CN104529382A - Graphene/aluminosilicate polymer composite material prepared through graphene oxide in-situ reduction and preparation method thereof - Google Patents
Graphene/aluminosilicate polymer composite material prepared through graphene oxide in-situ reduction and preparation method thereof Download PDFInfo
- Publication number
- CN104529382A CN104529382A CN201510018448.0A CN201510018448A CN104529382A CN 104529382 A CN104529382 A CN 104529382A CN 201510018448 A CN201510018448 A CN 201510018448A CN 104529382 A CN104529382 A CN 104529382A
- Authority
- CN
- China
- Prior art keywords
- graphene
- graphene oxide
- aluminum silicate
- silicate polymer
- matrix material
- 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
Abstract
The invention relates to a graphene/aluminosilicate polymer composite material prepared through graphene oxide in-situ reduction and a preparation method of the graphene/aluminosilicate polymer composite material. The graphene/aluminosilicate polymer composite material and the preparation method aim at solving the problems that an existing aluminosilicate polymer is low in mechanical performance and poor in tenacity, and due to the fact that graphene powder is directly added, agglomeration dispersity is poor. The graphene/aluminosilicate polymer composite material prepared through the graphene oxide in-situ reduction is prepared through graphene oxide suspension liquid, alkali excitation solutions and aluminosilicate powder. The method comprises the steps that (1) the graphene oxide suspension liquid is prepared; (2) the alkali excitation solutions are prepared; (3) graphene oxide/alkali excitation mixed liquor is prepared; (4) graphene/aluminosilicate polymer sizing agents are prepared; (5) curing molding is carried out. The method is used for preparing the graphene/aluminosilicate polymer composite material. The preparation method is easy and convenient, low in cost, capable of achieving large-scale preparation and wide in application range.
Description
Technical field
The present invention relates to a kind of graphene/aluminum silicate polymer matrix material utilizing graphene oxide in-situ reducing to prepare and preparation method thereof.
Background technology
The environmental protection of aluminosilicate polymer material, preparation temperature is low, technique is simple, energy consumption is low, and have that density is low, cost is low, the advantage such as high temperature resistant, heat-resisting and flame retardant properties is good, be widely used in building and aviation field.But compare with traditional cement, the factors such as itself intrinsic fragility, poor toughness, physical strength are low seriously limit its range of application.Prepare aluminosilicate polymer based composites at present and mainly concentrate on particle and fiber reinforcement two kinds of forms, this study group obtains related ends all.But in existing fibre reinforcement, fiber and the simple mechanical bond of basal body interface change it from nanoscale and combine essence, and after pyroprocessing, the mismatch of fiber and basal body interface thermal expansivity again limit its whole structure and application conditions; Particulates reinforcements and matrix bonding state well, but need Granular composite even.
Graphene is a kind of monoatomic layer two dimensional crystal be connected to form with sp2 hydridization by carbon atom, has excellent mechanics and electric property, is widely used in pottery and polymer matrix composites as nanometer reinforcement.Compared to Graphene, surface of graphene oxide contains a large amount of oxy radicals and shows stronger wetting ability and easily disperse in an aqueous medium, there is good wettability and surfactivity, Graphene can be reduced to, series of advantages such as there is process stabilizing, easily process, cost is low in specific environment.By graphene oxide application in the composite, very important effect has been played improving in the over-all properties such as calorifics, electricity, mechanics of material.Current experience shows, Graphene is directly made an addition in the process of aluminosilicate polymer the shortcoming that there is Graphene reunion, bad dispersibility; And the research report made an addition to by graphene oxide in aluminosilicate polymer is less.
Summary of the invention
The present invention be to solve that existing aluminosilicate polymer mechanical property is low, poor toughness and directly add the problem of graphene powder reunion bad dispersibility, and provide a kind of graphene/aluminum silicate polymer matrix material utilizing graphene oxide in-situ reducing to prepare and preparation method thereof.
A kind of graphene/aluminum silicate polymer matrix material utilizing graphene oxide in-situ reducing to prepare of the present invention is prepared from by graphene oxide suspension, alkali-activated carbonatite solution and aluminosilicate powder;
Described graphene oxide suspension is mixed by graphene oxide powder and deionized water; The quality of described graphene oxide powder and the volume ratio of deionized water are (1 ~ 20) mg:1mL;
The silicon sol that described alkali-activated carbonatite solution is 25% ~ 45% by potassium hydroxide and mass concentration mixes; In described potassium hydroxide, potassium element and mass concentration are the mol ratio of element silicon in the silicon sol of 25% ~ 45% is 1:(0.5 ~ 1.5);
Graphene oxide powder in described graphene oxide suspension and the mass ratio of aluminosilicate powder are (0.01 ~ 0.15): 100;
In described aluminosilicate powder, the mol ratio of element silicon and aluminium element is 1:1;
In the described graphene/aluminum silicate polymer matrix material utilizing graphene oxide in-situ reducing to prepare, the mol ratio of element silicon and aluminium element is (1 ~ 4): 1.
The preparation method of a kind of graphene/aluminum silicate polymer matrix material utilizing graphene oxide in-situ reducing to prepare of the present invention carries out according to the following steps:
One, the preparation of graphene oxide suspension: graphene oxide powder ultrasonic is scattered in deionized water, supersound process 2h ~ 6h, obtains brown color graphene oxide suspension; The quality of described graphene oxide powder and the volume ratio of deionized water are (1 ~ 20) mg:1mL;
Two, the preparation of alkali-activated carbonatite solution: potassium hydroxide being joined mass concentration is in the silicon sol of 25% ~ 45%, magnetic agitation mixing 20h ~ 80h, obtains alkali-activated carbonatite solution; In described potassium hydroxide, potassium element and mass concentration are the mol ratio of element silicon in the silicon sol of 25% ~ 45% is 1:(0.5 ~ 1.5);
The preparation of three, graphene oxide/alkali-activated carbonatite mixed solution: brown color graphene oxide suspension step one obtained joins in the alkali-activated carbonatite solution that step 2 obtains, after magnetic agitation mixing 10min ~ 30min, be in-situ reducing 0.01h ~ 72h under the condition of 20 DEG C ~ 80 DEG C in temperature, obtain graphene oxide/alkali-activated carbonatite mixed solution;
Four, the preparation of graphene/aluminum silicate polymer slurry: graphene oxide step 3 obtained/alkali-activated carbonatite mixed solution is placed in the ice-water bath that temperature is 0 DEG C ~ 5 DEG C, add aluminosilicate powder again, ultrasonic and mechanical stirring 25min ~ 45min, obtain graphene/aluminum silicate polymer slip, then add deionized water, be adjusted to graphene/aluminum silicate polymer slip at shearing rate 60S
-1~ 80S
-1time viscosity be 150mPas ~ 500mPas, obtain graphene/aluminum silicate polymer slurry; In described aluminosilicate powder, the mol ratio of element silicon and aluminium element is 1:1;
Five, curing molding: graphene/aluminum silicate polymer slurry step 4 obtained is poured in mould, and be placed in exhaust in vacuum chamber, then being placed in temperature is maintenance 24h ~ 240h in the loft drier of 40 DEG C ~ 80 DEG C, obtains the graphene/aluminum silicate polymer matrix material utilizing graphene oxide in-situ reducing to prepare; In the described graphene/aluminum silicate polymer matrix material utilizing graphene oxide in-situ reducing to prepare, the mol ratio of element silicon and aluminium element is (1 ~ 4): 1;
Described in the powder of graphene oxide described in step one and step 4, the mass ratio of aluminosilicate powder is (0.01 ~ 0.15): 100.
The invention has the beneficial effects as follows:
The graphene/aluminum silicate polymer matrix material that the present invention prepares, take graphene oxide as raw material, utilize the wetting ability of surface of graphene oxide oxygen-containing functional group, can be easier to be scattered in water base silicate solutions, carry out reaction in－situ with aluminosilicate polymer alkali-activated carbonatite solution, and then polymerization obtains required matrix material simultaneously; Owing to there is bonding action between alkali-activated carbonatite solution and graphene oxide, graphene oxide is not easy to reunite, and in aluminosilicate polymer slurry, have dispersed and consistency preferably.After curing molding, obtain graphene/aluminum silicate polymer matrix material, technique is simple, and reducing degree is controlled, and obtained matrix material machinery performance is good, and density is about 1.1g/cm
3~ 1.5g/cm
3between, fracture toughness property can arrive 0.12MPam
1/2~ 0.21MPam
1/2bending strength can reach 10 ~ 20MPa, be improved compared to un-added body material, Young's modulus can reach 7GPa ~ 8GPa, the controlled easy adjustment of reducing degree of graphene/aluminum silicate polymer matrix material Graphene prepared by the present invention, solves the problem of Graphene bad dispersibility, easily reunion in aluminosilicate polymer; Preparation is simple, good manufacturability, and the Graphene after reduction is evenly distributed, good dispersity, and intensity is high, good toughness; And make aluminosilicate polymer material have more standby structure-function integration potential, preparation condition energy-conserving and environment-protective, can be used for structured material and the use of induction original paper.
Accompanying drawing explanation
Fig. 1 is the FT-IR comparison diagram of graphene oxide powder in Graphene in embodiment one step 3 in graphene oxide/alkali-activated carbonatite mixed solution after reduction and step one, wherein 1 is the FT-IR curve of graphene oxide powder in step one, and 2 is the FT-IR curve of Graphene in embodiment one step 3 in graphene oxide/alkali-activated carbonatite mixed solution after reduction;
Fig. 2 is the graphene/aluminum silicate polymer matrix material fracture SEM figure utilizing graphene oxide in-situ reducing to prepare that embodiment one obtains;
Fig. 3 is the XRD figure of the graphene/aluminum silicate polymer matrix material utilizing graphene oxide in-situ reducing to prepare that embodiment one obtains; Wherein 1 is quartzy phase, and A is the XRD curve of graphene/aluminum silicate polymer matrix material, and B is the XRD curve of metakaolin.
Embodiment
Embodiment one: a kind of graphene/aluminum silicate polymer matrix material utilizing graphene oxide in-situ reducing to prepare of present embodiment is prepared from by graphene oxide suspension, alkali-activated carbonatite solution and aluminosilicate powder;
Described graphene oxide suspension is mixed by graphene oxide powder and deionized water; The quality of described graphene oxide powder and the volume ratio of deionized water are (1 ~ 20) mg:1mL;
The silicon sol that described alkali-activated carbonatite solution is 25% ~ 45% by potassium hydroxide and mass concentration mixes; In described potassium hydroxide, potassium element and mass concentration are the mol ratio of element silicon in the silicon sol of 25% ~ 45% is 1:(0.5 ~ 1.5);
Graphene oxide powder in described graphene oxide suspension and the mass ratio of aluminosilicate powder are (0.01 ~ 0.15): 100;
In described aluminosilicate powder, the mol ratio of element silicon and aluminium element is 1:1;
In the described graphene/aluminum silicate polymer matrix material utilizing graphene oxide in-situ reducing to prepare, the mol ratio of element silicon and aluminium element is (1 ~ 4): 1.
Deionized water described in present embodiment is neutral.
The powder of aluminosilicate described in present embodiment is a kind of or wherein several mixture in metakaolin, flyash, volcanic ash, polynite and illite clay etc., is mixed by any ratio for during mixture.
Embodiment two: present embodiment and embodiment one unlike: the quality of described graphene oxide powder and the volume ratio of deionized water are 16.7mg:1mL.Other are identical with embodiment one.
Embodiment three: present embodiment and embodiment one or two unlike: in described potassium hydroxide, potassium element and mass concentration are the mol ratio of element silicon in the silicon sol of 25% ~ 45% is 1:1.Other are identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three unlike: in the described graphene/aluminum silicate polymer matrix material utilizing graphene oxide in-situ reducing to prepare, the mol ratio of element silicon and aluminium element is 2:1.Other are identical with one of embodiment one to three.
Embodiment five: the preparation method of a kind of graphene/aluminum silicate polymer matrix material utilizing graphene oxide in-situ reducing to prepare of present embodiment carries out according to the following steps:
One, the preparation of graphene oxide suspension: graphene oxide powder ultrasonic is scattered in deionized water, supersound process 2h ~ 6h, obtains brown color graphene oxide suspension; The quality of described graphene oxide powder and the volume ratio of deionized water are (1 ~ 20) mg:1mL;
Two, the preparation of alkali-activated carbonatite solution: potassium hydroxide being joined mass concentration is in the silicon sol of 25% ~ 45%, magnetic agitation mixing 20h ~ 80h, obtains alkali-activated carbonatite solution; In described potassium hydroxide, potassium element and mass concentration are the mol ratio of element silicon in the silicon sol of 25% ~ 45% is 1:(0.5 ~ 1.5);
The preparation of three, graphene oxide/alkali-activated carbonatite mixed solution: brown color graphene oxide suspension step one obtained joins in the alkali-activated carbonatite solution that step 2 obtains, after magnetic agitation mixing 10min ~ 30min, be in-situ reducing 0.01h ~ 72h under the condition of 20 DEG C ~ 80 DEG C in temperature, obtain graphene oxide/alkali-activated carbonatite mixed solution;
Four, the preparation of graphene/aluminum silicate polymer slurry: graphene oxide step 3 obtained/alkali-activated carbonatite mixed solution is placed in the ice-water bath that temperature is 0 DEG C ~ 5 DEG C, add aluminosilicate powder again, ultrasonic and mechanical stirring 25min ~ 45min, obtain graphene/aluminum silicate polymer slip, then add deionized water, be adjusted to graphene/aluminum silicate polymer slip at shearing rate 60S
-1~ 80S
-1time viscosity be 150mPas ~ 500mPas, obtain graphene/aluminum silicate polymer slurry; In described aluminosilicate powder, the mol ratio of element silicon and aluminium element is 1:1;
Five, curing molding: graphene/aluminum silicate polymer slurry step 4 obtained is poured in mould, and be placed in exhaust in vacuum chamber, then being placed in temperature is maintenance 24h ~ 240h in the loft drier of 40 DEG C ~ 80 DEG C, obtains the graphene/aluminum silicate polymer matrix material utilizing graphene oxide in-situ reducing to prepare; In the described graphene/aluminum silicate polymer matrix material utilizing graphene oxide in-situ reducing to prepare, the mol ratio of element silicon and aluminium element is (1 ~ 4): 1;
Described in the powder of graphene oxide described in step one and step 4, the mass ratio of aluminosilicate powder is (0.01 ~ 0.15): 100.
Deionized water described in present embodiment is neutral.
The powder of aluminosilicate described in present embodiment is a kind of or wherein several mixture in metakaolin, flyash, volcanic ash, polynite and illite clay etc., is mixed by any ratio for during mixture.
Embodiment six: present embodiment and embodiment five unlike: the quality of the powder of graphene oxide described in step one and the volume ratio of deionized water are 16.7mg:1mL.Other are identical with embodiment five.
Embodiment seven: present embodiment and embodiment five or six unlike: in potassium hydroxide described in step 2, potassium element and mass concentration are the mol ratio of element silicon in the silicon sol of 25% ~ 45% is 1:1.Other are identical with embodiment one or two.
Embodiment eight: one of present embodiment and embodiment five to seven unlike: be in-situ reducing 72h under the condition of 60 DEG C in temperature in step 3.Other are identical with one of embodiment five to seven.
Embodiment nine: one of present embodiment and embodiment five to eight unlike: being placed in temperature in step 5 is maintenance 168h in the loft drier of 60 DEG C.Other are identical with one of embodiment five to eight.
Embodiment ten: one of present embodiment and embodiment five to eight unlike: in the graphene/aluminum silicate polymer matrix material utilizing graphene oxide in-situ reducing to prepare described in step 5, the mol ratio of element silicon and aluminium element is 2:1.Other are identical with one of embodiment five to nine.
Beneficial effect of the present invention is verified by following examples:
Embodiment one: a kind of preparation method of the graphene/aluminum silicate polymer matrix material utilizing graphene oxide in-situ reducing to prepare carries out according to the following steps:
One, the preparation of graphene oxide suspension: be scattered in deionized water by graphene oxide powder ultrasonic, supersound process 5h, obtains brown color graphene oxide suspension; The quality of described graphene oxide powder and the volume ratio of deionized water are 16.7mg:1mL;
Two, the preparation of alkali-activated carbonatite solution: potassium hydroxide being joined mass concentration is in the silicon sol of 40%, magnetic agitation mixing 20h ~ 80h, obtains alkali-activated carbonatite solution; In described potassium hydroxide, potassium element and mass concentration are the mol ratio of element silicon in the silicon sol of 40% is 1:1;
The preparation of three, graphene oxide/alkali-activated carbonatite mixed solution: brown color graphene oxide suspension step one obtained joins in the alkali-activated carbonatite solution that step 2 obtains, after magnetic agitation mixing 15min, be in-situ reducing 72h under the condition of 60 DEG C in temperature, obtain graphene oxide/alkali-activated carbonatite mixed solution;
Four, the preparation of graphene/aluminum silicate polymer slurry: graphene oxide step 3 obtained/alkali-activated carbonatite mixed solution is placed in the ice-water bath that temperature is 0 DEG C ~ 5 DEG C, add metakaolin powder again, ultrasonic and mechanical stirring 25min ~ 45min, obtain graphene/aluminum silicate polymer slip, then add deionized water, be adjusted to graphene/aluminum silicate polymer slip at shearing rate 60S
-1~ 80S
-1time viscosity be 150mPas ~ 500mPas, obtain graphene/aluminum silicate polymer slurry; Kaolin is calcined 2h and is obtained by described metakaolin powder under temperature is 800 DEG C of conditions; In described metakaolin powder, the mol ratio of element silicon and aluminium element is 1:1;
Five, curing molding: graphene/aluminum silicate polymer slurry step 4 obtained is poured in mould, and be placed in exhaust in vacuum chamber, then being placed in temperature is maintenance 168h in the loft drier of 60 DEG C, obtains the graphene/aluminum silicate polymer matrix material utilizing graphene oxide in-situ reducing to prepare; In the described graphene/aluminum silicate polymer matrix material utilizing graphene oxide in-situ reducing to prepare, the mol ratio of element silicon and aluminium element is 2:1;
Described in the powder of graphene oxide described in step one and step 4, the mass ratio of metakaolin powder is 0.1:100.
Fig. 1 is the FT-IR comparison diagram of graphene oxide powder in Graphene in embodiment one step 3 in graphene oxide/alkali-activated carbonatite mixed solution after reduction and step one, wherein 1 is the FT-IR curve of graphene oxide powder in step one, and 2 is the FT-IR curve of Graphene in embodiment one step 3 in graphene oxide/alkali-activated carbonatite mixed solution after reduction; As can be seen from the change of Tu Zhong functional group, graphene oxide is reduced in alkali-activated carbonatite solution.
Fig. 2 is the graphene/aluminum silicate polymer matrix material fracture SEM figure utilizing graphene oxide in-situ reducing to prepare that embodiment one obtains; From figure, sample incision position can see that fracture is uneven with aluminosilicate polymer matrix in conjunction with fine and equally distributed Graphene, have corner angle to rise and fall comparatively mostly to be add Graphene after the effect that produces.
Fig. 3 is the XRD figure of the graphene/aluminum silicate polymer matrix material utilizing graphene oxide in-situ reducing to prepare that embodiment one obtains; Wherein 1 is quartzy phase, and A is the XRD curve of graphene/aluminum silicate polymer matrix material, and B is the XRD curve of metakaolin; As can be seen from the figure there is the feature amorphous peak of aluminosilicate polymer near 28 °, illustrate that the present invention utilizes graphene oxide in-situ reducing to prepare graphene/aluminum silicate polymer matrix material.The impurity that wherein peak of quartzy phase comes from raw material metakaolin has neither part nor lot in building-up reactions.
In the graphene/aluminum silicate polymer matrix material that what the present embodiment obtained utilize graphene oxide in-situ reducing to prepare, in graphene oxide and aluminosilicate polymer based composites, metakaolin mass ratio is 1%, and fracture toughness property is (0.11 ~ 0.17) MPa m
1/2, bending strength is (12.3 ~ 13.3) MPa, and Young's modulus is (5.8 ~ 6.2) GPa.
Embodiment two: the present embodiment and embodiment one difference are: the quality of the powder of graphene oxide described in step one and the volume ratio of deionized water are 7.5mg:1mL; Brown color graphene oxide suspension step one obtained in step 3 joins in the alkali-activated carbonatite solution that step 2 obtains, and after magnetic agitation mixing 15min, is in-situ reducing 5min under the condition of 25 DEG C in temperature.Other are identical with embodiment one.
In the graphene/aluminum silicate polymer matrix material that what the present embodiment obtained utilize graphene oxide in-situ reducing to prepare, in graphene oxide and aluminosilicate polymer based composites, metakaolin mass ratio is 0.3%, and fracture toughness property is (0.14 ~ 0.2) MPa m
1/2, bending strength is (17.5 ~ 18.3) MPa, and Young's modulus is (7.5 ~ 7.9) GPa.
Embodiment three: the present embodiment and embodiment one or two difference are: the quality of graphene oxide powder described in rapid one and the volume ratio of deionized water are 12.5mg:1mL.
In the graphene/aluminum silicate polymer matrix material that what the present embodiment obtained utilize graphene oxide in-situ reducing to prepare, in graphene oxide and aluminosilicate polymer based composites, metakaolin mass ratio is 0.5%, and fracture toughness property is (0.15 ~ 0.27) MPa m
1/2, bending strength is (9.3 ~ 10.7) MPa, and Young's modulus is (6.5 ~ 7.3) GPa.
Claims (10)
1. the graphene/aluminum silicate polymer matrix material utilizing graphene oxide in-situ reducing to prepare, is characterized in that the graphene/aluminum silicate polymer matrix material utilizing graphene oxide in-situ reducing to prepare is prepared from by graphene oxide suspension, alkali-activated carbonatite solution and aluminosilicate powder;
Described graphene oxide suspension is mixed by graphene oxide powder and deionized water; The quality of described graphene oxide powder and the volume ratio of deionized water are (1 ~ 20) mg:1mL;
The silicon sol that described alkali-activated carbonatite solution is 25% ~ 45% by potassium hydroxide and mass concentration mixes; In described potassium hydroxide, potassium element and mass concentration are the mol ratio of element silicon in the silicon sol of 25% ~ 45% is 1:(0.5 ~ 1.5);
Graphene oxide powder in described graphene oxide suspension and the mass ratio of aluminosilicate powder are (0.01 ~ 0.15): 100;
In described aluminosilicate powder, the mol ratio of element silicon and aluminium element is 1:1;
In the described graphene/aluminum silicate polymer matrix material utilizing graphene oxide in-situ reducing to prepare, the mol ratio of element silicon and aluminium element is (1 ~ 4): 1.
2. a kind of graphene/aluminum silicate polymer matrix material utilizing graphene oxide in-situ reducing to prepare according to claim 1, is characterized in that the quality of described graphene oxide powder and the volume ratio of deionized water are 16.7mg:1mL.
3. a kind of graphene/aluminum silicate polymer matrix material utilizing graphene oxide in-situ reducing to prepare according to claim 1, is characterized in that potassium element and mass concentration in described potassium hydroxide be the mol ratio of element silicon in the silicon sol of 25% ~ 45% are 1:1.
4. a kind of graphene/aluminum silicate polymer matrix material utilizing graphene oxide in-situ reducing to prepare according to claim 1, is characterized in that the mol ratio of element silicon and aluminium element in the described graphene/aluminum silicate polymer matrix material utilizing graphene oxide in-situ reducing to prepare is 2:1.
5. the preparation method of a kind of graphene/aluminum silicate polymer matrix material utilizing graphene oxide in-situ reducing to prepare as claimed in claim 1, is characterized in that the preparation method of the graphene/aluminum silicate polymer matrix material utilizing graphene oxide in-situ reducing to prepare carries out according to the following steps:
One, the preparation of graphene oxide suspension: graphene oxide powder ultrasonic is scattered in deionized water, supersound process 2h ~ 6h, obtains brown color graphene oxide suspension; The quality of described graphene oxide powder and the volume ratio of deionized water are (1 ~ 20) mg:1mL;
Two, the preparation of alkali-activated carbonatite solution: potassium hydroxide being joined mass concentration is in the silicon sol of 25% ~ 45%, magnetic agitation mixing 20h ~ 80h, obtains alkali-activated carbonatite solution; In described potassium hydroxide, potassium element and mass concentration are the mol ratio of element silicon in the silicon sol of 25% ~ 45% is 1:(0.5 ~ 1.5);
The preparation of three, graphene oxide/alkali-activated carbonatite mixed solution: brown color graphene oxide suspension step one obtained joins in the alkali-activated carbonatite solution that step 2 obtains, after magnetic agitation mixing 10min ~ 30min, be in-situ reducing 0.01h ~ 72h under the condition of 20 DEG C ~ 80 DEG C in temperature, obtain graphene oxide/alkali-activated carbonatite mixed solution;
Four, the preparation of graphene/aluminum silicate polymer slurry: graphene oxide step 3 obtained/alkali-activated carbonatite mixed solution is placed in the ice-water bath that temperature is 0 DEG C ~ 5 DEG C, add aluminosilicate powder again, ultrasonic and mechanical stirring 25min ~ 45min, obtain graphene/aluminum silicate polymer slip, then deionized water is added, being adjusted to graphene/aluminum silicate polymer slip viscosity when shearing rate 60S-1 ~ 80S-1 is 150mPas ~ 500mPas, obtains graphene/aluminum silicate polymer slurry; In described aluminosilicate powder, the mol ratio of element silicon and aluminium element is 1:1;
Five, curing molding: graphene/aluminum silicate polymer slurry step 4 obtained is poured in mould, and be placed in exhaust in vacuum chamber, then being placed in temperature is maintenance 24h ~ 240h in the loft drier of 40 DEG C ~ 80 DEG C, obtains the graphene/aluminum silicate polymer matrix material utilizing graphene oxide in-situ reducing to prepare; In the described graphene/aluminum silicate polymer matrix material utilizing graphene oxide in-situ reducing to prepare, the mol ratio of element silicon and aluminium element is (1 ~ 4): 1;
Described in the powder of graphene oxide described in step one and step 4, the mass ratio of aluminosilicate powder is (0.01 ~ 0.15): 100.
6. the preparation method of a kind of graphene/aluminum silicate polymer matrix material utilizing graphene oxide in-situ reducing to prepare according to claim 5, is characterized in that the quality of the powder of graphene oxide described in step one and the volume ratio of deionized water are 16.7mg:1mL.
7. the preparation method of a kind of graphene/aluminum silicate polymer matrix material utilizing graphene oxide in-situ reducing to prepare according to claim 5, is characterized in that potassium element and mass concentration in potassium hydroxide described in step 2 be the mol ratio of element silicon in the silicon sol of 25% ~ 45% are 1:1.
8. the preparation method of a kind of graphene/aluminum silicate polymer matrix material utilizing graphene oxide in-situ reducing to prepare according to claim 5, to is characterized in that in step 3 in-situ reducing 72h under temperature is the condition of 60 DEG C.
9. the preparation method of a kind of graphene/aluminum silicate polymer matrix material utilizing graphene oxide in-situ reducing to prepare according to claim 5, it is characterized in that being placed in step 5 temperature is maintenance 168h in the loft drier of 60 DEG C.
10. the preparation method of a kind of graphene/aluminum silicate polymer matrix material utilizing graphene oxide in-situ reducing to prepare according to claim 5, is characterized in that the mol ratio of element silicon and aluminium element in the graphene/aluminum silicate polymer matrix material utilizing graphene oxide in-situ reducing to prepare described in step 5 is 2:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510018448.0A CN104529382B (en) | 2015-01-14 | 2015-01-14 | A kind of preparation method of the graphene/aluminum silicate polymer composite utilizing graphene oxide in-situ reducing to prepare |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510018448.0A CN104529382B (en) | 2015-01-14 | 2015-01-14 | A kind of preparation method of the graphene/aluminum silicate polymer composite utilizing graphene oxide in-situ reducing to prepare |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104529382A true CN104529382A (en) | 2015-04-22 |
| CN104529382B CN104529382B (en) | 2016-07-06 |
Family
ID=52845070
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510018448.0A Active CN104529382B (en) | 2015-01-14 | 2015-01-14 | A kind of preparation method of the graphene/aluminum silicate polymer composite utilizing graphene oxide in-situ reducing to prepare |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104529382B (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106057479A (en) * | 2016-05-16 | 2016-10-26 | 中国科学院青海盐湖研究所 | Electrode material of molecular sieve/graphene composite supercapacitor and preparation method thereof and supercapacitor |
| CN107266709A (en) * | 2017-07-18 | 2017-10-20 | 成都新柯力化工科技有限公司 | A kind of plastics enhancing graphene ca silicate fibre composite and preparation method |
| CN107275005A (en) * | 2017-06-22 | 2017-10-20 | 安徽银力铸造有限公司 | A kind of preparation method of graphene coated polycrystalline mullite fibre composite conducting material |
| CN107778011A (en) * | 2017-11-17 | 2018-03-09 | 北京林业大学 | A kind of preparation method of graphene composite SiC wood ceramics material |
| CN108499522A (en) * | 2018-03-20 | 2018-09-07 | 清华大学 | Gangue hollow microballon/aluminosilicate polymer compound adsorbent and preparation method thereof |
| CN108546145A (en) * | 2018-05-15 | 2018-09-18 | 清华大学 | A kind of preparation method of high porosity aluminosilicate polymer material |
| CN108585935A (en) * | 2018-05-15 | 2018-09-28 | 清华大学 | Gangue hollow microballon/foamed al-si silicate polymer composite material and preparation |
| CN108676243A (en) * | 2018-05-28 | 2018-10-19 | 天津市伟星新型建材有限公司 | A kind of hybrid material, graphene modified heat resistant PE-RT tubing and preparation method thereof |
| CN110330278A (en) * | 2019-07-15 | 2019-10-15 | 哈尔滨工业大学 | A kind of method of 3D printing graphene oxide enhancing aluminosilicate polymer |
| CN111233384A (en) * | 2020-03-20 | 2020-06-05 | 盐城工学院 | Graphene oxide reinforced geopolymer and preparation method thereof |
| CN111253119A (en) * | 2020-03-20 | 2020-06-09 | 盐城工学院 | Graphene oxide-silane coupling agent-geopolymer composite material and preparation method thereof |
| CN112029363A (en) * | 2020-09-14 | 2020-12-04 | 苏州鼎奕通材料科技有限公司 | High-performance protective film, preparation method thereof and application of high-performance protective film in PC/PMMA composite board |
| CN113683989A (en) * | 2021-08-20 | 2021-11-23 | 广西完美木业集团有限公司 | Adhesive capable of improving compression resistance of plywood and preparation method thereof |
| CN113877532A (en) * | 2021-11-15 | 2022-01-04 | 东北大学 | Graphene oxide reinforced solid waste inorganic spherical adsorbent, preparation method and application thereof |
| CN113908806A (en) * | 2021-11-15 | 2022-01-11 | 东北大学 | Graphene/inorganic polymer composite adsorption material, preparation method and application thereof |
| CN116768579A (en) * | 2023-08-25 | 2023-09-19 | 山东高速德建集团有限公司 | Anti-cracking concrete for assembled building and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531493A (en) * | 2009-04-09 | 2009-09-16 | 哈尔滨工业大学 | Preparation method of strengthened aluminosilicate polymer composite material of stainless steel fiber web |
| KR101247125B1 (en) * | 2011-10-19 | 2013-04-01 | 한국세라믹기술원 | Manufacturing method of ceramic composites with high fracture strength |
| CN103143319A (en) * | 2013-03-01 | 2013-06-12 | 暨南大学 | Graphene/clay composite material, and preparation method and application thereof |
| CN103865114A (en) * | 2014-02-27 | 2014-06-18 | 上海工程技术大学 | Imvite/natural rubber composite and preparation method thereof |
| CN104232108A (en) * | 2014-09-10 | 2014-12-24 | 浙江碳谷上希材料科技有限公司 | Preparation method of pure inorganic composite membrane based on graphene |
-
2015
- 2015-01-14 CN CN201510018448.0A patent/CN104529382B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531493A (en) * | 2009-04-09 | 2009-09-16 | 哈尔滨工业大学 | Preparation method of strengthened aluminosilicate polymer composite material of stainless steel fiber web |
| KR101247125B1 (en) * | 2011-10-19 | 2013-04-01 | 한국세라믹기술원 | Manufacturing method of ceramic composites with high fracture strength |
| CN103143319A (en) * | 2013-03-01 | 2013-06-12 | 暨南大学 | Graphene/clay composite material, and preparation method and application thereof |
| CN103865114A (en) * | 2014-02-27 | 2014-06-18 | 上海工程技术大学 | Imvite/natural rubber composite and preparation method thereof |
| CN104232108A (en) * | 2014-09-10 | 2014-12-24 | 浙江碳谷上希材料科技有限公司 | Preparation method of pure inorganic composite membrane based on graphene |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106057479A (en) * | 2016-05-16 | 2016-10-26 | 中国科学院青海盐湖研究所 | Electrode material of molecular sieve/graphene composite supercapacitor and preparation method thereof and supercapacitor |
| CN107275005A (en) * | 2017-06-22 | 2017-10-20 | 安徽银力铸造有限公司 | A kind of preparation method of graphene coated polycrystalline mullite fibre composite conducting material |
| CN107266709A (en) * | 2017-07-18 | 2017-10-20 | 成都新柯力化工科技有限公司 | A kind of plastics enhancing graphene ca silicate fibre composite and preparation method |
| CN107778011A (en) * | 2017-11-17 | 2018-03-09 | 北京林业大学 | A kind of preparation method of graphene composite SiC wood ceramics material |
| CN108499522B (en) * | 2018-03-20 | 2020-08-21 | 清华大学 | Coal gangue cenosphere/aluminosilicate polymer composite adsorbent and preparation method thereof |
| CN108499522A (en) * | 2018-03-20 | 2018-09-07 | 清华大学 | Gangue hollow microballon/aluminosilicate polymer compound adsorbent and preparation method thereof |
| CN108546145A (en) * | 2018-05-15 | 2018-09-18 | 清华大学 | A kind of preparation method of high porosity aluminosilicate polymer material |
| CN108585935A (en) * | 2018-05-15 | 2018-09-28 | 清华大学 | Gangue hollow microballon/foamed al-si silicate polymer composite material and preparation |
| CN108585935B (en) * | 2018-05-15 | 2020-08-21 | 清华大学 | Coal gangue hollow microsphere/foamed aluminosilicate polymer composite material and preparation |
| CN108676243A (en) * | 2018-05-28 | 2018-10-19 | 天津市伟星新型建材有限公司 | A kind of hybrid material, graphene modified heat resistant PE-RT tubing and preparation method thereof |
| CN108676243B (en) * | 2018-05-28 | 2021-02-09 | 天津市伟星新型建材有限公司 | Hybrid material, graphene modified heat-resistant PE-RT pipe and preparation method thereof |
| CN110330278A (en) * | 2019-07-15 | 2019-10-15 | 哈尔滨工业大学 | A kind of method of 3D printing graphene oxide enhancing aluminosilicate polymer |
| CN111253119A (en) * | 2020-03-20 | 2020-06-09 | 盐城工学院 | Graphene oxide-silane coupling agent-geopolymer composite material and preparation method thereof |
| CN111233384A (en) * | 2020-03-20 | 2020-06-05 | 盐城工学院 | Graphene oxide reinforced geopolymer and preparation method thereof |
| CN111253119B (en) * | 2020-03-20 | 2021-03-02 | 盐城工学院 | Graphene oxide-silane coupling agent-geopolymer composite material and preparation method thereof |
| CN112029363A (en) * | 2020-09-14 | 2020-12-04 | 苏州鼎奕通材料科技有限公司 | High-performance protective film, preparation method thereof and application of high-performance protective film in PC/PMMA composite board |
| CN113683989A (en) * | 2021-08-20 | 2021-11-23 | 广西完美木业集团有限公司 | Adhesive capable of improving compression resistance of plywood and preparation method thereof |
| CN113877532A (en) * | 2021-11-15 | 2022-01-04 | 东北大学 | Graphene oxide reinforced solid waste inorganic spherical adsorbent, preparation method and application thereof |
| CN113908806A (en) * | 2021-11-15 | 2022-01-11 | 东北大学 | Graphene/inorganic polymer composite adsorption material, preparation method and application thereof |
| CN113908806B (en) * | 2021-11-15 | 2022-12-23 | 东北大学 | Graphene/inorganic polymer composite adsorption material, preparation method and application thereof |
| CN113877532B (en) * | 2021-11-15 | 2023-07-18 | 东北大学 | Graphene oxide reinforced solid waste inorganic spherical adsorbent, preparation method and application thereof |
| CN116768579A (en) * | 2023-08-25 | 2023-09-19 | 山东高速德建集团有限公司 | Anti-cracking concrete for assembled building and preparation method thereof |
| CN116768579B (en) * | 2023-08-25 | 2023-10-17 | 山东高速德建集团有限公司 | Anti-cracking concrete for assembled building and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104529382B (en) | 2016-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104529382A (en) | Graphene/aluminosilicate polymer composite material prepared through graphene oxide in-situ reduction and preparation method thereof | |
| US10208180B2 (en) | Method for producing a master mixture based on carbonaceous nanofillers and super plasticiser, and the use thereof in hardenable inorganic systems | |
| CN105693262B (en) | The fiber reinforced ceramic matrix composites and preparation method at graphene/carbon nano-tube interface | |
| CN104030634B (en) | A kind of high-strength and high ductility RPC of carbon-doped nanometer tube and preparation method thereof | |
| Bharj et al. | Experimental study on compressive strength of cement-CNT composite paste | |
| CN103923601B (en) | The preparation method of structure/suction ripple integrated composite | |
| CN105314999A (en) | Nano porous high-temperature-insulating material taking thixotropic colloid as template agent and preparation method for high-temperature-insulating material | |
| CN103204660B (en) | High-hardness artificial quartz stone plate and production process thereof | |
| CN107814552B (en) | Silicon dioxide heat insulation composite material and preparation method thereof | |
| CN105439505B (en) | A kind of SiO2 aeroges mortar and preparation method thereof | |
| CN104446306A (en) | Submicron inorganic whisker aerogel thermal insulation composite and preparation method thereof | |
| CN110467467B (en) | Bulk silicon carbide polymer precursor ceramic and blending and cracking preparation method | |
| CN104529429A (en) | Graphene/leucite nano-composite ceramic material generated in high-temperature in-situ mode and preparation method thereof | |
| CN109337469A (en) | A kind of water nano thermal insulation paint and preparation method | |
| Zheng et al. | Biomimetic swallow nest structure: a lightweight and high-strength thermal insulation material | |
| CN106146866B (en) | A kind of polyimide composite film and preparation method thereof | |
| CN114292073B (en) | Aeolian sand anti-freezing concrete capable of being printed in 3D mode and preparation method and using method thereof | |
| Zhu et al. | High strength aligned SiC nanowire reinforced SiC porous ceramics fabricated by 3D printing and chemical vapor infiltration | |
| CN115093173A (en) | Oil well set cement microstructure bionic reinforcing and toughening regulation and control method, cement paste system and application | |
| CN111807810A (en) | Preparation method of nanowire/silicon-aluminum aerogel composite material | |
| CN112062515B (en) | High-strength geopolymer closed-cell foam material prepared from silicon carbide and preparation method thereof | |
| CN110304878A (en) | A kind of high thermal conductivity high tenacity mass concrete and preparation method thereof | |
| CN107311177B (en) | A kind of carbide-graphite alkene composite granule and preparation method thereof | |
| Yang et al. | Preparation and characterization of clay aerogel composites reinforced by calcium sulfate whisker | |
| CN106220118A (en) | A kind of composite glass fiber reinforced plasterboard and manufacture method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |