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 of Al3+ substituting for Si4+(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 benefi cial to substitution of Al3+ for Si4+, and Al/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 benefi cial to the increase of Al/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 of Al3+ which can occupy the bridging tetrahedra sites in C-S-H structure is insuffi cient in hardened Portland cement pastes.
