污泥灰-水泥胶凝体系的力学性能及微观分析
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摘要
利用造纸污泥灰和生活污泥灰替代部分水泥制备胶凝材料,研究了污泥灰掺量对污泥灰-水泥胶凝体系力学性能的影响,采用X射线衍射、红外光谱、扫描电镜和能谱分析手段对胶凝体系水化产物的矿物组成、化学结构及微观形貌进行研究。结果表明,随着污泥灰掺量增加,胶凝体系抗压强度不断降低,当污泥灰掺量超过40%,试样3 d抗压强度比小于5%。当水泥掺量一定,提高造纸污泥灰的掺加比例有利于胶凝体系早期强度的增长,生活污泥灰可有效提高试样后期强度,但掺量不宜过多。随造纸污泥灰掺量提高,水化产物中氢氧化钙和C—S—H凝胶生成量增大,氢氧化钙晶体由片状发育为板状,紧紧包裹于C—S—H凝胶层状结构中,造纸污泥灰中含有的文石型Ca CO3晶体具有较高的力学强度,可桥接于水化试样微观裂隙两侧,阻碍裂隙的扩展,进而提高胶凝体系的力学强度。
The present paper intends to make an exploration of the mineral composition,the chemical structure and micro-morphology of the hydration products of the cementitious system via the X-ray diffraction,the infrared spectroscopy,as well as via the electronic scanning microscopy and energy dispersive spectrometry. As is known,the papermaking sludge-ash and the domestic sludge-ash can be used to replace part of cement so as to make the cementitious materials,whereas the effect of the sludge-ash content on the mechanical properties of the sludge cement cementitious system has also been examined. The results of our experimental studies indicate that,on the condition when the cement content is fixed,it is beneficial to increase the early strength of the cementitious samples by increasing the proportion of the papermaking sludge-ash,and,then,the latter strength of the samples can be effectively improved by the domestic sludge-ash,though the amount should not be too large. However,when the cement content rate decreases,the compressive strength of the cementitious system should also be constantly decreased correspondingly. For example,when the sludge ash content is over 40%,the 3-rd compressive strength ratio of the sample should be dropped by no more than 5%. The hydration products of the sludge ash-cement cementitious system may include the calcium hydroxide,ettringite,calcite,aragonite and C—S—H gel. On the other hand,the said papermaking sludge ash tends to be able to accelerate the hydration of the calcium silicate in the cement and give off more calcium hydroxide and C—S—H gel,so as to be able to promote the early strength of the cementitious system.Nevertheless,the activated Si O2 within the household sludge ash may experience at the later stage of hydration,can be affected by the OH-and then produce a large amount of C—S—H gel and gelled,so as to accelerate the increase of the 28 d strength of the cementitious system. In addition,with the increase of the sludgeash content,the amount of the calcium hydroxide and C—S—H gel in the hydrated products has also been increased,while the calcium hydroxide crystals were to be developed from the flakes to some plates,thus,tightly encapsulated in the C—S—H gel layer. And,since the aragonite Ca CO3 crystals contained in the papermaking sludge-ash enjoy high mechanical strength,they can join the both sides of the micro-crack of the hydration sample like a bridge,to impede the expansion of the crack and improve the mechanical strength of the cementitious system.
The present paper intends to make an exploration of the mineral composition,the chemical structure and micro-morphology of the hydration products of the cementitious system via the X-ray diffraction,the infrared spectroscopy,as well as via the electronic scanning microscopy and energy dispersive spectrometry. As is known,the papermaking sludge-ash and the domestic sludge-ash can be used to replace part of cement so as to make the cementitious materials,whereas the effect of the sludge-ash content on the mechanical properties of the sludge cement cementitious system has also been examined. The results of our experimental studies indicate that,on the condition when the cement content is fixed,it is beneficial to increase the early strength of the cementitious samples by increasing the proportion of the papermaking sludge-ash,and,then,the latter strength of the samples can be effectively improved by the domestic sludge-ash,though the amount should not be too large. However,when the cement content rate decreases,the compressive strength of the cementitious system should also be constantly decreased correspondingly. For example,when the sludge ash content is over 40%,the 3-rd compressive strength ratio of the sample should be dropped by no more than 5%. The hydration products of the sludge ash-cement cementitious system may include the calcium hydroxide,ettringite,calcite,aragonite and C—S—H gel. On the other hand,the said papermaking sludge ash tends to be able to accelerate the hydration of the calcium silicate in the cement and give off more calcium hydroxide and C—S—H gel,so as to be able to promote the early strength of the cementitious system.Nevertheless,the activated Si O2 within the household sludge ash may experience at the later stage of hydration,can be affected by the OH-and then produce a large amount of C—S—H gel and gelled,so as to accelerate the increase of the 28 d strength of the cementitious system. In addition,with the increase of the sludgeash content,the amount of the calcium hydroxide and C—S—H gel in the hydrated products has also been increased,while the calcium hydroxide crystals were to be developed from the flakes to some plates,thus,tightly encapsulated in the C—S—H gel layer. And,since the aragonite Ca CO3 crystals contained in the papermaking sludge-ash enjoy high mechanical strength,they can join the both sides of the micro-crack of the hydration sample like a bridge,to impede the expansion of the crack and improve the mechanical strength of the cementitious system.
引文
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[2] HAN Qing(韩卿),RUAN Xiujuan(阮秀娟),ZHANGTuo(张拓). Study on technology of paper sludge backfill-ing into paper web[J]. Journal of Shaanxi University ofScience&Technology(陕西科技大学学报),2016,34(6):25-28.
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[5] WEI Guoxia(魏国侠),LIU Hanqiao(刘汉桥),XUXian(徐仙). Glass-ceramics made by ash fromsludge incinerator[J]. China Ceramics(中国陶瓷),2015,51(5):46-49.
[6] XIAO Yuhui(肖玉辉),ZHOU Min(周旻),WANG Teng(王腾). Research on sewage sludge ash based compositeportland cement[J]. China Water&Wastewater(中国给水排水),2017,33(21):104-108.
[7] JOOHWA T. Sludge ash as filler for portland cement con-crete[J]. Journal of Environmental Engineering,1987,113(2):345-349.
[8] CYR M,COUTAND M,CLASTRES P. Technologicaland environmental behavior of sewage sludge ash(SSA)in cement-based materials[J]. Cement and Concrete Re-search,2007,37(8):1278-1289.
[9] CHEN M Z,BLANC D,GAUTIER M,et al. Environ-mental and technical assessments of the potential utiliza-tion of sewage sludge ashes(SSAs)as secondary raw ma-terials in construction[J]. Waste Management,2013,33(5):1268-1275.
[10] BAEZA F,PAYJ,GALAO O,et al. Blending of in-dustrial waste from different sources as partial substitu-tion of Portland cement in pastes and mortars[J]. Con-struction and Building Materials,2014,66:645-653.
[11] DAI Rui(戴睿),HU Chenyang(胡晨阳),FAN Zhifan(范志凡). The study of strength characteristics ofsludge concrete[J]. Coal Ash(粉煤灰),2016,5:10-12.
[12] CHEN Gang(陈港), LIU Yaping(刘雅萍),FANG Zhiqiang(方志强). Preparation of calciumcarbonate composite filler coated with titanium dioxideand its application in papermaking[J]. Journal of SouthChina University of Technology:Natural Science Edition(华南理工大学学报:自然科学版),2011,39(8):87-89.
[13] ZHANG Hongwei(张宏伟),YU Dede(于德德). Anal-ysis of pressure-resistance calculating model of carbon-nanotubes/carbon black/silicone rubber composite mate-rial[J]. Journal of Functional Materials(功能材料),2013,44(5):665-668.
[14] WANG Changlong(王长龙),NI Wen(倪文),LI Dezhong(李德忠),et al. Experimental study of using ShanxiLingqiu low-silica iron ore tailings to produce aerated con-crete[J]. Journal of China Coal Society(煤炭学报),2012,37(7):1129-1133.
[15] ZHANG Chunmei(章春梅),RAMACHANDRAN V S.Effect of calcium carbonate microaggregate on hydrationof three calcium silicate[J]. China Concrete(混凝土世界),2013(6):52-57.
[16] FENG Guorui(冯国瑞),REN Yafeng(任亚峰),ZHANGXuyan(张绪言). The activating experimental research offly ash for mining filling material in Tashan Mine[J]. Jour-nal of China Coal Society(煤炭学报),2011,36(5):272-275.
[17] DONG Jingliang(董晶亮),ZHANG Tingting(张婷婷),WANG Lijiu(王立久). Alkaliactivated modi-fied steel slag/Pishasand stone composites[J]. ActaMateriae Compositae Sinica(复合材料学报),2016,33(1):132-135.
[18] SHI Di(史迪),ZHANG Wensheng(张文生),YE Ji-ayuan(叶家元). Effects of curing condition on proper-ties,reaction products and microsetructure of calciumsilicat slag-based alkali-activated cementitious materials[J]. Journal of the Chinese Ceramic Society(硅酸盐学报),2017,45(8):1080-1085.
[19] MA Zhaoyang(马赵杨),DU Changwen(杜昌文),ZHOU Jianmi(周健民). Characterization of soil calciumcarbonate using mid-infrared photoacou[J]. Spectroscopyand Spectral Analysis(光谱学与光谱分析),2012,32(5):1255-1258.
[20] MOZGAWA W,DEJA J. Spectroscopic studies of alka-line activated slag geopolymers[J]. Journal of MolecularStructure,2009,924:434-441.
[21] WANG Lei(王磊),HE Zhen(何真),ZHANG Bo(张博). Polymerization mechanism of C—S—H:Identifiedby FTIR and NMR[J]. Journal of Building Materials(建筑材料学报),2011,14(4):447-451.
[22] FU Bo(傅博),YANG Changhui(杨长辉),CHENGZhenyun(程臻贇). Influence of high temperature onmicrostructure of alkali-activated slag cement pastes[J].Journal of Huazhong University of Technology:NaturalScience Edition(华中科技大学学报:自然科学版),2013,41(5):34-38.
[23] LI Xingkui(李兴奎),ZHUANG Jia(庄稼). Mechanicsperformance of OU cement paste reinforced by calciumcarbonate[J]. Oilfield Chemistry(油田化学),2015,32(3):323-327.
[2] HAN Qing(韩卿),RUAN Xiujuan(阮秀娟),ZHANGTuo(张拓). Study on technology of paper sludge backfill-ing into paper web[J]. Journal of Shaanxi University ofScience&Technology(陕西科技大学学报),2016,34(6):25-28.
[3] FAVA G,RUEELO M L,CORINALDESI V. Paper millsludge ash as supplementary cementitious material[J].Journal of Materials in Civil Engineering,2011,23(6):772-776.
[4] YUAN Yanyan(袁言言),HUANG Ying(黄瑛),ZHANG Dong(张冬). Energy utilization and pollu-tants emission in sewage sludge incinera[J]. Journalof Chinese Society of Power Engineering(环境工程学报),2016,36(11):935-939.
[5] WEI Guoxia(魏国侠),LIU Hanqiao(刘汉桥),XUXian(徐仙). Glass-ceramics made by ash fromsludge incinerator[J]. China Ceramics(中国陶瓷),2015,51(5):46-49.
[6] XIAO Yuhui(肖玉辉),ZHOU Min(周旻),WANG Teng(王腾). Research on sewage sludge ash based compositeportland cement[J]. China Water&Wastewater(中国给水排水),2017,33(21):104-108.
[7] JOOHWA T. Sludge ash as filler for portland cement con-crete[J]. Journal of Environmental Engineering,1987,113(2):345-349.
[8] CYR M,COUTAND M,CLASTRES P. Technologicaland environmental behavior of sewage sludge ash(SSA)in cement-based materials[J]. Cement and Concrete Re-search,2007,37(8):1278-1289.
[9] CHEN M Z,BLANC D,GAUTIER M,et al. Environ-mental and technical assessments of the potential utiliza-tion of sewage sludge ashes(SSAs)as secondary raw ma-terials in construction[J]. Waste Management,2013,33(5):1268-1275.
[10] BAEZA F,PAYJ,GALAO O,et al. Blending of in-dustrial waste from different sources as partial substitu-tion of Portland cement in pastes and mortars[J]. Con-struction and Building Materials,2014,66:645-653.
[11] DAI Rui(戴睿),HU Chenyang(胡晨阳),FAN Zhifan(范志凡). The study of strength characteristics ofsludge concrete[J]. Coal Ash(粉煤灰),2016,5:10-12.
[12] CHEN Gang(陈港), LIU Yaping(刘雅萍),FANG Zhiqiang(方志强). Preparation of calciumcarbonate composite filler coated with titanium dioxideand its application in papermaking[J]. Journal of SouthChina University of Technology:Natural Science Edition(华南理工大学学报:自然科学版),2011,39(8):87-89.
[13] ZHANG Hongwei(张宏伟),YU Dede(于德德). Anal-ysis of pressure-resistance calculating model of carbon-nanotubes/carbon black/silicone rubber composite mate-rial[J]. Journal of Functional Materials(功能材料),2013,44(5):665-668.
[14] WANG Changlong(王长龙),NI Wen(倪文),LI Dezhong(李德忠),et al. Experimental study of using ShanxiLingqiu low-silica iron ore tailings to produce aerated con-crete[J]. Journal of China Coal Society(煤炭学报),2012,37(7):1129-1133.
[15] ZHANG Chunmei(章春梅),RAMACHANDRAN V S.Effect of calcium carbonate microaggregate on hydrationof three calcium silicate[J]. China Concrete(混凝土世界),2013(6):52-57.
[16] FENG Guorui(冯国瑞),REN Yafeng(任亚峰),ZHANGXuyan(张绪言). The activating experimental research offly ash for mining filling material in Tashan Mine[J]. Jour-nal of China Coal Society(煤炭学报),2011,36(5):272-275.
[17] DONG Jingliang(董晶亮),ZHANG Tingting(张婷婷),WANG Lijiu(王立久). Alkaliactivated modi-fied steel slag/Pishasand stone composites[J]. ActaMateriae Compositae Sinica(复合材料学报),2016,33(1):132-135.
[18] SHI Di(史迪),ZHANG Wensheng(张文生),YE Ji-ayuan(叶家元). Effects of curing condition on proper-ties,reaction products and microsetructure of calciumsilicat slag-based alkali-activated cementitious materials[J]. Journal of the Chinese Ceramic Society(硅酸盐学报),2017,45(8):1080-1085.
[19] MA Zhaoyang(马赵杨),DU Changwen(杜昌文),ZHOU Jianmi(周健民). Characterization of soil calciumcarbonate using mid-infrared photoacou[J]. Spectroscopyand Spectral Analysis(光谱学与光谱分析),2012,32(5):1255-1258.
[20] MOZGAWA W,DEJA J. Spectroscopic studies of alka-line activated slag geopolymers[J]. Journal of MolecularStructure,2009,924:434-441.
[21] WANG Lei(王磊),HE Zhen(何真),ZHANG Bo(张博). Polymerization mechanism of C—S—H:Identifiedby FTIR and NMR[J]. Journal of Building Materials(建筑材料学报),2011,14(4):447-451.
[22] FU Bo(傅博),YANG Changhui(杨长辉),CHENGZhenyun(程臻贇). Influence of high temperature onmicrostructure of alkali-activated slag cement pastes[J].Journal of Huazhong University of Technology:NaturalScience Edition(华中科技大学学报:自然科学版),2013,41(5):34-38.
[23] LI Xingkui(李兴奎),ZHUANG Jia(庄稼). Mechanicsperformance of OU cement paste reinforced by calciumcarbonate[J]. Oilfield Chemistry(油田化学),2015,32(3):323-327.
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