蒸养和蒸压条件下粉煤灰水泥浆体中铝配位分布规律
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摘要
采用XRD、~(27 )Al核磁共振测试方法,研究了蒸养和蒸压条件下粉煤灰水泥浆体中铝配位分布的规律。结果表明:蒸养温度升高可提高粉煤灰火山灰效应,增大四配位铝(Al[4])进入C-S-H的数量,促进水钙沸石矿物生成;加快AFt中六配位铝(Al[6])向AFm转化,增大第三类水化铝酸盐(Third aluminate hydrate,TAH)、含硅水化石榴石、水化石榴石中Al[6]生成量,但不影响莫来石中五配位铝(Al[5])的配位状态。蒸压养护提高粉煤灰火山灰效应显著高于蒸养,升高蒸压温度和延长蒸压时间,可明显提高含铝托勃莫来石和水钙沸石的生成量;同时,不仅可提高AFt、AFm分解向TAH转化程度,而且促进粉煤灰反应形成水化氢氧铝钙石、水化铝酸二钙和TAH,增大莫来石中Al[5]向Al[6]转化程度,使TAH在Al[6]分布中成为主体含铝相。
The distribution of aluminum ions coordination in Portland cement pastes with fly ash at steam-cured and autoclaved condition was investigated by XRD and ~(27 )Al magic angle spinning(MAS)nuclear magnetic resonance(NMR).The results indicate that raising the steam-cured temperature can enhance the pozzolanic effect of fly ash,increase the degree of tetrahedral coordination Al ~(3+)(Al[4])entering into the C-S-H structure,and promote the formation of gismondine.Meanwhile,it also can accelerate the transformation from hexa-coordination Al ~(3+)(Al[6])in AFt to AFm,and increase the amount of Al[6]in TAH(Third aluminate hydrate),katoite silication and katoite.But the penta-coordination Al ~(3+)(Al[5])in mullite will be not influenced.The pozzolanic effect of fly ash at autoclaved condition is significantly higher than that at steam-cured condition,and raising the autoclaved temperature and prolonging the cured age can significantly increase the formation amount of Al-tobermorite and gismondine.In addition,they can not only increase the degree of AFt and AFm transforming to TAH,but also improve the formation of calcium aluminum oxide hydroxide hydrate,Ca_2Al_2O_5·6H_2O and TAH through the reaction of fly ash,and increase the transformation of Al[5]in mullite to Al[6],resulting in that TAH will be the major aluminum-containing phase for the distribution of the Al[6].
The distribution of aluminum ions coordination in Portland cement pastes with fly ash at steam-cured and autoclaved condition was investigated by XRD and ~(27 )Al magic angle spinning(MAS)nuclear magnetic resonance(NMR).The results indicate that raising the steam-cured temperature can enhance the pozzolanic effect of fly ash,increase the degree of tetrahedral coordination Al ~(3+)(Al[4])entering into the C-S-H structure,and promote the formation of gismondine.Meanwhile,it also can accelerate the transformation from hexa-coordination Al ~(3+)(Al[6])in AFt to AFm,and increase the amount of Al[6]in TAH(Third aluminate hydrate),katoite silication and katoite.But the penta-coordination Al ~(3+)(Al[5])in mullite will be not influenced.The pozzolanic effect of fly ash at autoclaved condition is significantly higher than that at steam-cured condition,and raising the autoclaved temperature and prolonging the cured age can significantly increase the formation amount of Al-tobermorite and gismondine.In addition,they can not only increase the degree of AFt and AFm transforming to TAH,but also improve the formation of calcium aluminum oxide hydroxide hydrate,Ca_2Al_2O_5·6H_2O and TAH through the reaction of fly ash,and increase the transformation of Al[5]in mullite to Al[6],resulting in that TAH will be the major aluminum-containing phase for the distribution of the Al[6].
引文
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[16]Meller N,Kyritsis K,Hall C.The hydrothermal decomposition of calcium monosulfoaluminate 14-hydrate to katoite hydrogarnet andβ-anhydrite:an in-situ synchrotron X-ray diffraction study[J].Journal of Solid State Chemistry,2009,182(10):2743-2747.
[17]Yang Nanru,Yue Wenhai.Atlas manual of inorganic non-metallic materials[M].Wuhan:Wuhan University of Technology Press,2000(in Chinese).杨南如,岳文海.无机非金属材料图谱手册[M].武汉:武汉工业大学出版社,2000.
[2]Hu C G,Hu S G,Ding Q J,et al.Effect of curing regime on degree of Al 3+substituting for Si 4+in C-S-H gels of hardened Portland cement pastes[J].Journal of Wuhan University of Technology-Mater Sci Ed,2014,29(3):546-552.
[3]Gir2o A V,Richardson I G,Porteneuve C B,et al.Composition,morphology and nanostructure of C-S-H in white Portland cement pastes hydrated at 55°C[J].Cement and Concrete Research,2007,37(12):1571-1582.
[4]Gir2o A V,Richardson I G,Taylor R,et al.Composition,morphology and nanostructure of C-S-H in 70%white Portland cement-30%fly ash blends hydrated at55°C[J].Cement and Concrete Research,2010,40(9):1350-1359.
[5]Gir2o A V,Richardson I G,Porteneuve C B,et al.Composition,morphology and nanostructure of C-S-H in white Portland cement-fly ash blends hydrated at 85℃[J].Advances in Applied Ceramics,2007,106(6):283-293.
[6]Bach T T H,Coumes C C D,Pochard I,et al.Influence of temperature on the hydration products of low pH cements[J].Cement and Concrete Research,2012,42(6):805-817.
[7]Cheyrezy M,Maret V,Frouin L.Microstructural analysis of RPC(reactive powder concrete)[J].Cement and Concrete Research,1995,25(7):1491-1500.
[8]Yazlcl H,Yardlmcl M Y,Yigiter H,et al.Mechanical properties of reactive powder concrete containing high volumes of ground granulated blast furnace slag[J].Cement and Concrete Composites,2010,32(8):639-648.
[9]Zanni H,Cheyrezy M,Maret V,et al.Investigation of hydration and pozzolanic reaction in reactive power concrete(RPC)using 29Si NMR[J].Cement and Concrete Research,1996,26(1):93-100.
[10]Andersen M D,Jakobsen H J,Skibsted J.Incorporation of aluminum in the calcium silicate hydrate(C-S-H)of hydrated Portland cements:a high-field 27 Al and 29Si MAS NMR investigation[J].Inorganic Chemistry,2003,42(7):2280-2287.
[11]Andersen M D,Jakobsen H J,Skibsted J.A new aluminium-hydrate species in hydrated Portland cements characterized by 27 Al and 29Si MAS NMR spectroscopy[J].Cement and Concrete Research,2006,36(1):3-17.
[12]Hu Chengguang.Effect of temperature and sulfate attack on microstructure of C-S-H in Portland cement pastes with fly ash[D].Wuhan:Wuhan University of Technology,2014(in Chinese).胡晨光.温度和硫酸盐侵蚀对粉煤灰水泥浆体C-S-H微结构的影响研究[D].武汉:武汉理工大学,2014.
[13]Lippmaa E,Maegi M,Samoson A,et al.Structural studies of silicates by solid-state high-resolution 29Si NMR[J].Journal American Chemical Society,1980,11(41):4889-4893.
[14]Renaudin G,Russias J,Leroux F,et al.Structural characterization of C-S-H and C-A-S-H samples-Part II:local environment investigated by spectroscopic analyses[J].Journal Solid State Chemistry,2009,182(12):3320-3329.
[15]Andersen M D,Jakobsen H J,Skibsted J.Characterization of white Portland cement hydration and the C-S-H structure in the presence of sodium aluminate by 27 Al and29Si MAS NMR spectroscopy[J].Cement and Concrete Research,2004,34(5):857-868.
[16]Meller N,Kyritsis K,Hall C.The hydrothermal decomposition of calcium monosulfoaluminate 14-hydrate to katoite hydrogarnet andβ-anhydrite:an in-situ synchrotron X-ray diffraction study[J].Journal of Solid State Chemistry,2009,182(10):2743-2747.
[17]Yang Nanru,Yue Wenhai.Atlas manual of inorganic non-metallic materials[M].Wuhan:Wuhan University of Technology Press,2000(in Chinese).杨南如,岳文海.无机非金属材料图谱手册[M].武汉:武汉工业大学出版社,2000.