed of described solubility calcium saline solution be preferably 1～
200ml/min, more preferably 20～150ml/min, be further preferably 50～150ml/min, most preferably 50～100ml/min.
After adding solubility calcium saline solution, under conditions of heated and stirred, add silicate solutions；Described heated and stirred
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 that the present invention provides, the temperature of described heated and stirred is preferably 35
℃；In other embodiments that the present invention provides, the temperature of described heated and stirred is preferably 45 DEG C；Turning of described heated and stirred
Speed be preferably 150～500rpm, more preferably 200～500rpm, be further preferably 300～500rpm, most preferably 300～
400rpm；The silicate that silicate in described silicate solutions is well known to those skilled in the art, there is no special limit
System, is preferably sodium silicate, potassium silicate and one or more in magnesium silicate in the present invention；In described silicate solutions silicate with
In solubility calcium saline solution, the mol ratio of soluble calcium salt is preferably 1:(0.9～1.2), more preferably 1:(1～1.1), optimum
Elect 1:1 as；In described silicate solutions the mass concentration of silicate be preferably 0.1%～50%, more preferably 0.1%～
20%, it is further preferably 2%～20%, most preferably 5%～20%；Described silicate solutions preferably employs constant pressure funnel and adds
Enter；The addition speed of described silicate solutions is preferably 1～200ml/min, and more preferably 20～150ml/min are further preferably
40～100ml/min, most preferably 50～80ml/min；In some embodiments that the present invention provides, described silicate solutions
Addition speed be preferably 50ml/min.
After silicate solutions has been added, then heat and react under conditions of stirring；The speed of described stirring is preferred
Being 150～500rpm, more preferably 200～400rpm, be further preferably 200～300rpm, most preferably 200～250rpm；Institute
The temperature stating reaction is preferably 50 DEG C～120 DEG C, and more preferably 60 DEG C～100 DEG C are further preferably 60 DEG C～90 DEG C, most preferably
60 DEG C～80 DEG C；The time of described reaction is preferably greater than equal to 24h, and more preferably 24～60h, be further preferably 24～50h,
It is preferably 24～48h；In some embodiments that the present invention provides, the temperature of described reaction is preferably 80 DEG C, described reaction
Time is preferably 24h；In some embodiments that the present invention provides, the temperature of described reaction is preferably 70 DEG C, described reaction
Time is preferably 36h；In other embodiments that the present invention provides, the temperature of described reaction is preferably 60 DEG C, described reaction
Time be preferably 48h.
After reaction terminates, preferably washing with water, remove saline solution, obtaining superficial growth has the modification of calcium silicates nano-particle
Graphene.
The present invention generates cement main component calcium silicates nano-particle 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 promotes water
The generation of hydrated product calcium silicates, growth in mud, reduce nuisance calcium hydroxide and the generation of acicular substance, improves the strong of cement
Degree；And this modified graphene can effectively solve to reunite present in existing Graphene addition manner, disperse the problems such as the most thorough.
Present invention also offers a kind of modified graphene/cement composite material, including above-mentioned modified graphene and cement；Its
In, the cement that described cement is well known to those skilled in the art, there is no special restriction, in the present invention be preferably 32.5,
32.5R, 42.5,42.5R, alumina cement and one or more in sulphate aluminium cement.
Present invention also offers the preparation method of a kind of above-mentioned modified graphene/cement composite material, including B1) by above-mentioned
Modified graphene mixes with water, obtains modified graphite aqueous solution；B2) by described modified graphite aqueous solution and cement mixing,
Obtain modified graphene/cement composite material.
In the present invention, modified graphene concentration of polymer solution be preferably 0.05%～20%, more preferably 0.1%～
10%, most preferably 0.5%～5%；The Functionality, quality and appealing design of modified graphene solution elects the 0.01%～5% of cement quality as, more excellent
Elect 0.05%～3% as, most preferably 0.1%～2%；The cement that described cement is well known to those skilled in the art, and
Without special restriction, the present invention is preferably 32.5,32.5R, 42.5,42.5R, alumina cement and in sulphate aluminium cement
Plant or multiple.Modified graphene adds in the way of aqueous solution during cement mixing, and whipping procedure according to national standard is
Can.Stirring terminates, and obtains modified graphene/cement composite material, puts into maintenance in mould.
The present invention generates cement main component calcium silicates nano-particle 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 promotes water
The generation of hydrated product calcium silicates in mud, reduces nuisance calcium hydroxide and the generation of acicular substance, improves the intensity of cement；And
And this modified graphene can effectively solve to reunite present in existing Graphene addition manner, disperse the problems such as the most thorough.
In order to further illustrate the present invention, a kind of modified graphene present invention provided below in conjunction with embodiment and water thereof
The preparation method of mud composite is described in detail.
Reagent used in following example is commercially available.
Embodiment 1
1.1 take 1000g graphene oxide water solution, and content 0.5% carries out supersound process, ultrasonic 30min at 40 DEG C, surpasses
Acoustic frequency 50Hz；
1.2 add the NaOH solution of 5%, and regulation pH value of solution is 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
Experimental temperature 60 DEG C, rotating speed 300rpm；
1.4 use constant pressure funnel to be slowly added to and the 10% of calcium ion same molar with the speed of 50ml/min
Na2SiO3Solution, Control release temperature 35 DEG C, rotating speed 300rpm；
1.5 were warming up to 80 DEG C, with continuously stirred 24 hours of 200rpm rotating speed；
The solution with water obtained in 1.5 is cleaned by 1.6, removes saline solution, obtains modified graphite aqueous solution.It is dissolved in
Water is made into the aqueous solution that mass concentration is 2%；
1.7 join in 42.5R cement according to the adding proportion of 1% that modified graphene Mass Solution is cement quality,
Prepare modified graphene cement paste, after maintenance, carry out Morphology analysis.And synchronization prepares traditional cements and only starches (i.e. without changing
The cement paste of property Graphene), it is analyzed with it.
Utilize scanning electron microscope that graphene oxide used in embodiment 1 is analyzed, obtain its scanning electron microscope
Photo, as shown in Figure 1.
Utilize scanning electron microscope that the modified graphene obtained in embodiment 1 is analyzed, obtain its scanning electron microscope
Photo, as shown in Figure 2.
Utilize scanning electron microscope clean to the cement of the modified graphene/cement composite material after maintenance in embodiment 1
Slurry is only starched with traditional cements and to be analyzed, and obtains its stereoscan photograph, as shown in Fig. 3～Fig. 6, after wherein Fig. 3 is maintenance 7 days
The stereoscan photograph only starched of traditional cements；Fig. 4 is that the cement of the modified graphene/cement composite material after maintenance 7 days is clean
The stereoscan photograph of slurry；Fig. 5 is the stereoscan photograph that the traditional cements after maintenance 14 days is starched only；After Fig. 6 is maintenance 14 days
The stereoscan photograph of cement paste of modified graphene/cement composite material.
From Fig. 3～Fig. 6, after maintenance 7 days, Microcosmic Comparative Analysis finds, traditional cements is only starched section and be there is more pin
Shape material, this will produce considerable influence to strength of cement, and the cement paste section needle-like of modified graphene/cement composite material
Material is the most less, combines the tightst between material.Maintenance 14 day data, result is consistent.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% carries out supersound process, ultrasonic 30min at 40 DEG C, surpasses
Acoustic frequency 50Hz；
2.2 add the ammonia spirit of 1%, and regulation pH value of solution is 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
Experimental temperature 50 DEG C, rotating speed 400rpm；
2.4 use constant pressure funnel to be slowly added to and the 10% of calcium ion same molar with the speed of 50ml/min
Na2SiO3Solution, Control release temperature 45 C, rotating speed 400rpm；
2.5 were warming up to 70 DEG C, with continuously stirred 36 hours of 250rpm rotating speed；
The solution with water obtained in 2.5 is cleaned by 2.6, removes saline solution, obtains modified graphite aqueous solution.It is dissolved in
Water is made into the aqueous solution that mass concentration is 1%；
2.7 join in 42.5R cement according to the adding proportion of 0.5% that modified graphene solution is cement quality, system
Standby modified graphene cement paste, prepares 40*40*160mm cement mortar according to the proportioning of standard cement mortar, carries out after maintenance
Performance test.And synchronization prepares traditional cements and only starch, it is analyzed with it.Microscopic appearance result is consistent with embodiment 1.
Macro-mechanical property is shown in Table 1, data analysis from table 1, and the mechanical property of modified graphene/cement composite material obtains
To promoting largely, the change with microscopic appearance coincide.
The fracture resistance analysis result of cement paste in table 1 embodiment 2
Embodiment 3
3.1 take 1000g graphene oxide water solution, content 2%, carry out supersound process, ultrasonic 50min, surpass at 45 DEG C
Acoustic frequency 50Hz；
3.2 add the KOH solution of 2%, and regulation pH value of solution is 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
Test temperature 55 DEG C, rotating speed 300rpm；
3.4 use constant pressure funnel to be slowly added to and the 8% of calcium ion same molar with the speed of 50ml/min
Na2SiO3Solution, Control release temperature 35 DEG C, rotating speed 300rpm；
3.5 were warming up to 60 DEG C, with continuously stirred 48 hours of 200rpm rotating speed；
The solution with water obtained in 3.5 is cleaned by 3.6, removes saline solution, obtains modified graphite aqueous solution.It is dissolved in
Water is made into the aqueous solution that mass concentration is 0.5%；
3.7 join in 42.5 cement according to the adding proportion of 2% that modified graphene solution is cement quality, according to mark
The proportioning of quasi-cement mortar prepares 40*40*160mm cement mortar, carries out performance test after maintenance.And synchronization prepares traditional cements
Clean slurry, is analyzed with it, and both performance test data are shown in Table 2.
The compressive property analysis result of cement paste in table 2 embodiment 3
Claims (10)
1. the preparation method of a modified graphene, it is characterised in that including:
A) graphene oxide water solution, soluble calcium salt are mixed with silicate, heat under conditions of stirring and react,
The modified graphene of calcium silicates nano-particle is had to superficial growth.
Preparation method the most according to claim 1, it is characterised in that described step A) particularly as follows:
A1) pH value of graphene oxide water solution is regulated to faintly acid or neutrality, then add under conditions of heated and stirred
Solubility calcium saline solution；
A2) under conditions of heated and stirred, silicate solutions is added to step A1) in the reactant liquor that obtains, then the bar in stirring
Under part, heating is reacted, and obtaining superficial growth has the modified graphene of calcium silicates nano-particle.
Preparation method the most according to claim 2, it is characterised in that described step A1) particularly as follows:
After graphene oxide water solution is carried out supersound process, then its pH value is regulated to 5～7, then at the bar of heated and stirred
Solubility calcium saline solution is added under part.
Preparation method the most according to claim 2, it is characterised in that graphene oxide in described graphene oxide water solution
Mass concentration be 0.01%～5%；
Soluble calcium salt in described solubility calcium saline solution is CaCl2And/or Ca (NO3)2；In described solubility calcium saline solution
The mass concentration of soluble calcium salt is 0.1%～20%；
Silicate in described silicate solutions is sodium silicate, potassium silicate and one or more in magnesium silicate；Described silicate
In solution, the mass concentration of silicate is 0.1%～20%.
Preparation method the most according to claim 2, it is characterised in that described step A1) in heated and stirred, step A2) in
Heated and stirred is each independently 150～500rpm with the rotating speed of stirring；
The speed that described solubility calcium saline solution adds is 1～200ml/min；
The speed that described silicate solutions adds is 1～200ml/min.
Preparation method the most according to claim 2, it is characterised in that described step A1) in the temperature of heated and stirred be 20
DEG C～80 DEG C；Step A2) in the temperature of heated and stirred be 20 DEG C～100 DEG C；The temperature of described reaction is 50 DEG C～120 DEG C；Institute
State the time of reaction more than or equal to 24h.
Preparation method the most according to claim 2, it is characterised in that in described solubility calcium saline solution soluble calcium salt with
In graphene oxide water solution, the mass ratio of graphene oxide is 0.1 ‰～10%；Solubility in described solubility calcium saline solution
Calcium salt is 1:(0.9～1.2 with the mol ratio of silicate in silicate solutions).
8. modified graphene/cement composite material, it is characterised in that include prepared by claim 1～7 any one
Modified graphene and cement.
9. the preparation method of modified graphene/cement composite material, it is characterised in that including:
B1) modified graphene prepared by any one of claim 1～7 is mixed with water, obtain modified graphite aqueous solution；
B2) by described modified graphite aqueous solution and cement mixing, modified graphene/cement composite material is obtained.
Preparation method the most according to claim 9, it is characterised in that modified graphite in described modified graphite aqueous solution
The mass concentration of alkene is 0.05%～20%；Quality is cement quality 0.01%～the 5% of described modified graphite aqueous solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610707671.0A CN106315573B (en) | 2016-08-23 | 2016-08-23 | The preparation method of modified graphene and its cement composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610707671.0A CN106315573B (en) | 2016-08-23 | 2016-08-23 | The preparation method of modified graphene and its cement composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106315573A true CN106315573A (en) | 2017-01-11 |
| CN106315573B CN106315573B (en) | 2019-02-12 |
Family
ID=57742190
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610707671.0A Active CN106315573B (en) | 2016-08-23 | 2016-08-23 | The preparation method of modified graphene and its cement composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106315573B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| CN110790528A (en) * | 2019-11-28 | 2020-02-14 | 北京服装学院 | Preparation method and application of micro-nano crystal nucleus composite material |
| CN110981298A (en) * | 2019-11-28 | 2020-04-10 | 浙江大学 | Graphene oxide-nano mineral enhanced geopolymer material and preparation method thereof |
| CN112479625A (en) * | 2020-11-06 | 2021-03-12 | 安徽工业大学 | Preparation method of graphene modified cement and product thereof |
| CN112794318A (en) * | 2021-01-28 | 2021-05-14 | 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 |
| CN114441573A (en) * | 2021-12-29 | 2022-05-06 | 广西科技大学 | Preparation method of novel scanning electron microscope sample convenient for observing morphology of graphene-regulated cement hydrated crystal |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104803625A (en) * | 2014-11-04 | 2015-07-29 | 江苏苏博特新材料股份有限公司 | Nano-suspension concrete early strength accelerator and preparation method thereof |
| CN104876204A (en) * | 2015-05-21 | 2015-09-02 | 东南大学 | Method for modifying graphene oxide |
-
2016
- 2016-08-23 CN CN201610707671.0A patent/CN106315573B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104803625A (en) * | 2014-11-04 | 2015-07-29 | 江苏苏博特新材料股份有限公司 | Nano-suspension concrete early strength accelerator and preparation method thereof |
| CN104876204A (en) * | 2015-05-21 | 2015-09-02 | 东南大学 | Method for modifying graphene oxide |
Non-Patent Citations (3)
| Title |
|---|
| FAKHIM BABAK ET AL;: "Preparation and Mechanical Properties of Graphene Oxide: Cement Nanocomposites", 《THE SCIENTIFIC WORLD JOURNAL》 * |
| MEHDI MEHRALI ET AL;: "Synthesis, Mechanical Properties, and in Vitro Biocompatibility with Osteoblasts of Calcium Silicate−Reduced Graphene Oxide Composites", 《ACS APPL.MATER.INTERFACES》 * |
| 刘琼等: "石墨烯和碳纳米管水泥基复合材料研究进展", 《混凝土与水泥制品》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110790528A (en) * | 2019-11-28 | 2020-02-14 | 北京服装学院 | Preparation method and application of micro-nano crystal nucleus composite material |
| CN110981298A (en) * | 2019-11-28 | 2020-04-10 | 浙江大学 | Graphene oxide-nano mineral enhanced geopolymer material and preparation method thereof |
| 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 |
| CN112479625A (en) * | 2020-11-06 | 2021-03-12 | 安徽工业大学 | Preparation method of graphene modified cement and product thereof |
| CN112479625B (en) * | 2020-11-06 | 2022-04-12 | 安徽工业大学 | Preparation method of graphene modified cement and product thereof |
| CN112794318A (en) * | 2021-01-28 | 2021-05-14 | 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 |
| CN114441573A (en) * | 2021-12-29 | 2022-05-06 | 广西科技大学 | Preparation method of novel scanning electron microscope sample convenient for observing morphology of graphene-regulated cement hydrated crystal |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106315573B (en) | 2019-02-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106315573A (en) | Preparation method of modified graphene and cement composite material thereof | |
| CN101671848B (en) | Preparation method of high length-diameter ratio anhydrous calcium sulfate whisker | |
| CN110156367A (en) | By the method for Industrial Solid Waste wet-milling preparation nanometer C-S-H gel early strength agent | |
| CN107954623B (en) | Preparation method for in-situ growth of nano particles on surface of solid waste | |
| CN104291350B (en) | A kind of technique of K-feldspar powder hydro-thermal alkaline process synthesis analcime | |
| CN109650398A (en) | A kind of hydrated calcium silicate early strength agent and preparation method thereof | |
| CN107723800A (en) | The method of Microwave-assisted synthesis calcium sulfate crystal whiskers in inorganic salt solution | |
| CN106745161B (en) | The method of nanometer calcium sulfate and calcium sulfate crystal whiskers is prepared in a kind of alcohol-water mixed system | |
| CN105883886B (en) | A kind of method that high-purity αsemiwatergypsum powder is prepared using salt chemical engineering accessory substance | |
| CN107082433B (en) | A kind of eakleite and its preparation method and application | |
| CN105780121B (en) | A kind of method using flyash as Material synthesis tobermorite whisker | |
| CN104790024A (en) | Preparation method for aragonite calcium carbonate whisker with high length-diameter ratio | |
| CN101311372B (en) | Low-temperature molten salt thermal inversion preparation method of aporate-crystal antifungin whiskers | |
| CN101348937A (en) | Preparation of high length-diameter ratio magnesium hydroxide sulfate hydrate whisker | |
| CN104480523A (en) | Improved method for preparing superfine high length-diameter-ratio anhydrous calcium sulfate crystal whiskers by using hydrothermal process | |
| CN102618931A (en) | Method for preparing calcium sulfate whiskers | |
| CN103774208A (en) | Green hydrothermal synthesis method for non-porous high-crystallized magnesium borate nanowhisker | |
| CN101319378A (en) | Preparation method of alkali type magnesium sulfate crystal whisker | |
| CN102674380A (en) | Method for synthesizing tobermorite whiskers by sodium silicate | |
| CN102618094B (en) | Method for grafting graphene oxide on biphenyl thermotropic liquid crystal compound | |
| CN106517267A (en) | Preparation method of basic magnesium sulfate whiskers | |
| CN104402006A (en) | Method for preparing meso-porous silica material by using silicon micro-powder | |
| CN110526272A (en) | A kind of micro-nano structure CeCO3The preparation process of OH | |
| CN104988576B (en) | The preparation method of alkali magnesium sulfate crystal whisker | |
| CN114921851B (en) | Calcium carbonate whisker prepared by carbide slag carbonization and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |