Dispersion characteristics of graphene in cement paste
-
摘要: 为研究水泥净浆中石墨烯的分散方式和分散程度的评价方法,采用不同阴离子表面活性剂作分散助剂分散石墨烯材料,通过高速物理搅拌与超声分散方法制备石墨烯分散液。采用紫外-可见分光光度法、静置沉降法、电阻率、SEM及能谱测试观测石墨烯在碱性溶液、水泥净浆及其水泥净浆水化硬化产物中的分布方式,分析它们的分散均匀性。结果表明:在水泥基材料碱性环境中,具有耐碱性高亲油基团的分散剂,引入一定程度气泡微珠有助于提高石墨烯的分散均匀性和经时稳定性及削弱石墨烯在水泥净浆中的上浮效应,同时,其断面石墨烯分散均匀性能够提高30%。采用分光光度计法、静置法和电阻法评价石墨烯在碱性溶液中的分散效果,简单有效。Abstract: In order to evaluate the dispersion method and dispersion degree of graphene in pure cement mud, different anionic surfactants were used as dispersion graphene materials, and graphene dispersion was prepared by high-speed physical mixing and ultrasonic dispersion methods.Their dispersion uniformity was analyzed by UV-visible spectrophotometry, static settlement, resistivity, SEM and energy spectroscopy test to observe the distribution of graphene in alkaline solutions, pure cement mud, and its pure cement mud hydrochemical hardening products.The results show that in the pure cement mud alkaline environment, the introduction of bubble microbeads helps to improve the dispersion uniformity of graphene and the stability for time and weaken the floating effect of graphene in pure cement mud. At the same time, the cross-section graphene dispersion uniformity can be improved by 30%. The dispersion effect of graphene in alkaline solution was evaluated by visible spectrophotometry, static settlement and resistivity, which is simple and effective.
-
Key words:
- graphene /
- cement paste /
- alkaline environment /
- dispersion performance /
- evaluation method
-
表 1 石墨烯的物理参数
Table 1. Physical parameters of graphene
Model Density/(g·cm−3) Purity
/%Conductivity characteristic Tensile modulus/GPa Electrical conductivity/(Ω−1·cm−1) Resistivity/(mΩ·cm) K-1 0.2 >99.5 7.14 1.4 1000 表 2 所用分散剂类型
Table 2. Types of dispersants used
Reagent
numberReagent type KT1 D.BASF plurafac LF221: An alkoxy compound of a nonbranched fatty alcohol KT2 Coconut diethanol amide 6501: Coconut oil fatty acid diethanolamide KT3 Triton(TM) CF-10 surfactant: Water-soluble non-ionic surfactant KT4 303: Fatty alcohol polyoxyethylene ether sodium sulfate surfactant KT5 Dispersible liquid A: olyvinylpyrrolidone (PVP) KT6 Polycarboxylate superplasticizer HWR-S KT7 Plant polyene phenol polyoxyethylene ether Nsf-10e KT8 0.02% A5 hardening accelerating WR-A KT9 MZY-A5 HPWR-S KT10 Rosin modified polymer SY-1 表 3 试剂类型
Table 3. Reagent type
Reagent number Group Reagent type A(pH=7) B(pH>7) 100 mL water 100 mL NaOH 20 mg graphene 1 KT1 - Add None Add 2 KT2 - Add None Add 3 KT3 - Add None Add 4 KT4 - Add None Add 5 KT6 - Add None Add 6 Blank - Add None Add 7 - KT3 None Add Add 8 - KT1 None Add Add 9 - KT2 None Add Add 10 - KT6 None Add Add 11 - KT4 None Add Add 12 - KT7 None Add Add 13 - KT8 None Add Add 14 - KT5 None Add Add 15 - KT5 Add None Add 16 - KT9 None Add Add 17 - KT10 None Add Add 18 - Blank None Add Add -
[1] 吴林烽. 氧化石墨烯纳米片对水泥基材料性能的影响[D]. 重庆: 重庆大学, 2017.WU Linfeng. Effect of graphene oxide nanosheets on properties of cementitious materials[D]. Chongqing: Chongqing University, 2017(in Chinese). [2] 匡达, 胡文彬. 石墨烯复合材料的研究进展[J]. 无机材料学报, 2013, 28(3):235-246. doi: 10.3724/SP.J.1077.2013.12345KUANG Da, HU Wenbin. Development of graphene composites[J]. Journal of Inorganic Materials,2013,28(3):235-246(in Chinese). doi: 10.3724/SP.J.1077.2013.12345 [3] 陈冠雄, 谈紫琪, 赵元, 等. 面向能源领域的石墨烯研究[J]. 中国科学: 化学, 2013, 43(6):704-715. doi: 10.1360/032013-77CHEN Guanxiong, TAN Ziqi, ZHAO Yuan, et al. Applications of graphene for energy storage and conversion[J]. Chinese Science: Chemistry,2013,43(6):704-715(in Chinese). doi: 10.1360/032013-77 [4] FEHER A, GOSPODAREV I A, GRISHAEV V I, et al. Effect of defects on the quasiparticle spectra of graphite and graphene[J]. Low Temperature Physics,2009,35(8):862-871. doi: 10.1063/1.3224726 [5] WEI J C, INAM F. Processing of epoxy/graphene nanocomposites: Effects of surfactants[J]. Journal of Polymer Science & Applications,2017,1(1):1000101. [6] LEE C G, WEI X D, KYSAR J W, et al. Measurement of the elastic properties and intrinsic strength of monolayer grapheme[J]. Science,2008,321(5887):385-388. doi: 10.1126/science.1157996 [7] LIN C Q, WEI W, HU Y H. Catalytic behavior of graphene oxide for cement hydration process[J]. Journal of Physics and Chemistry of Solids,2015,89(3):128-133. doi: 10.1016/j.jpcs.2015.11.002 [8] LV S H, MA Y J, QIU C C, et al. Effect of graphene oxide nanosheets of microstructure and mechanical properties of cement composites[J]. Construction and Building Materials,2013,49:121-127. doi: 10.1016/j.conbuildmat.2013.08.022 [9] LV S H, LIU J J, SUN T, et al. Effect of GO nanosheets on shapes of cement hydration crystals and their formation process[J]. Construction and Building Materials,2014,64:231-239. doi: 10.1016/j.conbuildmat.2014.04.061 [10] HORSZCZARUK E, MIJOWSKA E, KALENCZUK R J, et al. Nanocomposite of cement/graphene oxide—Impact on hydration kinetics and Young’s modulus[J]. Construction and Building Materials,2015,78:234-242. doi: 10.1016/j.conbuildmat.2014.12.009 [11] ZHU P, LI H, LING Q, et al. Mechanical properties and microstructure of a graphene oxide-cement composite[J]. Cement and Concrete Composites,2015,58:140-147. doi: 10.1016/j.cemconcomp.2015.02.001 [12] BABAK F, ABOLFAZL H, ALIMORAD R, at al. Preparation and mechanical properties of graphene oxide: Cement nanocomposites[J]. The Scientific World Journal,2014,2014(4):276323. doi: 10.1155/2014/276323 [13] SAMUEL C, ZHU P, JAY G S, et al. Nano reinforced cement and concrete composites and new perspective from graphene oxide[J]. Construction and Building Materials,2014,73:113-124. doi: 10.1016/j.conbuildmat.2014.09.040 [14] 王琴, 王健, 刘伯伟, 等. 多壁碳纳米管水泥基复合材料的压敏性能研究[J]. 硅酸盐通报, 2016, 35(9):2733-2740. doi: 10.16552/j.cnki.issn1001-1625.2016.09.007WANG Qin, WANG Jian, LIU Bowei, et al. Study on pressure sensitivity of multiwalled carbon nanotubes cement-based composites[J]. Silicate Bulletin,2016,35(9):2733-2740(in Chinese). doi: 10.16552/j.cnki.issn1001-1625.2016.09.007 [15] 杜涛. 氧化石墨烯水泥基复合材料性能研究[D]. 哈尔滨: 哈尔滨工业大学, 2014.DU Tao. Study on properties of graphene oxide cement-based composites[D]. Harbin: Harbin Institute of Technology, 2014(in Chinese). [16] 彭晖, 戈娅萍, 杨振天, 等. 氧化石墨烯增强水泥基复合材料的力学性能及微观结构[J]. 复合材料学报, 2018, 35(8):2132-2139. doi: 10.13801/j.cnki.fhclxb.20170919.001PENG Hui, GE Yaping, YANG Zhentian, et al. Mechanical properties and microstructure of graphene oxide reinforced cementbased composites[J]. Acta Materiae Compositae Sinica,2018,35(8):2132-2139(in Chinese). doi: 10.13801/j.cnki.fhclxb.20170919.001 [17] 吴其胜, 陈宝锐, 诸华军, 等. 热压制备改性石墨烯-水泥基复合材料: 改善微观结构、导热性能和力学性能[J]. 材料导报, 2018, 32(10):1701-1706. doi: 10.11896/j.issn.1005-023X.2018.10.025WU Qisheng, CHEN Baorui, ZHU Huajun, et al. Preparation of modified graphene-cement composites by hot pressing: Improvement of microstructure, thermal conductivity and mechanical properties[J]. Materials Report,2018,32(10):1701-1706(in Chinese). doi: 10.11896/j.issn.1005-023X.2018.10.025 [18] 韩瑞杰, 程忠庆, 高屹, 等. 多层石墨烯/钢纤维复合砂浆导电性能研究[J]. 硅酸盐通报, 2020, 39(1):34-40. doi: 10.16552/j.cnki.issn1001-1625.2020.01.004HAN Ruijie, CHENG Zhongqing, GAO Qi, et al. Study on electrical conductivity of multilayer graphene/steel fiber composite mortar[J]. Silicate Bulletin,2020,39(1):34-40(in Chinese). doi: 10.16552/j.cnki.issn1001-1625.2020.01.004 [19] SHAH S P, KONSTA-GDOUTOS M S, METAXA Z S. Advanced cement based nanocomposites[M]. Netherlands: Springer, 2011: 313-327. [20] 吕生华, 罗潇倩, 张佳, 等. 氧化石墨烯调控水泥基材料形成大规模规整结构及其性能表征[J]. 材料导报, 2017, 31(24):10-14. doi: 10.11896/j.issn.1005-023X.2017.024.003LV Shenghua, LUO Xiaoqian, ZHANG Jia, et al. Graphene oxide regulates the formation of large-scale structure and characterization of cementitious materials[J]. Materials Report,2017,31(24):10-14(in Chinese). doi: 10.11896/j.issn.1005-023X.2017.024.003 [21] YAN X T, ZHENG D P, YANG H B, et al. Study of optimizing graphene oxide dispersion and properties of the resulting cement mortars[J]. Construction and Building Materials,2020,257:119477. doi: 10.1016/j.conbuildmat.2020.119477 [22] ALKHATEB H, Al-OSTAZ A, CHENG A H D, et al. Materials genome for graphene-cement nanocomposites[J]. Journal of Nanomechanics and Micromechanics,2013,3(3):67-77. doi: 10.1061/(ASCE)NM.2153-5477.0000055 [23] 徐凯丽, 张云升. 分散剂种类及浓度对石墨烯水性浆料稳定性的影响[C]. 西安: 第一届先进材料前沿学术会议, 2016: 170-174.XU Kaili, ZHANG Yunsheng. Effect of dispersant type and concentration on the stability of graphene aqueous slurry[C]. Xi'an: The First Advanced Materials Frontiers Academic Conference, 2016: 170-174(in Chinese). [24] 魏伟, 吕伟, 杨全红. 高浓度石墨烯水系分散液及其气液界面自组装膜[J]. 新型炭材料, 2011, 26(1):36-40.WEI Wei, LV Wei, YANG Quanhong. Graphene aqueous dispersion and its gas liquid interface self-assembled monolayer[J]. New Carbon Materials,2011,26(1):36-40(in Chinese). [25] 王建. 氧化石墨烯在水环境中絮凝行为及作用机制研究[D]. 北京: 华北电力大学, 2018.WANG Jian. Investigation of graphene oxide coagulation behaviour and interaction mechanism in water environment[D]. Beijing: North China Electric Power University, 2018(in Chinese). [26] 何真, 祝雯, 张丽君, 等. 粉煤灰对水泥砂浆早期电学行为与开裂敏感性影响研究[J]. 长江科学院院报, 2005(2):43-46. doi: 10.3969/j.issn.1001-5485.2005.02.012HE Zhen, ZHU Wen, ZHANG Lijun, et al. Effect of fly ash on early electrical behavior and cracking sensitivity of cement mortar[J]. Journal of the Changjiang Academy of Sciences,2005(2):43-46(in Chinese). doi: 10.3969/j.issn.1001-5485.2005.02.012 [27] LV J Y, TIAN B, QUAN L, et al. Study on the in fluence of benign temperature induced admixture on thermal induced performance of cement concrete[C]. 2021 World Transport Convention. Xi'an: China Highway & Transportation Society , 2021: 167-173.