Chemical shrinkage behavior and prediction model of cement-based composite paste with the addition of graphene oxide
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摘要: 为了揭示氧化石墨烯/水泥复合净浆(GO/C)的化学收缩特性,采用体积法对不同水灰比(0.3、0.4、0.5)和不同氧化石墨烯(GO)质量分数(0wt%、0.01wt%、0.02wt%、0.03wt%、0.04wt%、0.05wt%)的水泥复合净浆试件化学收缩进行了测定。试验结果显示:随着水灰比的增加,GO/C化学收缩显著增大。同水灰比条件下掺有氧化石墨烯的GO/C试件前期化学收缩较普通水泥净浆有所下降,当GO质量分数为0.04wt%时,收缩值达到最小;在后期水化中,GO/C试件的化学收缩增长速度明显快于普通水泥净浆。分析表明,GO对水泥净浆孔结构的调控作用和对水化产物氢氧化钙晶体的键合行为是其影响水泥净浆化学收缩性能的主要原因。同时,通过收缩模型与试验值对比发现,现有的普通水泥化学收缩模型无法精准预测GO/C的化学收缩情况,因此,为考虑GO的影响,试验在吴浪模型的基础上,引入
$K(\xi , t)$ 函数作为影响参数,并通过曲线拟合得到其具体表达式,从而建立起适用于GO/C化学收缩的预测模型。Abstract: In order to reveal the chemical shrinkage characteristics of graphene oxide cement composite paste (GO/C), the chemical shrinkage of cement composite paste with different water-cement ratio (0.3, 0.4, 0.5) and different mass fractions of graphene oxide (GO) (0wt%, 0.01wt%, 0.02wt%, 0.03wt%, 0.04wt% and 0.05wt%). The results show that the chemical shrinkage of GO/C is significantly increased with an increase in water-cement ratio. At the same water-cement ratio, the early chemical shrinkage of GO/C is lower than that of ordinary cement paste, and when the mass fraction of GO is 0.04wt%, the shrinkage value reaches the minimum. However, the growth rate of chemical shrinkage of GO/C specimens is obviously faster than that of ordinary cement paste in later hydration process. The analysis shows that the influence of GO on the chemical shrinkage of cement paste is mainly attributed to the regulation of GO on the pore structure of cement paste and the bonding behavior of GO with calcium hydroxide crystal. Furthermore, based on the comparison results of existing shrinkage models, it is found that the chemical shrinkage models of ordinary cement cannot accurately predict the chemical shrinkage of GO/C. Therefore, in order to consider the effect of GO,$K(\xi , t)$ function is introduced as an influence parameter on the basis of Wu Lang model, and its specific expression is obtained by curve fitting. Finally, a prediction model suitable for GO/C chemical shrinkage was established. -
表 1 水泥的主要技术指标
Table 1. The properties of cement.
Mass fraction/wt% Chemical analysis Density/
(g·cm−3)Specific
surface area/
(m2·kg−1)Compressive
strength at
28 days/MPaFlexural
strength at
28 days/MPaSiO2 Al2O3 Fe2O3 CaO MgO SO3 Loss of ignition 22.53 4.42 2.06 62.71 3.55 0.35 2.84 3.09 345 48.3 7.6 表 2 氧化石墨烯(GO)元素分析
Table 2. Elemental analysis of graphene oxide (GO)
Element mass fraction/wt% Carbon Hydrogen Nitrogen Sulphur Oxygen 49-56 0-1 0-1 0-2 41-50 表 3 水泥复合净浆配合比
Table 3. Mix proportions (by mass) of cement composite pastes
Group Number Water-cement
ratio ($w $/c)Dosage of
GO/wt%Ⅰ GO/C-0.30-0.03 0.30 0.03 GO/C-0.40-0.03 0.40 0.03 GO/C-0.50-0.03 0.50 0.03 Ⅱ GO/C-0.40-0.00 0.40 0.00 GO/C-0.40-0.01 0.40 0.01 GO/C-0.40-0.02 0.40 0.02 GO/C-0.40-0.03 0.40 0.03 GO/C-0.40-0.04 0.40 0.04 GO/C-0.40-0.05 0.40 0.05 表 4 四种矿物成分在不同水灰比环境下的水化参数
Table 4. Hydration parameters of four mineral components under different water cement ratios
Mineral component $w/c$ $ {\tau }_{X}({T}_{0})$ $m$ ${\alpha _{X{\rm{,0}}}}$ ${E_{{\rm{a}}X}}$ ${\alpha _X}(t)$ C3S 0.3 13.5 1.86 0.02 37.39 ${\alpha _{{{\rm{C}}_{\rm{3}}}{\rm{S}}}}(t) = {\rm{1}}{\rm{.02 - }}\exp ( - {({\rm{0}}{\rm{.0398(}}t - {t_{X,0}}))^{{\rm{1}}{\rm{.86}}}})$ 0.4 12.7 1.78 ${\alpha _{{{\rm{C}}_{\rm{3}}}{\rm{S}}}}(t) = {\rm{1}}{\rm{.02 - }}\exp ( - {({\rm{0}}{\rm{.0442(}}t - {t_{X,0}}))^{{\rm{1}}{\rm{.78}}}})$ 0.5 11.9 1.72 ${\alpha _{{{\rm{C}}_{\rm{3}}}{\rm{S}}}}(t) = {\rm{1}}{\rm{.02 - }}\exp ( - {({\rm{0}}{\rm{.0489(}}t - {t_{X,0}}))^{{\rm{1}}{\rm{.72}}}})$ C2S 0.3 71.2 1.1 0 20.78 ${\alpha _{{{\rm{C}}_{\rm{2}}}{\rm{S}}}}(t) = {\rm{1}}{\rm{.00 - }}\exp ( - {({\rm{0}}{\rm{.0128(}}t - {t_{X,0}}))^{{\rm{1}}{\rm{.10}}}})$ 0.4 65.3 1.04 ${\alpha _{{{\rm{C}}_{\rm{2}}}{\rm{S}}}}(t) = {\rm{1}}{\rm{.00 - }}\exp ( - {({\rm{0}}{\rm{.0147(}}t - {t_{X,0}}))^{{\rm{1}}{\rm{.04}}}})$ 0.5 60.9 0.96 ${\alpha _{{{\rm{C}}_{\rm{2}}}{\rm{S}}}}(t) = {\rm{1}}{\rm{.00 - }}\exp ( - {({\rm{0}}{\rm{.0171(}}t - {t_{X,0}}))^{{\rm{0}}{\rm{.96}}}})$ C3A 0.3 57.7 1.14 0.04 35.71 ${\alpha _{{{\rm{C}}_{\rm{3}}}{\rm{A}}}}(t) = {\rm{1}}{\rm{.04 - }}\exp ( - {({\rm{0}}{\rm{.0152(}}t - {t_{X,0}}))^{{\rm{1}}{\rm{.14}}}})$ 0.4 53.4 1.06 ${\alpha _{{{\rm{C}}_{\rm{3}}}{\rm{A}}}}(t) = {\rm{1}}{\rm{.04 - }}\exp ( - {({\rm{0}}{\rm{.0177(}}t - {t_{X,0}}))^{{\rm{1}}{\rm{.06}}}})$ 0.5 49.2 1.00 ${\alpha _{{{\rm{C}}_{\rm{3}}}{\rm{A}}}}(t) = {\rm{1}}{\rm{.04 - }}\exp ( - {({\rm{0}}{\rm{.0203(}}t - {t_{X,0}}))^{{\rm{1}}{\rm{.00}}}})$ C4AF 0.3 27.0 2.44 0.40 34.90 ${\alpha _{{{\rm{C}}_{\rm{4}}}{\rm{AF}}}}(t) = {\rm{1}}{\rm{.40 - }}\exp ( - {({\rm{0}}{\rm{.0152(}}t - {t_{X,0}}))^{{\rm{2}}{\rm{.44}}}})$ 0.4 23.9 2.38 ${\alpha _{{{\rm{C}}_{\rm{4}}}{\rm{AF}}}}(t) = {\rm{1}}{\rm{.40 - }}\exp ( - {({\rm{0}}{\rm{.0176(}}t - {t_{{\rm{X,0}}}}))^{{\rm{2}}{\rm{.38}}}})$ 0.5 21.4 2.30 ${\alpha _{{{\rm{C}}_{\rm{4}}}{\rm{AF}}}}(t) = {\rm{1}}{\rm{.40 - }}\exp ( - {({\rm{0}}{\rm{.0203(}}t - {t_{X,0}}))^{{\rm{2}}{\rm{.30}}}})$ Notes: τX(T0)—Characteristic time of the reaction at a constant reference temperature T0 = 293 K; m—Exponent that defines the reaction order; αX,0 and αX(t)—Degrees of hydration threshold of clinker X at the end of the dissolution period and the time of t, respectively; EaX—Activation energy of the chemical reaction for the clinker X. 表 5
$K(\xi ,t)$ 函数拟合结果Table 5. Fitting results of
$K(\xi ,t)$ Number $\xi /{\rm{wt}}\% $ Fitted values R-square ${K_0}$ ${A_1}$ $a$ ${A_2}$ $b$ K-0.00 0.00 1.647 1.450 0.594 0.869 0.001 0.9625 K-0.01 0.01 1.296 1.082 0.459 0.648 0.003 0.9758 K-0.02 0.02 1.247 1.504 0.789 0.565 0.005 0.9600 K-0.03 0.03 1.419 1.248 0.559 0.697 0.002 0.9710 K-0.04 0.04 1.423 1.340 0.813 0.791 0.002 0.9102 K-0.05 0.05 1.436 1.386 0.809 0.811 0.002 0.9541 Notes: ξ—Mass fraction of GO; K0, A1, a, A2 and b—Parameters of $K(\xi ,t)$. -
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