为从分子尺度优化C-S-H微结构提供理论依据,采用模拟大体积混凝土内部变温历程的养护制度,运用29Si魔角旋转核磁共振(29Si MAS NMR)结合去卷积技术,研究了变温条件下Ba(OH)2掺量为1.0%时对水泥浆体C-S-H微结构的影响规律。结果表明:在变温条件下掺加Ba(OH)2提高了水泥浆体中硅酸盐矿物水化程度,尤其在水化早期(3 d)时硅酸盐矿物水化程度增幅较大,进而使C-S-H结构中硅氧四面体二聚体数量增加,导致其C-S-H平均分子链长(MCL)显著低于纯水泥浆体,避免了纯水泥浆体在降温阶段出现C-S-H的MCL降低的现象。同时,掺加Ba(OH)2进一步降低了水泥浆体在变温过程下C-S-H中Al3+取代Si4+的程度。
采用XRD、29Si和27 Al NMR等测试手段,研究了聚环氧琥珀酸对水泥浆体铝离子配位结构的影响机理。结果表明,聚环氧琥珀酸能阻止硅酸盐矿物水化,抑制掺杂在Alite和Belite矿中的四配位铝(Al[4])参与水化,不利于铝氧四面体进入到C-S-H结构取代硅氧四面体,促使浆体中Al[4]向六配位铝(Al[6])转化。聚环氧琥珀酸掺量存在一个最佳值,掺量较小时,聚环氧琥珀酸与水泥浆体中Ca2+键合后带正电荷,极易与SO42-结合形成螯合物,促使AFt、AFm中Al[6]向TAH(Third aluminum hydrate)中Al[6]转化,达到抑制AFt、AFm结晶的作用;当掺量较大时,聚环氧琥珀酸通过Ca2+桥连另外的聚环氧琥珀酸形成环状结构,降低了聚环氧琥珀酸固化SO42-的程度,进而使大量TAH中Al[6]逐步向AFm、AFt中Al[6]转化,反而促进了AFt结晶形成。
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.
