基于热动力学的磷酸镁水泥水化机理

doi:10.11901/1005.3093.2017.236

材料研究学报

2018, Vol. 32

Issue (4): 247-254 DOI: 10.11901/1005.3093.2017.236

研究论文

本期目录 | 过刊浏览

基于热动力学的磷酸镁水泥水化机理

戴丰乐^1,², 汪宏涛¹(

), 姜自超¹, 赵思勰¹

1 后勤工程学院化学与材料工程系重庆 401311
2 中国人民解放军96726部队清远 511500

Hydration Mechanism of Magnesium Phosphate Cement Based on Thermokinetics

Fengle DAI^1,², Hongtao WANG¹(

), Zichao JIANG¹, Sixie ZHAO¹

1 Department of Chemistry and Engineering, Logistical Engineering University, Chongqing 401311, China
2 The 96726 Unit of PLA, Qingyuan 511500, China

引用本文:

戴丰乐, 汪宏涛, 姜自超, 赵思勰. 基于热动力学的磷酸镁水泥水化机理[J]. 材料研究学报, 2018, 32(4): 247-254.
Fengle DAI, Hongtao WANG, Zichao JIANG, Sixie ZHAO. Hydration Mechanism of Magnesium Phosphate Cement Based on Thermokinetics[J]. Chinese Journal of Materials Research, 2018, 32(4): 247-254.

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摘要:

使用等温微量量热仪测试磷酸镁水泥的水化放热行为,基于热动力学方法研究了磷酸镁水泥的水化机理。结果表明：根据各水化阶段不同的主要反应,可将磷酸镁水泥的水化划分为初始期、MgO溶解期、[Mg(H₂O)]₆²⁺生成期、MKP加速生成期、MKP减速生成期和稳定期。磷酸镁水泥的水化需要酸性环境激发,随着水化反应的进行水化体系中的H⁺逐渐消耗,MgO的微溶和水解使水化中后期的水化体系向碱性环境变化。水化的早期产物MKP晶体快速生长并搭接构成磷酸镁水泥整体结构的框架,磷酸镁水泥的抗压强度快速提高。水化8 h后MKP生成量增长的幅度下降,磷酸镁水泥抗压强度的提高主要源于MKP晶体的联结。

关键词 ：无机非金属材料, 磷酸镁水泥, 水化, 动力学, 水化机理

Abstract：

The hydration heat release behavior of magnesium phosphate cement (MPC) was investigated by isothermal calorimeter. Results show that according to the feature of reaction processes, the hydration of MPC could be divided into five periods, such as the initiation, dissolution of MgO, growth of Mg(H₂O)₆²⁺, accelerating growth of MgKPO₄·6H₂O (MKP), as well as decelerating growth and stable period of MKP. Meanwhile, the activation energy of each stage was acquired by Arrhenius formula. The hydration of MPC needed to be excited by the acidic environment. With the extend of hydration time, H⁺ was consumed in the hydration system, and then the hydration system became alkaline gradually because of the slightly soluble nature and hydrolysis of MgO in water. In the early hydration stage of MPC the hydration product MKP crystallites grew and interconnected rapidly, which formed the frame of the whole structure of MPC and the compressive strength of MPC increased rapidly. After 8h of hydration, the growth rate of MKP decreased significantly, whilst the increase of compressive strength of MPC mainly depended on the integrity of interconnection of MKP crystallites.

Key words： inorganic non-metallic materials magnesium phosphate cement hydration kinetics hydration mechanism

收稿日期: 2017-04-07

基金资助:资助项目国家自然科学基金(51272283),重庆市自然科学基金(cstc2012jjB50009)

作者简介:

作者简介戴丰乐,男,1992年生, 硕士

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表1 重烧氧化镁的化学成分

图1 磷酸镁水泥的水化放热特征曲线

图2 293 K时的累计放热量和Knudsen公式拟合效果

表2 293 K时阶段B-F的水化动力学参数

图3 293 K时阶段B-阶段F的拟合效果

表3 303 K时阶段B-F的水化动力学参数和表观活化能

图4 lnK与1/T的关系

图5 抗压强度与水化时间的关系

图6 不同水化龄期的XRD图谱

图7 各水化龄期的差热分析和质量损失

图8 不同水化龄期的微观形貌

图9 pH值的变化曲线

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