基于界面改性的碳纳米管水泥基复合材料力学性能
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摘要
针对碳纳米管水泥基复合材料中碳纳米管与水泥基体界面结合弱的技术问题,以聚乙烯醇和聚丙烯酰胺分别作为界面桥连剂,探究桥连剂通过强化碳纳米管与水泥基体间的界面对碳纳米管水泥基复合材料力学性能的增强效果;利用阿拉伯树胶作为碳纳米管的水性分散剂,采用普通和表面带有羧基的2种碳纳米管制备5组不同碳纳米管掺量的水泥基复合材料,对其进行了不同龄期的抗压、抗折强度测试,并利用扫描电子显微镜(SEM)在断口处对碳纳米管与水泥基体界面区进行了微结构分析。结果表明:采用羧基碳纳米管并掺入桥连剂的水泥基复合材料力学强度得到最大提升,相较于配合比相同但未加入碳纳米管的基准组,加入桥连剂的羧基碳纳米管水泥基复合材料28 d抗折、抗压强度分别提升了47.4%和22.7%,仅加入羧基碳纳米管的水泥基复合材料则提高了15.4%和8.84%;SEM测试发现加入桥连剂的碳纳米管水泥基复合材料破坏断口处碳纳米管与水泥基体连接处结构密实,未加入桥连剂试件断口处碳纳米管被完全拔出,说明桥连剂改善了碳纳米管与水泥基体间界面结合,使二者近似成为一个整体进行受力,增强了碳纳米管的拔出效应,水泥基体断裂时碳纳米管拔出吸收了更多的破坏能,显著改善了水泥基复合材料的宏观力学性能。
Aiming at the technical problems of weak bonding capacity of interface between carbon nanotubes and cement substrate in carbon nanotubes reinforced cement composites. Polyvinyl alcohol and polyacrylamide were used as interfacial bridging agents to investigate the effect of bridging agents on the mechanical properties of carbon nanotube-based cement composites by strengthening the interface between the carbon nanotubes and the cement matrix, Arabic gum was used as water-based dispersant for carbon nanotubes. Five kinds of cement-based composites with different amounts of carbon nanotubes were prepared by using two kinds of carbon nanotubes with common and surface carboxyl groups. Different ages compressive, flexural strength of specimens were tested. The microstructure of the interfacial region of carbon nanotubes and cement was analyzed by scanning electron microscopy(SEM) at the fracture site. The results show that the mechanical strength of cement-based composites with carbon nanotubes and bridging agents is maximized. The 28-day flexural strength and compressive strength of the carboxy nanotube cement composites added with bridging agent are 47.4% and 22.7% higher than those of the same group without the addition of carbon nanotubes. The 28-day flexural strength and compressive strength of the carboxy nanotube cement composites are 15.4% and 8.84% higher than baseline group. The SEM test found that the carbon nanotubes and the cement matrix are closely connected at the fracture site of the carbon nanotubes cement-matrix composite material added with the bridging agent, while the carbon nanotubes at the fractures of the specimens without the bridging agent are completely pulled out.This shows that the bridging agent improves the bonding between the carbon nanotubes and the cement matrix, so that the two are approximately subjected to a force. The pull-out effect of carbon nanotubes is enhanced, more damage can be absorbed by the carbon nanotubes when the cement matrix is broken, and the macro-mechanical properties of the cement matrix composites are significantly improved.
Aiming at the technical problems of weak bonding capacity of interface between carbon nanotubes and cement substrate in carbon nanotubes reinforced cement composites. Polyvinyl alcohol and polyacrylamide were used as interfacial bridging agents to investigate the effect of bridging agents on the mechanical properties of carbon nanotube-based cement composites by strengthening the interface between the carbon nanotubes and the cement matrix, Arabic gum was used as water-based dispersant for carbon nanotubes. Five kinds of cement-based composites with different amounts of carbon nanotubes were prepared by using two kinds of carbon nanotubes with common and surface carboxyl groups. Different ages compressive, flexural strength of specimens were tested. The microstructure of the interfacial region of carbon nanotubes and cement was analyzed by scanning electron microscopy(SEM) at the fracture site. The results show that the mechanical strength of cement-based composites with carbon nanotubes and bridging agents is maximized. The 28-day flexural strength and compressive strength of the carboxy nanotube cement composites added with bridging agent are 47.4% and 22.7% higher than those of the same group without the addition of carbon nanotubes. The 28-day flexural strength and compressive strength of the carboxy nanotube cement composites are 15.4% and 8.84% higher than baseline group. The SEM test found that the carbon nanotubes and the cement matrix are closely connected at the fracture site of the carbon nanotubes cement-matrix composite material added with the bridging agent, while the carbon nanotubes at the fractures of the specimens without the bridging agent are completely pulled out.This shows that the bridging agent improves the bonding between the carbon nanotubes and the cement matrix, so that the two are approximately subjected to a force. The pull-out effect of carbon nanotubes is enhanced, more damage can be absorbed by the carbon nanotubes when the cement matrix is broken, and the macro-mechanical properties of the cement matrix composites are significantly improved.
引文
[1] 王德刚.碳纳米管增强水泥基复合材料力学性能模拟[D].大连:大连理工大学,2011. WANG De-gang.Mechanical simulation of carbon nanotube reinforced cement composites[D].Dalian:Dalian University of Technology,2011.
[2] 韩瑜.碳纳米管的分散性及其水泥基复合材料力学性能[D].大连:大连理工大学,2013. HAN Yu.Dispersion of carbon nanotubes and the mechanical properties of carbon nanotubes reinforced cement-based composites[D].Dalian:Dalian University of Technology,2013.
[3] 张喜娥.碳纳米管水泥基复合材料的力学性能和抗冻性能研究[J].硅酸盐通报,2015,34(9):2686-2690. ZHANG Xi-e.Mechanical and frost resistance performance of multi-walled carbon nanotubes reinforced cement composites[J].Bulletin of the Chinese Ceramic Society,2015,34(9):2686-2690.
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[5] 吕生华,孙婷,刘晶晶,等.氧化石墨烯纳米片层对水泥基复合材料的增韧效果及作用机制[J].复合材料学报,2014,31(3):644-652. LU Sheng-hua,SUN Ting,LIU Jing-jing,et al.Toughening effect and mechanism of graphene oxide nanosheets on cement matrix composites[J].Acta Materia Compositae Sinica,2014,31(3):644-652.
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[8] LAHIRI I,SEELABOYINA R,HWANG J Y,et al.Enhanced field emission from multi-walled carbon nanotubes grown on pure copper substrate[J].Carbon,2010,48(5):1531-1538.
[9] YAN J,LIU J,FAN Z,et al.High-performance supercapacitor electrodes based on highly corrugated grapheme sheets[J].Carbon,2012,50(6):2179-2188.
[10] JIN H,HELLER D A,KALBACOVA M,et al.Detection of single-molecule H2O2 signalling from epidermal growth factor receptor using fluorescent single-walled carbon nanotubes[J].Nature Nanotechnology,2010,5(4):302-309.
[11] KAUFFMAN D R,SORESCU D C,SCHOFIELD D P,et al.Understanding the sensor response of metal-decorated carbon nanotubes[J].Nano Letters,2010,10(3):958-963.
[12] 王梦博.碳纳米管水泥基复合材料的力学与抗渗透性研究[D].哈尔滨:哈尔滨工业大学,2013. WANG Meng-bo.Research on mechanism and impervious behavious of cement based composites with carbon nanotube[D].Harbin:Harbin Institute of Technology,2013.
[13] 刘巧玲.碳纳米管增强水泥基复合材料多尺度性能及机理研究[D].南京:东南大学,2015. LIU Qiao-ling.Multi-scale properties and mechanism of carbon nanotubes/cement nanocomposites[D].Nanjing:Southeast University,2015.
[14] 罗健林,段忠东.碳纳米管的分散性及其增强水泥材料力学性能[J].建筑结构学报,2008,29(增):246-250. LUO Jian-lin,DUAN Zhong-dong.Dispersivity of multi-walled carbon nanotubes (MWCNT) and mechanical properties of MWCNT reinforced cement-based composite[J].Journal of Building Structures,2008,29(S):246-250.
[15] 唐倩兰,黄俊,田国鑫.碳纳米管分散性及其水泥基复合材料力学性能的研究进展[J].功能材料,2017,48(6):6042-6049. TANG Qian-lan,HUANG Jun,TIAN Guo-xin.Dispersion of carbon nanotubes and research progress on mechanical properties of carbon nanotubes cement-based composites[J].Journal of Functional Materials,2017,48(6):6042-6049.
[16] NASIBULINA L I,ANOSHKIN I V,NASIBULIN A G,et al.Effect of carbon nanotube aqueous dispersion quality on mechanical properties of cement composite[J].Journal of Nanomaterials,2012(2012):1-6.
[17] HAN B G,YU X,OU J P.Multifunctional and smart carbon nanotube reinforced cement-based materials[M]//GOPALAKRISHNAN K,BIRGISSON B,TAYLOR P,et al.Nanotechnology in Civil Infrastructure.Berlin:Springer,2011:1-47.
[18] SUN G,LIANG R,LU Z,et al.Mechanism of cement/carbon nanotube composites with enhanced mechanical properties achieved by interfacial strengthening[J].Construction & Building Materials,2016,115:87-92.
[19] EKINCIOGLU O,OZKUL M H,STRUBLE L J,et al.Optimization of material characteristics of macro-defect free cement[J].Cement & Concrete Composites,2012,34(4):556-565.
[20] 李永鹏,何锐,陈拴发,等.聚丙烯酰胺与羟乙基纤维素对砂浆性能的影响[J].武汉理工大学学报,2012,34(7):28-31. LI Yong-peng,HE Rui,CHEN Shuan-fa,et al.Effect of polyacrylamide and hydroxyethyl cellulose ether on the performance of the cement mortar[J].Journal of Wuhan University of Technology,2012,34(7):28-31.
[21] 李庚英,王培铭.碳纳米管-水泥基复合材料的力学性能和微观结构[J].硅酸盐学报,2005,33(1):105-108. LI Geng-ying,WANG Pei-ming.Microstructure and mechanical properties of carbon nanotubes-cement matrix composites[J].Journal of the Chinese Ceramic Society,2005,33(1):105-108.
[22] 刘帅.碳纳米管的分散性及其水泥基复合材料耐久性能[D].大连:大连理工大学,2015. LIU Shuai.Dispersion of carbon nanotubes and the durability of carbon nanotubes reinforced cement-based composites[D].Dalian:Dalian University of Technology,2015.
[23] 李素华.PVA纤维增强水泥基复合材料力学性能试验研究[D].武汉:湖北工业大学,2011. LI Su-hua.Experimental research on the mechanical properties of PVA fiber reinforced cementitious composite[D].Wuhan:Hubei University of Technology,2011.
[2] 韩瑜.碳纳米管的分散性及其水泥基复合材料力学性能[D].大连:大连理工大学,2013. HAN Yu.Dispersion of carbon nanotubes and the mechanical properties of carbon nanotubes reinforced cement-based composites[D].Dalian:Dalian University of Technology,2013.
[3] 张喜娥.碳纳米管水泥基复合材料的力学性能和抗冻性能研究[J].硅酸盐通报,2015,34(9):2686-2690. ZHANG Xi-e.Mechanical and frost resistance performance of multi-walled carbon nanotubes reinforced cement composites[J].Bulletin of the Chinese Ceramic Society,2015,34(9):2686-2690.
[4] 王宝民,张源,韩愈,等.纳米碳纤维增强水泥基复合材料的探讨[J].材料导报,2013,27(1):144-146. WANG Bao-min,ZHANG Yuan,HAN Yu,et al.Probe of carbon nanofibers reinforced cement-based composite[J].Materials Review,2013,27(1):144-146.
[5] 吕生华,孙婷,刘晶晶,等.氧化石墨烯纳米片层对水泥基复合材料的增韧效果及作用机制[J].复合材料学报,2014,31(3):644-652. LU Sheng-hua,SUN Ting,LIU Jing-jing,et al.Toughening effect and mechanism of graphene oxide nanosheets on cement matrix composites[J].Acta Materia Compositae Sinica,2014,31(3):644-652.
[6] LIU Z,TABAKMAN S,WELSHER K,et al.Carbon nanotubes in biology and medicine:In vitro and in vivo detection,imaging and drug delivery[J].Nano Research,2009,2(2):85-120.
[7] KUZNETZOV A A,LEE S B,ZHANG M,et al.Electron field emission from transparent multiwalled carbon nanotube sheets for inverted field emission displays[J].Carbon,2010,48(1):41-46.
[8] LAHIRI I,SEELABOYINA R,HWANG J Y,et al.Enhanced field emission from multi-walled carbon nanotubes grown on pure copper substrate[J].Carbon,2010,48(5):1531-1538.
[9] YAN J,LIU J,FAN Z,et al.High-performance supercapacitor electrodes based on highly corrugated grapheme sheets[J].Carbon,2012,50(6):2179-2188.
[10] JIN H,HELLER D A,KALBACOVA M,et al.Detection of single-molecule H2O2 signalling from epidermal growth factor receptor using fluorescent single-walled carbon nanotubes[J].Nature Nanotechnology,2010,5(4):302-309.
[11] KAUFFMAN D R,SORESCU D C,SCHOFIELD D P,et al.Understanding the sensor response of metal-decorated carbon nanotubes[J].Nano Letters,2010,10(3):958-963.
[12] 王梦博.碳纳米管水泥基复合材料的力学与抗渗透性研究[D].哈尔滨:哈尔滨工业大学,2013. WANG Meng-bo.Research on mechanism and impervious behavious of cement based composites with carbon nanotube[D].Harbin:Harbin Institute of Technology,2013.
[13] 刘巧玲.碳纳米管增强水泥基复合材料多尺度性能及机理研究[D].南京:东南大学,2015. LIU Qiao-ling.Multi-scale properties and mechanism of carbon nanotubes/cement nanocomposites[D].Nanjing:Southeast University,2015.
[14] 罗健林,段忠东.碳纳米管的分散性及其增强水泥材料力学性能[J].建筑结构学报,2008,29(增):246-250. LUO Jian-lin,DUAN Zhong-dong.Dispersivity of multi-walled carbon nanotubes (MWCNT) and mechanical properties of MWCNT reinforced cement-based composite[J].Journal of Building Structures,2008,29(S):246-250.
[15] 唐倩兰,黄俊,田国鑫.碳纳米管分散性及其水泥基复合材料力学性能的研究进展[J].功能材料,2017,48(6):6042-6049. TANG Qian-lan,HUANG Jun,TIAN Guo-xin.Dispersion of carbon nanotubes and research progress on mechanical properties of carbon nanotubes cement-based composites[J].Journal of Functional Materials,2017,48(6):6042-6049.
[16] NASIBULINA L I,ANOSHKIN I V,NASIBULIN A G,et al.Effect of carbon nanotube aqueous dispersion quality on mechanical properties of cement composite[J].Journal of Nanomaterials,2012(2012):1-6.
[17] HAN B G,YU X,OU J P.Multifunctional and smart carbon nanotube reinforced cement-based materials[M]//GOPALAKRISHNAN K,BIRGISSON B,TAYLOR P,et al.Nanotechnology in Civil Infrastructure.Berlin:Springer,2011:1-47.
[18] SUN G,LIANG R,LU Z,et al.Mechanism of cement/carbon nanotube composites with enhanced mechanical properties achieved by interfacial strengthening[J].Construction & Building Materials,2016,115:87-92.
[19] EKINCIOGLU O,OZKUL M H,STRUBLE L J,et al.Optimization of material characteristics of macro-defect free cement[J].Cement & Concrete Composites,2012,34(4):556-565.
[20] 李永鹏,何锐,陈拴发,等.聚丙烯酰胺与羟乙基纤维素对砂浆性能的影响[J].武汉理工大学学报,2012,34(7):28-31. LI Yong-peng,HE Rui,CHEN Shuan-fa,et al.Effect of polyacrylamide and hydroxyethyl cellulose ether on the performance of the cement mortar[J].Journal of Wuhan University of Technology,2012,34(7):28-31.
[21] 李庚英,王培铭.碳纳米管-水泥基复合材料的力学性能和微观结构[J].硅酸盐学报,2005,33(1):105-108. LI Geng-ying,WANG Pei-ming.Microstructure and mechanical properties of carbon nanotubes-cement matrix composites[J].Journal of the Chinese Ceramic Society,2005,33(1):105-108.
[22] 刘帅.碳纳米管的分散性及其水泥基复合材料耐久性能[D].大连:大连理工大学,2015. LIU Shuai.Dispersion of carbon nanotubes and the durability of carbon nanotubes reinforced cement-based composites[D].Dalian:Dalian University of Technology,2015.
[23] 李素华.PVA纤维增强水泥基复合材料力学性能试验研究[D].武汉:湖北工业大学,2011. LI Su-hua.Experimental research on the mechanical properties of PVA fiber reinforced cementitious composite[D].Wuhan:Hubei University of Technology,2011.
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