CN112299768B - Graphene functionalized cement-based material and preparation method thereof - Google Patents
Graphene functionalized cement-based material and preparation method thereof Download PDFInfo
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- CN112299768B CN112299768B CN202011274825.4A CN202011274825A CN112299768B CN 112299768 B CN112299768 B CN 112299768B CN 202011274825 A CN202011274825 A CN 202011274825A CN 112299768 B CN112299768 B CN 112299768B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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 discloses a graphene functionalized cement-based material and a preparation method thereof, wherein the preparation method comprises the following steps: step 1, stirring and mixing cement powder and a carbon source uniformly; and 2, placing the mixture of the carbon source and the cement powder obtained in the step 1 into a high-temperature furnace, and heating the high-temperature furnace to 500-700 ℃ for calcining to obtain the graphene functionalized cement-based material. According to the invention, the carbon source and the cement material are uniformly mixed, and the in-situ growth of graphene in the cement matrix is realized under the environment of 500-700 ℃, namely, graphene lamella grow in situ on the surface of cement powder, and the basic components of cement are maintained, so that the compressive strength of the cement material is finally improved, the complicated chemical modification and physical ultrasonic dispersion processes of the original technical method are overcome, and the preparation cost is reduced.
Description
Technical Field
The invention belongs to the technical field of novel building materials, and particularly relates to a graphene functionalized cement-based material and a preparation method thereof.
Background
The application of graphene to modified cement materials is the most potential functional material at present. The existing graphene concrete preparation method is mainly characterized in that after commercial graphene is subjected to surface modification, a high-power ultrasonic dispersion instrument is used for preparing a temporarily stable graphene aqueous solution, and then the mixed solution is added into a cementing material for mixing concrete. The preparation method has the problems that the operation is complex, the purchase cost of the commercial graphene is high, the unit price of 1g of graphene reaches about 800 yuan in the current market price, and even if the graphene can be prepared in a small batch in a laboratory, the engineering application is difficult. Therefore, the graphene concrete preparation technology still faces the problems of high price, difficult physical mixing and the like, so that the graphene concrete preparation technology cannot be applied to engineering.
Compared with graphene concrete, graphene oxide concrete which is the most widely researched currently omits the complicated process of surface modification in preparation, but the preparation of an aqueous solution is still carried out by using an ultrasonic instrument.
Therefore, the development of a simple and cheap preparation process of a multifunctional cement-based material with uniform mixing of graphene and a cement material is urgent.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a graphene functionalized cement-based material and a preparation method thereof, which are simple to operate and low in price.
The invention is realized by the following technical scheme:
a preparation method of a graphene functionalized cement-based material comprises the following steps:
step 1, stirring and mixing cement powder and a carbon source uniformly;
and 2, placing the mixture of the carbon source and the cement powder obtained in the step 1 into a high-temperature furnace, and heating the high-temperature furnace to the temperature of 500-700 ℃ for calcining to obtain the graphene functionalized cement-based material.
Preferably, in step 1, the carbon source is glucose, sucrose, wheat straw powder or corn straw powder.
Preferably, in the step 1, the mass of the carbon source accounts for 3% -10% of the total mass of the cement powder and the carbon source;
preferably, in the step 1, the stirring time is 12h-72 h.
Preferably, in the step 2, the calcination time is 0.5h-10 h.
The graphene functionalized cement-based material prepared by the preparation method is adopted.
Compared with the prior art, the invention has the following beneficial technical effects:
according to the invention, the carbon source and the cement material are uniformly mixed, and the in-situ growth of graphene in the cement matrix is realized under the environment of 500-700 ℃, namely, the graphene lamella grows in situ on the surface of the cement powder, the basic components of the cement are maintained, and the compressive strength of the cement material is finally improved. Since the graphene grows from the surface of the cement powder particles, the agglomeration phenomenon caused by strong van der Waals force among nano materials is directly avoided, and uniform dispersion can be realized. In the aspect of improvement of the preparation process, the complex chemical modification and physical ultrasonic dispersion process of the prior art method are overcome. From the economical point of view, the cost of the raw materials adopted by the method is far lower than that of the commercial graphene oxide and graphene, the method has more potential engineering application value, the method for synthesizing the graphene functionalized cement material can be expanded to large-scale commercial application, and the method is favorable for subsequent pilot plant test, pilot plant test and further commercialization of the cement material. The method disclosed by the invention breaks through the engineering application problem of directly doping the graphene with the cement material, breaks through the technical problem of uniformly doping the graphene with the cement material matrix, fills the blank of basic theory research and engineering technology application in the field, and further promotes the further progress of the graphene functionalized cement material to the engineering application.
Furthermore, the method utilizes cheap glucose, sucrose and wheat straw as the graphene preparation raw materials, so that the material preparation cost is greatly reduced.
According to the material prepared by the method, as the graphene grows from the surface of the cement powder particles, the agglomeration phenomenon caused by strong van der Waals force among nano materials is directly avoided, the uniform dispersion of the graphene can be realized, and the performance of the prepared material is improved. The maximum compression strength enhancement range of the neat paste block prepared from the graphene modified cement material (the graphene doping amount is 0.05 wt%, and the water-cement ratio is 0.35) compared with that of a blank control group is up to 20%, and the enhancement range of the neat paste block prepared from the graphene functionalized cement material (the graphene doping amount is 0.05 wt%, and the water-cement ratio is 0.35) prepared by the method can reach 30% -112%. After the strength is improved, the use amount of materials can be saved, thereby greatly reducing the construction cost.
Drawings
Fig. 1 is a powder photograph of graphene, cement powder and graphene functionalized cement prepared by the present invention;
fig. 2 is an XRD chart of graphene, cement powder and graphene functionalized cement prepared by the present invention;
fig. 3 is a raman spectrum of the functionalized graphene, cement and graphene water mud powder prepared by the method.
Fig. 4 is a photograph of the graphene functionalized cement prepared by the stirring device in the laboratory.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The graphene functionalized cement-based material in-situ growth preparation method comprises the following steps:
step 1, stirring and mixing cement powder and a carbon source for 12-72 hours to uniformly mix the cement powder and the carbon source; the carbon source is glucose, sucrose, wheat straw powder or corn straw powder, the mass of the obtained graphene accounts for 3% -10% of the total mass of the cement powder and the carbon source, and the yields of the carbon source, namely the glucose, the sucrose, the wheat straw powder and the corn straw powder, for producing the graphene are respectively 5%, 4% and 4.5%.
And 2, putting the mixture of the carbon source and the cement which is fully and uniformly stirred in the step 1 into a high-temperature furnace, heating the high-temperature furnace to 500-700 ℃, and keeping the temperature for 0.5-10 h.
And 3, naturally cooling to room temperature, and taking out the fired sample from the muffle furnace.
And 4, pouring the fired mixture and the polycarboxylic acid high-efficiency water reducing agent powder into a stirrer to stir for 10-30 minutes.
Step 5, preparing the material pure pulp obtained in the step 4 into a standard 50mm3And (5) maintaining the prepared module for 14 days according to the standard of testing mechanical properties.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1
Step 1, stirring and mixing cement powder and glucose for 24 hours to uniformly mix the cement powder and the glucose; wherein the mass of the glucose accounts for 3 percent of the total mass of the cement powder and the glucose.
And 2, putting the mixture of the carbon source and the cement which is fully and uniformly stirred in the step 1 into a high-temperature furnace, heating the high-temperature furnace to 550 ℃, and keeping the temperature for 4 hours.
And 3, naturally cooling to room temperature, and taking the fired sample out of the furnace.
And 4, pouring the fired mixture and the polycarboxylic acid high-efficiency water reducing agent powder into a stirrer to stir for 10 minutes.
Step 5, preparing the material pure pulp obtained in the step 4 into a standard 50mm3And (5) maintaining the prepared module for 14 days according to the standard of testing mechanical properties.
Example 2
Step 1, stirring and mixing cement powder and glucose for 24 hours to uniformly mix the cement powder and the glucose; wherein the mass of the glucose accounts for 6 percent of the total mass of the cement powder and the glucose.
And 2, putting the mixture of the carbon source and the cement which is fully and uniformly stirred in the step 1 into a high-temperature furnace, heating the high-temperature furnace to 550 ℃, and keeping the temperature for 4 hours.
And 3, naturally cooling to room temperature, and taking the fired sample out of the furnace.
And 4, pouring the fired mixture and the polycarboxylic acid high-efficiency water reducing agent powder into a stirrer to stir for 10 minutes.
Step 5, preparing the material pure pulp obtained in the step 4 into a standard 50mm3And (5) maintaining the prepared module for 14 days according to the standard of testing mechanical properties.
Example 3
Step 1, stirring and mixing cement powder and glucose for 24 hours to uniformly mix the cement powder and the glucose; wherein the mass of the glucose accounts for 10% of the total mass of the cement powder and the glucose.
And 2, putting the mixture of the carbon source and the cement which is fully and uniformly stirred in the step 1 into a high-temperature furnace, heating the high-temperature furnace to 550 ℃, and keeping the temperature for 4 hours.
And 3, naturally cooling to room temperature, and taking the fired sample out of the furnace.
And 4, pouring the fired mixture and the polycarboxylic acid high-efficiency water reducing agent powder into a stirrer to stir for 10 minutes.
Step 5, preparing the material pure pulp obtained in the step 4 into a standard 50mm3And (5) maintaining the prepared module for 14 days according to the standard of testing mechanical properties.
Example 4
Step 1, stirring and mixing cement powder and cane sugar for 12 hours to uniformly mix the cement powder and the cane sugar; wherein the mass of the sucrose accounts for 10% of the total mass of the cement powder and the sucrose.
And 2, putting the mixture of the carbon source and the cement which is fully and uniformly stirred in the step 1 into a high-temperature furnace, heating the high-temperature furnace to 550 ℃, and keeping the temperature for 2 hours.
And 3, naturally cooling to room temperature, and taking the fired sample out of the furnace.
And 4, pouring the fired mixture and the polycarboxylic acid high-efficiency water reducing agent powder into a stirrer to stir for 30 minutes.
Step 5, preparing the material pure slurry obtained in the step 4 into a standard 50mm3And (5) maintaining the prepared module for 14 days according to the standard of testing mechanical properties.
Example 5
Step 1, stirring and mixing cement powder and wheat straw powder for 36 hours to uniformly mix the cement powder and the wheat straw powder; wherein the wheat straw powder accounts for 10% of the total mass of the cement powder and the wheat straw powder.
And 2, putting the mixture of the carbon source and the cement which is fully and uniformly stirred in the step 1 into a high-temperature furnace, heating the high-temperature furnace to 600 ℃, and keeping the temperature for 0.5 h.
And 3, naturally cooling to room temperature, and taking the fired sample out of the furnace.
And 4, pouring the fired mixture and the polycarboxylic acid high-efficiency water reducing agent powder into a stirrer to stir for 20 minutes.
Step 5, preparing the material pure pulp obtained in the step 4 into a standard 50mm3And (5) maintaining the prepared module for 14 days according to the standard of testing mechanical properties.
Example 6
Step 1, stirring and mixing cement powder and wheat straw powder for 72 hours to uniformly mix the cement powder and the wheat straw powder; wherein the mass of the wheat straw powder accounts for 10% of the total mass of the cement powder and the corn straw powder.
And 2, putting the mixture of the carbon source and the cement which is fully and uniformly stirred in the step 1 into a high-temperature furnace, heating the high-temperature furnace to 550 ℃, and keeping the temperature for 10 hours.
And 3, naturally cooling to room temperature, and taking the fired sample out of the furnace.
And 4, pouring the fired mixture and the polycarboxylic acid high-efficiency water reducing agent powder into a stirrer to stir for 30 minutes.
Step 5, preparing the material pure pulp obtained in the step 4 into a standard 50mm3Module to be made according to the standard for testing mechanical propertiesThe prepared modules were maintained for 14 days.
Comparative example 1
Step 1, putting cement powder into a high-temperature furnace, heating the high-temperature furnace to 600 ℃, and keeping the temperature for 4 hours.
And 2, naturally cooling to room temperature, and taking the fired sample out of the furnace.
And 3, pouring the fired mixture and the polycarboxylic acid high-efficiency water reducing agent powder into a stirrer to stir for 10 minutes.
Step 4, preparing the material pure pulp obtained in the step 3 into the standard 50mm3And (5) maintaining the prepared module for 14 days according to the standard of testing mechanical properties.
And characterizing the graphene functionalized cement material prepared in the embodiment by XRD and Raman spectroscopy.
Fig. 1 is a photograph of graphene sample powder prepared from glucose, synthesized in comparative example 1 and example 3, a photograph of pure cement material powder, and a photograph of graphene-functionalized cement powder, and it was found that the color of the cement material was changed to brown-gray after the graphene was functionalized. As shown in fig. 2, XRD data of the materials synthesized by the glucose prepared graphene of the present invention and the comparative example 1 and the example 3 shows that the material has characteristic peaks of graphene and cement material, which indicates that the graphene functionalized cement matrix indeed has two types of materials, namely graphene and cement. As shown in fig. 3, for raman data of the graphene prepared from glucose according to the present invention and the materials synthesized in comparative example 1 and example 3, it can be seen from the raman data of the graphene functionalized cement material that the material has characteristic peaks of both graphene and cement material, which further proves that the graphene functionalized cement matrix has both graphene and cement materials.
As shown in Table 1, the compressive strength of the net slurry test block prepared by the method of the invention can be enhanced by 30-112%.
Table 1 shows the compressive strength data of the net slurry test blocks prepared in examples 1-3 of the present invention and comparative example 1
Fig. 4 is a photograph of the graphene functionalized cement prepared by the stirring device in the laboratory, and the experiment shows that the preparation idea of the invention has a prospect of industrial application.
According to the method, cheap glucose, cane sugar and wheat straw are used as graphene preparation raw materials, and in-situ growth of graphene in a cement matrix is realized. From the research perspective, the method realizes the scientific problem that the graphene is dispersed in the cement matrix; from the engineering application point of view, the method realizes the technical problem of preparing the material on a large scale. In the aspect of improvement of the preparation process, the complex chemical modification and physical ultrasonic dispersion process of the prior art method are overcome. From the economic aspect, the cost of the raw materials adopted by the method is far lower than that of the commercial graphene oxide and graphene, and the method has more potential engineering application value. The method disclosed by the invention breaks through the engineering application problem of directly doping the graphene with the cement material, breaks through the technical problem of uniformly doping the graphene with the cement material matrix, fills the blank of basic theory research and engineering technology application in the field, and further promotes the further progress of the graphene functionalized cement material to the engineering application.
Claims (4)
1. A preparation method of a graphene functionalized cement-based material is characterized by comprising the following steps:
step 1, stirring and mixing cement powder and a carbon source uniformly;
step 2, placing the mixture of the carbon source and the cement powder obtained in the step 1 into a high-temperature furnace, and heating the high-temperature furnace to 500-700 ℃ for calcining to obtain the graphene functionalized cement-based material;
in the step 1, the carbon source is glucose or sucrose;
in the step 1, the mass of the carbon source accounts for 3-10% of the total mass of the cement powder and the carbon source.
2. The method for preparing the graphene-functionalized cement-based material according to claim 1, wherein in the step 1, the stirring time is 12-72 hours.
3. The method for preparing a graphene-functionalized cement-based material according to claim 1, wherein in the step 2, the calcination time is 0.5h to 10 h.
4. The graphene functionalized cement-based material prepared by the preparation method of any one of claims 1 to 3.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140323607A1 (en) * | 2013-04-30 | 2014-10-30 | Alfaisal University | Composition of nanocomposite containing graphene sheets |
| CN104891483A (en) * | 2015-06-03 | 2015-09-09 | 常州大学 | Preparation method of three-dimensional graphene |
| US20160130149A1 (en) * | 2013-07-17 | 2016-05-12 | Peerless Worldwide, Llc | Process for the synthesis of graphene and graphene derivatives from greenhouse gases and other carbonaceous waste products |
| CN106315568A (en) * | 2016-08-23 | 2017-01-11 | 黄云鸿 | Preparation method of graphene and graphene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20170075992A (en) * | 2015-12-24 | 2017-07-04 | 김동기 | A functional cement method and functional cement containing graphene |
| CN110028279B (en) * | 2019-05-10 | 2021-05-25 | 济南大学 | Method for preparing nano modified cement-based biomass material by calcining straw ash at high temperature |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140323607A1 (en) * | 2013-04-30 | 2014-10-30 | Alfaisal University | Composition of nanocomposite containing graphene sheets |
| US20160130149A1 (en) * | 2013-07-17 | 2016-05-12 | Peerless Worldwide, Llc | Process for the synthesis of graphene and graphene derivatives from greenhouse gases and other carbonaceous waste products |
| CN104891483A (en) * | 2015-06-03 | 2015-09-09 | 常州大学 | Preparation method of three-dimensional graphene |
| CN106315568A (en) * | 2016-08-23 | 2017-01-11 | 黄云鸿 | Preparation method of graphene and graphene |
Non-Patent Citations (1)
| Title |
|---|
| A novel cement-based hybrid material;Albert G Nasibulin等;《New Journal of Physics》;New Journal of Physics;20090206;第11卷;第1-10页 * |
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