The effect of curing regime on degree ofAl3+ substituting for Si^4+ (Al/Si ratio) in C-S-H gels of hardened Portland cement pastes was investigated by 29Si magic angel spinning (MAS) nuclear magnetic resonance ...The effect of curing regime on degree ofAl3+ substituting for Si^4+ (Al/Si ratio) in C-S-H gels of hardened Portland cement pastes was investigated by 29Si magic angel spinning (MAS) nuclear magnetic resonance (NMR) with deconvolution technique. The curing regimes included the constant temperature (20, 40, 60 and 80 ℃) and variable temperature (simulated internal temperature of mass concrete with 60 ℃ peak). The results indicate that constant temperature of 20 ℃ is beneficial to substitution ofAl3+ for Si4+, and AI/Si ratio changes to be steady after 180 d. The increase of Al/Si ratio at 40 ℃is less than that at 20℃ for 28 d. The other three regimes of high temperature increase Al/Si ratio only before 3 d, on the contrary to that from 3 to 28 d. However, the 20 ℃ curing stage from 28 to 180 d at variable temperature regime, is beneficial to the increase of AI/Si ratio which is still lower than that at constant temperature regime of 20 ℃ for the same age. A nonlinear relation exists between the Al/Si ratio and temperature variation or mean chain length (MCL) of C-S-H gels, furthermore, the amount ofAl3+ which can occupy the bridging tetrahedra sites in C-S-H structure is insufficient in hardened Portland cement pastes.展开更多
基于大体积混凝土内部的温度变化,利用27 Al魔角旋转核磁共振(27 Al MAS NMR)结合去卷积技术,研究变温下SO2-4对水泥硬化浆体中Al 3+配位分布的影响。结果表明,变温的高温阶段促进AFt、TAH(third aluminum hydrate)和掺杂在C-S-H结构中(...基于大体积混凝土内部的温度变化,利用27 Al魔角旋转核磁共振(27 Al MAS NMR)结合去卷积技术,研究变温下SO2-4对水泥硬化浆体中Al 3+配位分布的影响。结果表明,变温的高温阶段促进AFt、TAH(third aluminum hydrate)和掺杂在C-S-H结构中(C-S-A-H)的四配位铝(Al[4])向AFm转化;降温阶段促进TAH生成,利于AFm和C-S-A-H中Al[4]向AFt转化;而变温后20℃常温不仅利于AFt向AFm转化,TAH向Al[4]转变,而且利于Al[4]进入高钙硅比(Ca/Si)C-S-H结构。在5%Na2SO4溶液中,SO2-4在侵蚀3d时首先对AFm侵蚀,对TAH和C-S-A-H中Al[4]侵蚀作用较小;变温过程的高温加快SO2-4对AFm和TAH的侵蚀,并且对C-S-A-H凝胶有脱铝作用;变温后20℃常温有利于C-S-H凝胶与硫酸根竞争Al[4],低Ca/Si的C-S-A-H凝胶具有较强的抗SO2-4脱铝能力。展开更多
基金Funded by the Major State Basic Research Development Program of China(973 Program)(No.2009CB623201)National Natural Science Foundation of China(No.51302070)
文摘The effect of curing regime on degree ofAl3+ substituting for Si^4+ (Al/Si ratio) in C-S-H gels of hardened Portland cement pastes was investigated by 29Si magic angel spinning (MAS) nuclear magnetic resonance (NMR) with deconvolution technique. The curing regimes included the constant temperature (20, 40, 60 and 80 ℃) and variable temperature (simulated internal temperature of mass concrete with 60 ℃ peak). The results indicate that constant temperature of 20 ℃ is beneficial to substitution ofAl3+ for Si4+, and AI/Si ratio changes to be steady after 180 d. The increase of Al/Si ratio at 40 ℃is less than that at 20℃ for 28 d. The other three regimes of high temperature increase Al/Si ratio only before 3 d, on the contrary to that from 3 to 28 d. However, the 20 ℃ curing stage from 28 to 180 d at variable temperature regime, is beneficial to the increase of AI/Si ratio which is still lower than that at constant temperature regime of 20 ℃ for the same age. A nonlinear relation exists between the Al/Si ratio and temperature variation or mean chain length (MCL) of C-S-H gels, furthermore, the amount ofAl3+ which can occupy the bridging tetrahedra sites in C-S-H structure is insufficient in hardened Portland cement pastes.
文摘基于大体积混凝土内部的温度变化,利用27 Al魔角旋转核磁共振(27 Al MAS NMR)结合去卷积技术,研究变温下SO2-4对水泥硬化浆体中Al 3+配位分布的影响。结果表明,变温的高温阶段促进AFt、TAH(third aluminum hydrate)和掺杂在C-S-H结构中(C-S-A-H)的四配位铝(Al[4])向AFm转化;降温阶段促进TAH生成,利于AFm和C-S-A-H中Al[4]向AFt转化;而变温后20℃常温不仅利于AFt向AFm转化,TAH向Al[4]转变,而且利于Al[4]进入高钙硅比(Ca/Si)C-S-H结构。在5%Na2SO4溶液中,SO2-4在侵蚀3d时首先对AFm侵蚀,对TAH和C-S-A-H中Al[4]侵蚀作用较小;变温过程的高温加快SO2-4对AFm和TAH的侵蚀,并且对C-S-A-H凝胶有脱铝作用;变温后20℃常温有利于C-S-H凝胶与硫酸根竞争Al[4],低Ca/Si的C-S-A-H凝胶具有较强的抗SO2-4脱铝能力。