WO2020155516A1 - 一种石墨烯改性水泥基复合材料及其制备方法 - Google Patents

一种石墨烯改性水泥基复合材料及其制备方法 Download PDF

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WO2020155516A1
WO2020155516A1 PCT/CN2019/091066 CN2019091066W WO2020155516A1 WO 2020155516 A1 WO2020155516 A1 WO 2020155516A1 CN 2019091066 W CN2019091066 W CN 2019091066W WO 2020155516 A1 WO2020155516 A1 WO 2020155516A1
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graphene
cement
based composite
composite material
water
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朱继华
裴纯
邢锋
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Shenzhen University
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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
    • C04B28/02—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 containing hydraulic cements other than calcium sulfates
    • C04B28/04—Portland cements
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C01B32/19—Preparation by exfoliation
    • 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
    • C04B20/02—Treatment
    • C04B20/026—Comminuting, e.g. by grinding or breaking; Defibrillating fibres other than asbestos

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  • the invention relates to the technical field of composite material preparation, in particular to a graphene modified cement-based composite material and a preparation method thereof.
  • graphene-modified cement-based composite materials can not only improve mechanical properties, but also play multiple functions to promote the sustainable development of the graphene industry.
  • the literature shows that the incorporation of a small amount of graphene can significantly improve the performance of cement-based materials.
  • graphene oxide due to the low yield of graphene, the relatively considerable cost, and van der Waals interaction, graphene has a tendency to agglomerate, which hinders the wide application of graphene in industry. Therefore, graphene oxide (GO) is mostly used in graphene-modified cement-based composite materials.
  • the surface of graphene oxide has abundant functional groups, which weaken the van der Waals interaction between the layers, making it hydrophilic and easier to disperse in the cement matrix.
  • Lv Shenghua Lv Shenghua’s research group reported that when 0.03% of graphene oxide is added to cement at a weight ratio of cement, its tensile and flexural strengths at 28 days increase by 78.6% and 60.7%, respectively.
  • the graphene oxide content is 0.05%, and the compressive strength is increased by 47.9%.
  • the increase in mechanical properties is explained as the increase in toughness due to the addition of graphene oxide.
  • Li Xiangyu’s team also reported that 0.04% of graphene oxide increased the tensile strength by 67% due to the reduced secondary adsorption rate.
  • the preparation methods of graphene mainly include epitaxial growth method, chemical vapor deposition (CVD), micromechanical exfoliation method, redox method and liquid phase exfoliation method.
  • CVD chemical vapor deposition
  • micromechanical exfoliation method mainly include epitaxial growth method, chemical vapor deposition (CVD), micromechanical exfoliation method, redox method and liquid phase exfoliation method.
  • SDS sodium dodecyl sulfate
  • the maximum production rate of CVD is 1.0g/h, while the production rate can reach 5.3g/h in the liquid phase stripping method.
  • the preparation of a large amount of stable graphene aqueous dispersion is the prerequisite for the preparation of graphene-modified cement-based composite materials.
  • the liquid-phase exfoliation method is a preparation method with the highest yield of graphene at this stage, and it is expected to become a feasible preparation process for practical industrial applications of graphene.
  • the resulting graphene particles are usually stabilized by surfactant molecules, such as SDS and sodium cholate, and polymers.
  • surfactant molecules such as SDS and sodium cholate, and polymers.
  • the purpose of the present invention is to provide a graphene-modified cement-based composite material and a preparation method thereof, and aims to provide a low-cost, easy-to-operate, and large-scale preparation of aqueous graphene dispersions.
  • Method, and graphene aqueous dispersion can be used in cement pouring to improve the performance of cement.
  • a graphene-modified cement-based composite material includes cement and a dispersion liquid for dispersing the cement.
  • the dispersion liquid includes a water-soluble polymer, graphene, and deionized water.
  • the water-soluble polymer is selected from polyvinyl alcohol, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinylpyrrolidone, polymaleic anhydride, polyquaternary ammonium salt , Polyethylene glycol, polyethylene oxide, polyacrylic acid, polyacrylamide, and polyvinylpyrrolidone.
  • the water-soluble polymer is polyvinyl alcohol.
  • the mass ratio of the dispersion to the cement is 0.3 to 0.6.
  • the mass concentration of the water-soluble polymer is 1% to 6%.
  • the mass concentration of the graphene is 0.08-4.5 mg/mL.
  • a method for preparing the cement-based composite material of the present invention which comprises the steps:
  • the cement is mixed with the dispersion to obtain the cement-based composite material.
  • stirring is performed at a speed of 7000-21000 revolutions per minute.
  • stirring time is 5-60 minutes.
  • centrifugation is performed at a speed of 5000-10000 rpm for 5-60 minutes.
  • the graphene is prepared from graphite.
  • the water-soluble polymer is dissolved in water to match the surface energy of the solution with the graphene.
  • water-soluble polymers can be used as stabilizers to prevent the aggregation of graphene in a three-dimensional space by adsorbing on the surface of the graphene, so that the graphene is stably dispersed in water.
  • the dispersion liquid still has good stability after standing for a long time.
  • the dispersion is used instead of water to pour cement.
  • the compressive performance, flexural strength and thermal conductivity of the cement-based composite material of the present invention have been significantly improved, thanks to graphene and water-soluble polymer Synergistic modification of cement-based materials.
  • Figure 1a is a schematic diagram of the relationship between graphene concentration and absorbance in a specific embodiment of the present invention.
  • Figure 1b shows images of graphene/PVA dispersions freshly prepared and left to stand for 6 hours, 12 hours, 7 days, 14 days, and 28 days.
  • Figure 2a is a transmission electron microscope image of graphene nanosheets in a specific embodiment of the invention.
  • Figure 2b is another TEM image of the graphene nanosheets in the specific embodiment of the present invention, and the upper figure shows the SAED pattern.
  • Figure 2c shows the Raman spectra of graphite and graphene produced in a specific embodiment of the invention.
  • Figure 3a is a schematic diagram of the workability of the fresh cement paste of the cement-based composite material in a specific embodiment of the present invention.
  • Fig. 3b is a schematic diagram of the compressive strength of cement-based composite materials at different hydration times in specific embodiments of the present invention.
  • Figure 3c is a schematic diagram of the flexural strength of the cement-based composite material in a specific embodiment of the present invention.
  • Figure 3d is a schematic diagram of the thermal conductivity of the cement-based composite material in a specific embodiment of the present invention.
  • Figure 4 shows ordinary cement (PVA concentration 1.8wt.%) (a, b) and modified cement (graphene concentration in water 1.4g/L, PVA concentration 1.8wt.%) under different magnifications in specific embodiments of the present invention.
  • the present invention provides a graphene-modified cement-based composite material and a preparation method thereof.
  • the present invention will be described in further detail below. It should be understood that the specific embodiments described here are only used to explain the present invention, but not to limit the present invention.
  • the embodiment of the present invention provides a graphene-modified cement-based composite material, which includes cement and a dispersion liquid for dispersing the cement, and the dispersion liquid includes a water-soluble polymer, graphene, and deionized water.
  • the graphene is prepared from graphite, and the water-soluble polymer is dissolved in water to match the surface energy of the solution with the graphene, thereby increasing the yield of graphene.
  • water-soluble polymers can be used as stabilizers to prevent the aggregation of graphene in a three-dimensional space by adsorbing on the surface of the graphene, so that the graphene is stably dispersed in water. Studies have found that the dispersion liquid still has good stability after standing for a long time.
  • composite material technology to develop high-performance multifunctional building materials is a continuous demand for the development of civil engineering.
  • Composite materials have strong mechanical properties and durability, and have multiple functions, which can be widely used in future infrastructure projects.
  • Graphene has received extensive research attention due to its unique mechanical properties, high specific surface area and electron transport capabilities, and can significantly improve the physical properties of cement at a very low dosage.
  • the dispersion liquid described in the embodiment of the present invention has high production efficiency and low cost, and can be directly used for cement pouring instead of water.
  • the compressive performance, flexural strength and thermal conductivity of the cement-based composite material are significantly improved. This is due to the coupling modification of water-soluble polymers and graphene to cement-based materials, and it can be applied to the application of the mass concrete construction industry.
  • the water-soluble polymer is selected from polyvinyl alcohol, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinylpyrrolidone, polymaleic anhydride, poly One or more of quaternary amine salt, polyethylene glycol, polyethylene oxide, polyacrylic acid, polyacrylamide, and polyvinylpyrrolidone, but not limited thereto.
  • the water-soluble polymer is polyvinyl alcohol (PVA).
  • PVA polyvinyl alcohol
  • the mass ratio of the dispersion to the cement is 0.3 to 0.6.
  • the mass concentration of the water-soluble polymer in the dispersion is 1% to 6%.
  • the polymer concentration is too low, the surface energy of the solution does not match the van der Waals force between graphite flakes, the preparation efficiency of graphene is low, and the obtained graphene has poor dispersion effect, which is easy to cause agglomeration;
  • the polymer concentration is too high , The solution is too viscous to be used for the preparation of graphene, and when used for pouring cement-based composite materials, too much gas will be introduced, which will increase the porosity of cement-based materials, which is detrimental to the mechanical properties of cement-based materials influences.
  • the mass concentration of graphene in the dispersion is 0.08-4.5 mg/mL.
  • concentration of the polymer in the dispersion is different, the concentration of the graphene produced changes accordingly.
  • the graphene dispersion corresponding to the polymer concentration is added to the cement-based composite material, it can be effectively and uniformly dispersed in the cement-based material, and affect the performance of the cement-based material without being accompanied by agglomeration.
  • the embodiment of the present invention provides a method for preparing a cement-based composite material, which includes the following steps:
  • the cement is mixed with the dispersion to obtain the cement-based composite material.
  • the water-soluble polymer in order to increase the yield of graphene produced by liquid phase shear exfoliation, is dissolved in water to match the surface energy of the solution with the graphene.
  • water-soluble polymers can be used as stabilizers to prevent the aggregation of graphene in a three-dimensional space by adsorbing on the surface of the graphene, so that the graphene is stably dispersed in water. Studies have found that the dispersion liquid still has good stability after standing for a long time.
  • the dispersion prepared by the shear peeling method has high production efficiency and low cost.
  • graphene has received extensive research attention due to its unique mechanical properties, high specific surface area, and electron transport capability, and can significantly improve the physical properties of cement at a very low dosage.
  • the dispersion prepared by adopting the shear peeling method has high production efficiency and low cost, and can be directly used for cement pouring instead of water.
  • the compressive performance, flexural strength and thermal conductivity of the cement-based composite material have been significantly improved.
  • the water-soluble polymer is not only a stabilizer in the preparation of graphene, but also a polymer modifier for cement-based materials.
  • the turbulent flow-induced shearing and exfoliation causes the graphite plane to slide relatively until it is completely exfoliated, forming free-floating graphene.
  • the graphene is then combined with the water-soluble polymer in the solution to prevent the graphene from re-polymerizing into graphite.
  • the stirring is performed at a speed of 7000-21000 revolutions per minute. In some embodiments, the stirring time is 5-60 minutes.
  • centrifugal treatment is used to remove large graphite and graphene particles to obtain a pure dispersion containing graphene and water-soluble polymer.
  • centrifugation is performed at 5000-10000 rpm for 5-60 minutes.
  • graphite flakes were purchased from Sigma-Aldrich.
  • P.II52.5R Portland cement was purchased from Ludao (Yunfu) Co., Ltd.
  • Cement-based composite materials are prepared by mixing cement with a certain amount of graphene/PVA dispersion.
  • the water-cement ratio is fixed at 0.5, and the mass ratio of PVA to cement (poly-rubber ratio) is maintained at 1.8%.
  • the size of the test mold is 20 ⁇ 20 ⁇ 20mm 3 and 10 ⁇ 10 ⁇ 40mm 3 . In order to perform parallel experiments and reduce errors, 6 samples were prepared on each measuring point. After 24h demoulding, the specimens continue to be cured according to standard curing conditions (20 ⁇ 2°C, relative humidity 95%) until before the test.
  • thermogravimetric analysis TGA
  • 20 ml of the dispersion was vacuum filtered with an alumina membrane with a pore size of 0.2 ⁇ m.
  • the resulting film was then rinsed with deionized water several times to remove PVA, and then vacuum dried at 75° C. for 48 h, and then weighed to calculate the graphene concentration.
  • NETZSCH STA 409PC thermogravimetric analyzer was used for TGA measurement.
  • a PerkinElmer Lambda 750 spectrometer was used to measure the ultraviolet-visible absorption spectrum.
  • FEI-talos 200kV field emission transmission electron microscope (FETEM) was used to study the morphology of graphene.
  • the Raman spectrum of the prepared graphene was measured by a Renishaw laser confocal Raman microscope.
  • the concentration of graphene in the dispersion was determined by vacuum filtration, TGA and absorbance methods.
  • Figure 1a shows the relationship between graphene concentration and absorbance.
  • the absorbance of the dispersion increases linearly with the increase of graphene concentration. By linear fitting, the absorbance coefficient is 0.615mg/(mL ⁇ m).
  • the concentration of graphene in the dispersion can be determined by the relationship between absorbance and concentration.
  • the concentration of graphene in the newly prepared dispersion is 1.4 mg/mL, which is consistent with the result of thermogravimetric method.
  • the quality of the obtained graphene was evaluated by transmission electron microscopy and Raman spectroscopy.
  • the number of graphene layers is small, and the edge images show that the graphene sheets are 2-5 layers.
  • a copper grid can be observed underneath it, which indicates that graphene has only a limited number of stacked layers.
  • Raman spectroscopy was used to characterize the defects introduced in the dispersion process of graphene. As shown in Figure 2c, the representative Raman spectra of graphite and the obtained graphene are compared.
  • the performance of hydrated cement depends on the characteristics of its microstructure.
  • Figure 4 shows the curing of ordinary cement (PVA concentration 1.8wt.%) (a, b) and modified cement (graphene concentration in water 1.4g/L, PVA concentration 1.8wt.%) (c, d) under different magnifications.
  • 7 The SEM image of the crystal morphology of Tianhou; the EDS spectra of ordinary cement and graphene/PVA cement-based composite materials are shown in Figure eh and il, respectively.
  • needle-like crystals and flocculent crystals appear, which represent cement hydration products of ettringite and hydrated calcium silicate gel (C-S-H), respectively.
  • PVA and graphene affect the size, shape and distribution of hydration products by promoting the hydration process of cement, changing the internal structure of cement hydration from a microscopic point of view, fundamentally improving the mechanical strength of cement-based composites, thereby greatly extending The service life. Since the graphene is well dispersed, the heat conduction circuit is improved, and the thermal conductivity is improved. The good thermal conductivity of graphene can accelerate the diffusion of cement hydration heat, reduce the temperature difference between the inside and outside of the cement, thereby reducing the possibility of thermal cracking.
  • the preparation of low-cost and high-efficiency graphene aqueous dispersions is very important for their large-scale practical industrial applications.
  • water-soluble PVA is used as a shearing solution solute and stabilizer, and commercial graphite flakes can be exfoliated into few layers of graphene, which can be stably dispersed in water.
  • the graphene/PVA dispersion is used instead of water for the cement-based material pouring directly.
  • the test results of the examples of the present invention show that graphene and PVA polymers have a significant impact on the formation and performance of cement hydrated crystals and the microstructure of the hydrated cement paste, and have an important impact on the mechanical strength and thermal conductivity of the cement paste.
  • polyvinyl alcohol is not only a stabilizer in the preparation of graphene, but also a polymer modifier for cement-based materials.

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Abstract

一种石墨烯改性水泥基复合材料及其制备方法。石墨烯改性水泥基复合材料包括水泥和用于分散水泥的分散液，分散液包括水溶性聚合物、石墨烯和去离子水。石墨烯由石墨经剪切剥离得到，将水溶性聚合物溶于水中，使溶液表面能与石墨烯相匹配，同时水溶性聚合物可以作为稳定剂，通过吸附在石墨烯表面，在三维空间上阻止石墨烯聚集，使石墨烯稳定分散在水中。

Description

一种石墨烯改性水泥基复合材料及其制备方法 技术领域
本发明涉及复合材料制备技术领域，尤其涉及一种石墨烯改性水泥基复合材料及其制备方法。
背景技术
石墨烯作为一种单层二维碳质新型纳米材料，自2004年由Geim与Novoselov首次通过“微机械剥离法”制得以来，便得到广泛的关注与研究。石墨烯一系列优异的性能引起了广泛的关注，并且在石墨烯的制备、功能化和应用方面巨大的成就。迄今为止，石墨烯在超级电容器、生物传感器、燃料电池、薄膜材料等领域得到广泛研究，并在水泥胶凝材料中的应用也有报道。水泥混凝土是最重要的人造建筑材料。水泥胶凝材料在土木工程中的应用数量惊人。为了满足土木工程建设的需求，用于水泥胶凝材料的原材料需具备成本低、制作方法简易等特点。保证混凝土的和易性、强度和耐久性，最大限度地降低成本，是商品混凝土在市场竞争中的首要要求。
石墨烯改性水泥基复合材料的开发不仅可以提高机械性能，而且可以发挥多重功能，促进石墨烯产业的可持续发展。文献表明，少量石墨烯的掺入即可显著改善水泥基材料的性能。但由于石墨烯的产率低、成本相对可观、范德华相互作用导致石墨烯有团聚倾向，阻碍了石墨烯在工业中的广泛应用。因此，石墨烯改性水泥基复合材料大多采用氧化石墨烯(GO)。氧化石墨烯表面附有丰富的官能团，削弱了各层之间的范德华相互作用，使其具有亲水性，更容易在水泥基质中分散。吕生华课题组报道，当按水泥重量比0.03％的氧化石墨烯加入水泥时，其在28d时的拉伸和弯曲强度分别提高78.6％和60.7％。氧化石墨烯含量为0.05％，抗压强度提高47.9％。机械性能的增强被解释为由于氧化石墨烯的加入，导致韧性的增强。李翔宇的团队也报道了0.04％的氧化石墨烯由于降低了二次吸附率而使得拉伸强度提高了67％。胡云行团队也报道了当氧化石墨烯掺量为0.5％时，水泥基复合材料抗压强度提高35.7％；当微波固化与氧化石墨烯掺杂作用时，水泥基材料抗压强度提高126.6％。然而，氧化石墨烯并不是一种理想的水泥基改 性材料，它还存在一些重要的缺陷：氧化物的存在导致导电性差，其力学性能和导热性能无法与石墨烯相比；氧化程度的不确定性提高了掺氧化石墨烯胶凝材料的不均匀性；氧化石墨烯的制造过程一般需要大量的强酸，这使得其成本居高不下，阻碍了其大规模应用。
目前石墨烯的制备方法主要有外延生长法、化学气相沉积(CVD)、微机械剥离法、氧化还原法和液相剥离法等。在上述方法中，对石墨烯不同制备方法的生产速率进行了分析，得到在十二烷基硫酸钠(SDS)的存在下，湿法搅拌介质铣削的最大生产速率为1.5-2.5g/h，CVD最高生产速率为1.0g/h，而在液相剥离法生产速率能达到5.3g/h。制备大量的、稳定的石墨烯水相分散液是制备石墨烯改性水泥基复合材料的前提。液相剥离法是现阶段石墨烯产率最高的一种制备方法，有望成为可行的石墨烯实际工业应用的制备工艺。为了提高产率，溶液的表面能与石墨烯相近(46.7mN/m)时，可作为良好的分散介质剥离石墨制备石墨烯，由此制得的石墨烯颗粒通常由表面活性剂分子稳定，如SDS和胆酸钠，以及聚合物。Craciun课题组在表面活性剂胆酸钠的辅助下，通过液体剥离法制备了石墨烯。用表面活性剂功能化石墨烯制备了改性混凝土试块，并进行了测试。结果表明，混凝土的抗压强度、抗弯强度和透水性能均有较大提高。而表面活性剂在水泥中的作用及改性机理尚未揭示；且胆酸钠的掺入大大增加了胶凝材料的总成本，不适合大规模应用。鉴于上述原因，有必要开发一种低成本、易操作、能大量制备石墨烯水相分散液的方法。
因此，现有技术仍有待于改进和发展。
发明内容
鉴于上述现有技术的不足，本发明的目的在于提供一种石墨烯改性水泥基复合材料及其制备方法，旨在提供一种低成本、易操作、能大量制备石墨烯水相分散液的方法，并且石墨烯水相分散液能够用于水泥浇筑中，以提高水泥的性能。
本发明的技术方案如下：
一种石墨烯改性水泥基复合材料，其中，包括水泥和用于分散所述水泥的分散液，所述分散液包括水溶性聚合物、石墨烯和去离子水。
进一步地，所述水溶性聚合物选自聚乙烯醇、甲基纤维素、乙基纤维素、羧 甲基纤维素、羟乙基纤维素、聚乙烯吡咯烷酮、聚马来酸酐、聚季胺盐、聚乙二醇、聚环氧乙烷、聚丙烯酸、聚丙烯酰胺和聚乙烯基吡咯烷酮中的一种或多种。
再进一步地，所述水溶性聚合物为聚乙烯醇。
进一步地，所述分散液与所述水泥的质量比为0.3～0.6。
进一步地，所述分散液中，所述水溶性聚合物的质量浓度为1％～6％。
进一步地，所述分散液中，所述石墨烯的质量浓度为0.08～4.5mg/mL。
一种本发明所述的水泥基复合材料的制备方法，其中，包括步骤：
将水溶性聚合物溶解于去离子水中，接着加入石墨，并进行搅拌，再进行离心，得到所述分散液；
将水泥与所述分散液混合，得到所述水泥基复合材料。
进一步地，以每分钟7000～21000转的速度进行搅拌。
进一步地，所述搅拌的时间为5～60分钟。
进一步地，以5000～10000rpm速率离心5～60分钟。
有益效果：本发明中，所述石墨烯由石墨制备得到，为了提高制备石墨烯的产率，将水溶性聚合物溶于水中，使溶液表面能与石墨烯相匹配。同时，水溶性聚合物可以作为稳定剂，通过吸附在石墨烯表面，在三维空间上阻止石墨烯聚集，使石墨烯稳定分散在水中。所述分散液在长时间静置后依然具备很好的稳定性。采用所述分散液代替水浇注水泥，与普通水泥相比，本发明水泥基复合材料的抗压性能、抗弯强度及导热系数均得到了显著提高，这得益于石墨烯与水溶性聚合物对水泥基材料的协同改性作用。
附图说明
图1a为本发明具体实施例中石墨烯浓度与吸光度之间的关系示意图。
图1b新鲜制备和分别静置6小时、12小时、7天、14天、28天的石墨烯/PVA分散液图像。
图2a为本发明具体实施例中石墨烯纳米片的透射电镜图像。
图2b为本发明具体实施例中石墨烯纳米片的另一透射电镜图像，上图所示为SAED图形。
图2c为本发明具体实施例中石墨和所制得石墨烯的拉曼光谱。
图3a为本发明具体实施例中水泥基复合材料的新拌水泥浆体的和易性示意图。
图3b为本发明具体实施例中水泥基复合材料在不同水化时间的抗压强度示意图。
图3c为本发明具体实施例中水泥基复合材料的抗弯强度示意图。
图3d为本发明具体实施例中水泥基复合材料的导热系数示意图。
图4为本发明具体实施例中不同放大倍率下普通水泥(PVA浓度1.8wt.％)(a、b)和改性水泥(水中石墨烯浓度1.4g/L，PVA浓度1.8wt.％)(c、d)固化7天后晶体形貌的SEM图像；普通水泥和石墨烯/PVA水泥基复合材料的EDS谱图分别如图e-h、i-l所示。
具体实施方式
本发明提供一种石墨烯改性水泥基复合材料及其制备方法，为使本发明的目的、技术方案及效果更加清楚、明确，以下对本发明进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
本发明实施例提供一种石墨烯改性水泥基复合材料，其中，包括水泥和用于分散所述水泥的分散液，所述分散液包括水溶性聚合物、石墨烯和去离子水。
本实施例中，所述石墨烯由石墨制备得到，将水溶性聚合物溶于水中，使溶液表面能与石墨烯相匹配，从而提高了石墨烯的产率。同时，水溶性聚合物可以作为稳定剂，通过吸附在石墨烯表面，在三维空间上阻止石墨烯聚集，使石墨烯稳定分散在水中。研究发现，所述分散液在长时间静置后依然具备很好的稳定性。
利用复合材料技术开发高性能的多功能建筑材料是土木工程领域发展的持续需求。复合材料具有较强的机械性能和耐久性，并具有多种功能，可广泛应用于未来的基础设施项目。石墨烯因其独特的力学性能、高比表面积和电子传输能力得到广泛研究关注，可在极低的用量下显著改善水泥的物理性能。采用本发明实施例所述分散液，生产效率高，成本低，可替代水直接用于水泥浇注。与普通水泥相比，所述水泥基复合材料的抗压性能、抗弯强度及导热系数均得到了显著提高。这得益于水溶性聚合物与石墨烯对水泥基材料的耦合改性，并且能适用于大体积混凝土建筑行业的应用。
在一些实施方式中，所述水溶性聚合物选自聚乙烯醇、甲基纤维素、乙基纤维素、羧甲基纤维素、羟乙基纤维素、聚乙烯吡咯烷酮、聚马来酸酐、聚季胺盐、聚乙二醇、聚环氧乙烷、聚丙烯酸、聚丙烯酰胺和聚乙烯基吡咯烷酮等中的一种或多种，但不限于此。
在一些优选的实施方式中，所述水溶性聚合物为聚乙烯醇(PVA)。所述PVA的Mw＝31,000-50,000。
在一些实施方式中，所述分散液与所述水泥的质量比为0.3～0.6。
在一些实施方式中，所述分散液中，所述水溶性聚合物的质量浓度为1％～6％。当聚合物浓度过低时，溶液表面能与石墨片层间范德华力不相匹配，石墨烯的制备效率低下，且制得的石墨烯分散效果不佳，容易产生团聚；聚合物浓度过高时，溶液过于黏稠，无法很好的用于石墨烯的制备，且用来浇筑水泥基复合材料时，会引入过多的气体，使得水泥基材料孔隙率增大，对水泥基材料力学性能有不利影响。
在一些实施方式中，所述分散液中，石墨烯的质量浓度为0.08～4.5mg/mL。由于分散液中聚合物的浓度不同，因此制得的石墨烯浓度相应变化。当聚合物浓度与之相应的石墨烯分散液加入水泥基复合材料中时，可以有效的均匀分散于水泥基材料中，对水泥基材料的各项性能产生影响而不会伴随有团聚的发生。
本发明实施例提供一种水泥基复合材料的制备方法，其中，包括步骤：
将水溶性聚合物溶解于去离子水中，接着加入石墨，并进行搅拌，再进行离心，得到所述分散液；
将水泥与所述分散液混合，得到所述水泥基复合材料。
本实施例中，为了提高液相剪切剥离制备石墨烯的产率，将水溶性聚合物溶于水中，使溶液表面能与石墨烯相匹配。同时，水溶性聚合物可以作为稳定剂，通过吸附在石墨烯表面，在三维空间上阻止石墨烯聚集，使石墨烯稳定分散在水中。研究发现，所述分散液在长时间静置后依然具备很好的稳定性。采用剪切剥落法制备的分散液，生产效率高，成本低。
本实施例中，石墨烯因其独特的力学性能、高比表面积和电子传输能力得到广泛研究关注，可在极低的用量下显著改善水泥的物理性能。采用剪切剥落法制备的所述分散液，生产效率高，成本低，可替代水直接用于水泥浇注。与普通水 泥相比，所述水泥基复合材料的抗压性能、抗弯强度及导热系数均得到了显著提高。这是由于石墨烯和水溶性聚合物对水泥浆体的协同效应造成的，得益于水溶性聚合物与石墨烯对水泥基材料的耦合改性，并且能适用于大体积混凝土建筑行业的应用。在本实施例中，水溶性聚合物不仅是石墨烯制备中的稳定剂，而且是水泥基材料的聚合物改性剂。
本实施例中，利用搅拌处理，湍流诱导的剪切剥落导致石墨平面相对滑移，直至完全剥落，形成自由漂浮的石墨烯。石墨烯随后与溶液中的水溶性聚合物结合，防止石墨烯重新聚合成石墨。在一些实施方式中，以每分钟7000～21000转的速度进行搅拌。在一些实施方式中，所述搅拌的时间为5～60分钟。
本实施例中，利用离心处理，除去大的石墨和石墨烯颗粒，得到纯的含石墨烯与水溶性聚合物的分散液。在一些实施方式中，以5000～10000rpm速率离心5～60分钟。
下面通过具体实施例对本发明实施例进行详细说明。
1、材料
PVA(Mw＝31,000-50,000，87-89％水解)和石墨片购自Sigma-Aldrich。P.II52.5R硅酸盐水泥购自绿岛(云浮)有限公司。
2、石墨烯/PVA的分散液的制备
3.6wt.％PVA在磁力搅拌下溶解于95℃去离子水中。向溶液中加入5wt.％石墨薄片，并在商用高速搅拌机(Philips HR2096)中以每分钟21000转的速度进行搅拌。湍流诱导的剪切剥落导致石墨平面相对滑移，直至完全剥落，形成自由漂浮的石墨烯。石墨烯随后与溶液中的PVA结合，防止石墨烯重新聚合成石墨。该溶液搅拌30分钟，直到形成石墨烯和石墨混合分散液。以10000rpm速率离心30分钟，除去大的石墨和石墨烯颗粒，得到纯石墨烯/PVA分散液。分散液在室温下储存，直到进一步用于生产石墨烯/PVA改性水泥基复合材料。
3、水泥基复合材料的制备
通过水泥与一定量的石墨烯/PVA分散液的混合，制备水泥基复合材料。水灰比固定为0.5，PVA与水泥质量比(聚胶比)保持在1.8％。制备无石墨烯和PVA的普通水泥作为对照试样。试模尺寸为20×20×20mm 3和10×10×40mm 3。为了并行实验和误差减小，在每个测点上制备了6个样品。24h后脱模，试件继续 按照标准养护条件(20±2℃，相对湿度95％)养护，直到在测试之前。
4、石墨烯/PVA分散液的表征
为了得到分散液中石墨烯的浓度，进行了真空抽滤和热重分析(TGA)。20毫升的分散液用孔隙大小为0.2μm的氧化铝膜真空抽滤。所得薄膜随后用去离子水多次冲洗以除去PVA，随后在75℃下真空干燥48h，然后称重计算石墨烯浓度。采用NETZSCH STA 409PC热重分析仪进行TGA测量。为了得到分散液中石墨烯的浓度与吸光度线性关系，使用PerkinElmer Lambda 750光谱仪进行紫外可见吸收光谱测量。采用FEI-talos 200kV场发射透射电镜(FETEM)研究石墨烯的形貌。由Renishaw激光共聚焦拉曼显微镜对制得石墨烯拉曼光谱进行测量。
5、水泥基复合材料的性能及微观结构
参照标准ASTM C1437-15微坍落度试验，对水泥浆体的工作性能进行评价。抗压强度参照标准ASTM C349-14进行测定，抗弯强度参照标准ASTM C348-14进行测定。参照标准ASTM C177-13使用NETZSCH HFM 436/3/1E热导率分析仪进行热导率测试。每个系列测试6个样本，取平均值，根据标准差对结果进行评价。采用蔡司GeminiSEM 300场发射扫描电镜(FESEM)结合能谱仪(EDS)对石墨烯/PVA改性水泥基复合材料断口形貌及微观结构进行研究。
6、测试结果与分析
6.1、石墨烯/PVA分散液
为了提高液相剪切剥离制备石墨烯的产率，将PVA溶于水中，使溶液表面能与石墨烯相匹配。同时，PVA作为稳定剂，通过吸附在石墨烯表面，在三维空间上阻止石墨烯聚集。石墨烯分散液的稳定性对石墨烯的实际应用具有重要意义。通过观察新制备和分别静置6h、12h、7d、14d、28d的分散液的图像(见图1b)，可以看到分散液在长时间静置后依然具备很好的稳定性。采用真空抽滤、TGA和吸光度法测定了石墨烯在分散体中的浓度。图1a为石墨烯浓度与吸光度之间的关系。分散液的吸光度随石墨烯浓度的增加呈线性增加。通过线性拟合，得到吸光度系数为0.615mg/(mL·m)。石墨烯在分散液中的浓度可以通过吸光度与浓度的关系来确定。新制备的分散液中石墨烯的浓度为1.4mg/mL，与热重法结果一致。
采用透射电镜和拉曼光谱表征对所得石墨烯的质量进行了评价。图2a和图 2b中石墨烯层数较少，边缘图像显示石墨烯片层为2-5层。在其下方可以观察到铜栅，这表明石墨烯只存在有限数量的堆叠层。根据图2b中对应的SAED图形可以得出片状为结晶状，表面所制备的石墨烯具有较高的质量。利用拉曼光谱表征了石墨烯在分散过程中导入的缺陷。如图2c所示，比较了石墨和制得的石墨烯代表性拉曼光谱。石墨烯光谱中有一个小的D峰(～1350cm -1)，ID/IG比值为0.32，说明剥落过程对石墨烯边缘造成了较少的缺陷。另外，2D峰(～2700cm -1)代表2-5层石墨烯的特征峰，与TEM结果一致。
6.2、水泥基复合材料
用石墨烯/PVA分散液代替水浇注水泥试件，通过坍落度试验确定的新拌膏体的和易性如图3a所示。结果表明，占水泥重量1.8％的PVA与在水中浓度为0、0.2g/L、0.8g/L、1.4g/L石墨烯的浆料和易性分别比普通水泥提高5.2％、4.2％、1.6％，和降低6.2％。这一现象是由于石墨烯和PVA对水泥浆体和易性影响的协同效应造成的。不同石墨烯浓度水泥的抗压强度和抗弯强度如图3b和图3c所示。抗压强度随石墨烯浓度的增加而增加，石墨烯在水中浓度为1.4g/L时，固化7d、14d和28d抗压强度的最大增幅分别为71.1％、68.6％和66.9％(与含有占水泥重量为1.8％的PVA试件相比)。有趣的是，与普通水泥浆体相比，在没有石墨烯的情况下，含有1.8％PVA试件的抗压强度仅提升0.8％。PVA改性后水泥的抗弯强度比普通水泥提高36.2％。与普通水泥相比，1.4g/L石墨烯和1.8wt.％PVA的共同作用可提高106.5％的抗弯强度。石墨烯浓度对导热系数的影响如图3d所示。与未加入石墨烯的试样相比，导热系数最大提高了75.8％。
水化水泥的性能取决于其微观结构的特点。图4为不同放大倍率下普通水泥(PVA浓度1.8wt.％)(a、b)和改性水泥(水中石墨烯浓度1.4g/L，PVA浓度1.8wt.％)(c、d)固化7天后晶体形貌的SEM图像；普通水泥和石墨烯/PVA水泥基复合材料的EDS谱图分别如图e-h、i-l所示。在普通水泥的断口表面，出现针状结晶和絮凝状结晶，分别代表了钙矾石和水化硅酸钙凝胶(C-S-H)的水泥水化产物。在水泥中加入石墨烯后，形貌变化明显。分散良好的水泥和结晶水化产物的孔隙尺寸和形状与以往完全不同，可以观察到棒状钙矾石晶体簇和粒状C-S-H。钙矾石的结构由针状向棒状转变，说明石墨烯掺入水泥促进了水化过程。PVA在水泥中形成了三维空间结构，在水化水泥中趋于形成连续膜。在石墨烯/PVA偶联改 性胶凝材料中，与普通水泥浆体相比，水泥浆体分散性较好，通过能谱表征对其进行评价(见图4)，说明石墨烯在PVA的辅助下均匀分散在水泥浆料中，具有成核诱导作用。在水泥水化阶段，随着水的减少，PVA逐渐被限制在毛细管孔隙中，在水化水泥表面形成凝胶膜。该膜将水化水泥凝胶、未水化水泥颗粒和石墨烯包裹在一起，形成三维互穿网络结构，使水泥力学性能明显增强，尤其是在抗折强度上。PVA与石墨烯通过促进水泥水化过程，影响水化产物的大小、形状和分布，从微观角度改变水泥水化后的内部结构，从根本上提高了水泥基复合材料的机械强度，从而大大延长了使用寿命。由于石墨烯分散良好，改善了导热回路，提高了导热系数。石墨烯良好的导热性能可以加速水泥水化热的扩散，降低水泥内外温差，从而降低热开裂的可能性。
综上所述，低成本高效率的石墨烯水相分散液的制备对其大规模实际工业应用至关重要。在本发明实施例中，水溶性PVA作为剪切溶液溶质和稳定剂，可将商业石墨薄片剥落成少层石墨烯，稳定分散在水中。在水泥浇筑过程中，石墨烯/PVA分散液代替水直接用于水泥基材料的浇筑。本发明实施例测试结果表明，石墨烯和PVA聚合物对水泥水化晶体的形成和性能以及水化水泥浆体的微观结构有显著影响，对水泥浆体的力学强度和导热性能有重要影响。在本发明实施例中，聚乙烯醇不仅是石墨烯制备中的稳定剂，而且是水泥基材料的聚合物改性剂。
应当理解的是，本发明的应用不限于上述的举例，对本领域普通技术人员来说，可以根据上述说明加以改进或变换，所有这些改进和变换都应属于本发明所附权利要求的保护范围。

Claims (10)

  1. 一种石墨烯改性水泥基复合材料，其特征在于，包括水泥和用于分散所述水泥的分散液，所述分散液包括水溶性聚合物、石墨烯和去离子水。
  2. 根据权利要求1所述的石墨烯改性水泥基复合材料，其特征在于，所述水溶性聚合物选自聚乙烯醇、甲基纤维素、乙基纤维素、羧甲基纤维素、羟乙基纤维素、聚乙烯吡咯烷酮、聚马来酸酐、聚季胺盐、聚乙二醇、聚环氧乙烷、聚丙烯酸、聚丙烯酰胺和聚乙烯基吡咯烷酮中的一种或多种。
  3. 根据权利要求2所述的石墨烯改性水泥基复合材料，其特征在于，所述水溶性聚合物为聚乙烯醇。
  4. 根据权利要求1所述的石墨烯改性水泥基复合材料，其特征在于，所述分散液与所述水泥的质量比为0.3～0.6。
  5. 根据权利要求1所述的石墨烯改性水泥基复合材料，其特征在于，所述分散液中，所述水溶性聚合物的质量浓度为1％～6％。
  6. 根据权利要求1所述的石墨烯改性水泥基复合材料，其特征在于，所述分散液中，所述石墨烯的质量浓度为0.08～4.5mg/mL。
  7. 一种权利要求1-6任一项所述的石墨烯改性水泥基复合材料的制备方法，其特征在于，包括步骤：
    将水溶性聚合物溶解于去离子水中，接着加入石墨，并进行搅拌，再进行离心，得到所述分散液；
    将水泥与所述分散液混合，得到所述水泥基复合材料。
  8. 根据权利要求7所述的石墨烯改性水泥基复合材料的制备方法，其特征在于，以每分钟7000～21000转的速度进行搅拌。
  9. 根据权利要求7所述的石墨烯改性水泥基复合材料的制备方法，其特征在于，所述搅拌的时间为5～60分钟。
  10. 根据权利要求7所述的石墨烯改性水泥基复合材料的制备方法，其特征在于，以5000～10000rpm速率离心5～60分钟。
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