Study on preparation and properties of graphene/Ca(OH)2 nanocomposite in different temperatures
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摘要: 纳米Ca(OH)2对风化后的大理岩石质文物有良好的加固效果，在较低温度下得到性能优异的纳米颗粒对其成本降低和推广应用有重要意义。本研究通过调节反应温度，引入石墨烯量子点，制备得到了一系列石墨烯/Ca(OH)2纳米复合材料，并采用TEM、激光粒度仪、Raman、FTIR、UV-Vis、XRD、SEM、分光测色仪、压汞仪、硬度计、超声波测速仪等对材料形貌组成、相对动力学稳定性、碳酸化反应和模拟样品加固性能进行分析研究。结果表明反应温度的适当升高有利于石墨烯与Ca(OH)2的复合，以及纳米颗粒粒径的减小，在80℃下得到的产物相对动力学稳定性、碳酸化速率和加固性能较好；随着温度继续升高，90℃及以上所制备的材料转变为球状结晶，而且碳酸化后部分会保持为亚稳态球霰石物相，并未表现出更好的加固性能。Abstract: Graphene/Ca(OH)2 nanocomposite has a good consolidation effect on weathered marble artifacts. Preparation of this kind of material with excellent performance at lower temperatures plays an important role on its cost reduction and popularization. In this study, a series of graphene/Ca(OH)2 nanocomposites were prepared by adjusting the reaction temperature and addition of graphene quantum dot. The morphology, composition, relative kinetic stability, carbonation reaction and reinforcement property were studied by transmission electron microscope, laser particle analyzer, Raman spectroscopy, Fourier-transform infrared spectroscopy, UV-visible spectrometer, X-ray diffractometer, scanning electron microscope, colorimeter, mercury injection apparatus, leeb hardness tester and ultrasonic tester. The results showed that the appropriate increase of reaction temperature was conducive to the improvement of combination and the reduction of nanoparticle size. The products obtained at 80℃ exhibited good relative kinetic stability, fast carbonation rate and excellent reinforcement property, while the materials prepared at 90℃ and above grew into spherical crystals and did not show better properties, may due to the influence of calcium hydroxide transform to vaterite.
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Key words:
- graphene /
- nano material /
- calcium hydroxide /
- consolidation /
- graphene quantum dots
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图 1 石墨烯量子点(GQDs)/Ca(OH)2-60℃至95℃(a-e)及GQDs/Ca(OH)2-60℃中散落微小颗粒的TEM图像(f)
Figure 1. TEM images of samples graphene quantum dots (GQDs)/Ca(OH)2-60℃ to 95℃ (a-e) and the tiny particles in Ca(OH)2-60℃ (f) (Notes：image of GQDs/Ca(OH)2-80℃ is same with the result in ammoniated solution[14])
图 2 GQDs/Ca(OH)2-60℃至95℃平均粒径变化和粒径频率分布曲线半高宽变化
Figure 2. The average sizes and FWHM of the size distribution curve of the samples GQDs/Ca(OH)2-60℃ to 95℃
图 3 GQDs/Ca(OH)2-60℃至95℃样品的拉曼光谱(a)和红外光谱图(b)
Figure 3. Raman spectra (a) and FTIR results (b) of the samples GQDs/Ca(OH)2-60℃ to 95℃
图 4 GQDs/Ca(OH)2-60℃至95℃样品乙醇分散液的相对动力学稳定性
Figure 4. Colloidal relative kinetic stability of samples GQDs/Ca(OH)2-60℃ to 95℃ in ethanol
图 5 GQDs/Ca(OH)2-60℃至95℃样品碳酸化0−12天的物相组成：(a)Ca(OH)2，(b)方解石，(c)球霰石
Figure 5. Phase analysis of samples T GQDs/Ca(OH)2-60 to 95℃ carbonated for 0-12 days: (a) Ca(OH)2, (b) calcite, (c) vaterite
图 6 模拟样品加固后SEM图像：(a)QBS，(b)G/Ca60-C，(c)G/Ca70-C，(d)G/Ca80-C，(e)G/Ca90-C，(f)G/Ca95-C
Figure 6. SEM images of the simulated sample after reinforcement: (a) QBS, (b) G/Ca60-C, (c) G/Ca70-C, (d) G/Ca80-C, (e) G/Ca90-C, (f) G/Ca95-C
图 7 加固前后色度变化(a)和吸水率、孔隙率变化(b)
Figure 7. Chromatic aberration (a) and variation of water absorption and porosity (b) before and after consolidation
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