不同CO2养护压力下硫铝酸盐和硅酸盐水泥浆体早期微观结构

研究硫铝酸盐和硅酸盐水泥（CSA-OPC）浆体在不同碳养护压力下的早期碳化过程,通过X射线衍射、红外光谱、热重、压汞和扫描电镜等测试方法,表征碳化前后水泥浆体的物相组成和微观结构. 实验结果表明,CSA-OPC浆体的水化产物主要为钙矾石,碳化作用使钙矾石转变为碳酸钙和硫酸钙晶体;水泥中碳酸钙以3种晶型存在,其中方解石为主要存在形式. 碳化使半碳型的水化硫铝酸钙（Hc-AFm相）逐渐转化为单碳型的水化硫铝酸钙（Mc-AFm相）,碳化程度和碳化深度随着碳化压力的增加而递增. 碳化后CSA-OPC水化产物体积减小,样品总孔隙率增大、孔隙结构变疏松. 研究结果阐明了CSA-OPC浆体在早期碳化养护条件下的微结构变化过程,为制备基于硫铝酸盐水泥的高效碳汇材料提供了技术支撑.     

Carbonation of sulphoaluminate cement with layered double hydroxides

The increasing importance of the ecologically minded production of building materials makes it necessary to develop reasonable alternatives to the CO2-intense production of ordinary Portland cement （OPC）. The development of new or modified concrete is an important part of existing strategies to improve performance and minimize life-cycle costs. Therefore, we investigated carbonation resistance properties of sulphoaluminate cement （SAC） concrete incorporating layered double hydroxides （LDHs）. X-ray diffraction （XRD） and IR-spectroscopy were employed to characterize the component and structural changes of LDHs and cement paste before and after carbonation test. Carbonation resistance of concrete was experimentally evaluated. Finally, carbonation of Portland cement and SAC concrete was compared. The experimental results show that carbonation depth decreases remarkably with the addition of LDHs, especially the calcinated LDHs. Carbonation depth of SAC concrete is smaller than that of PC concrete regardless of curing time.     

超临界碳化对水泥基材料性能和孔径结构的影响

为了考察超临界碳化技术在水泥基材料改性方面的应用,研究超临界碳化对水泥基材料微观和宏观性能的影响,基于此设计了超临界二氧化碳碳化试验研究水泥砂浆、水泥净浆和混凝土试件的碳化深度、强度、孔径分布以及二氧化碳吸收量的变化。试验分析表明,超临界碳化可以快速实现水泥基材料的碳化,大幅提高试件强度,改善材料的孔径分布,使材料的中细径孔大幅降低,提高材料的抗渗透能力,为改善重金属等危害废物的水泥基固化效果提供了依据。同时超临界碳化可以将大量二氧化碳转化在碳酸钙中沉淀吸收,具有重要的环境保护意义。     

Test method to simulate the influence of the interface on the concrete carbonation process

A trial test method is introduced to form and magnify regular interface. Through researching on the carbonation of the magnifying interfacial transition zone (ITZ), the practical carbonation of the concrete can be simulated. Because the diffusion rate of CO₂ in the ITZ is several times greater than that in the bulk paste, the diffusion rate and direction of CO₂ will change and form a new carbonation front line. An interfacial effect zone caused by the ITZ will change the distribution of the complete carbonation zone and the partial carbonation zone. One of the important reasons for the formation of the partial carbonation zone was the existence of the interfacial effect zone. Consequently, the method mentioned in this paper provides a new way for researching on the microstructure of the cement based materials during the carbonation process.     

Carbonation resistance of sulphoaluminate cement-based high performance concrete

The influences of water/cement ratio and admixtures on carbonation resistance of sulphoaluminate cement-based high performance concrete (HPC) were investigated. The experimental results show that with the decreasing water/cement ratio, the carbonation depth of sulphoaluminate cement-based HPC is decreased remarkably, and the carbonation resistance capability is also improved with the adding admixtures. The morphologies and structure characteristics of sulphoaluminate cement hydration products before and after carbonation were analyzed using SEM and XRD. The analysis results reveal that the main hydration product of sulphoaluminate cement, that is ettringite (AFt), decomposes after carbonation. Funded by the National Natural Science Foundation of China (No.50872043)     

再生混凝土抗碳化性能试验研究及理论分析

通过快速碳化试验,以再生骨料掺量、水灰比、水泥用量、原始混凝土强度和矿物掺合料为影响因素,对再生混凝土的碳化性能进行研究。试验结果表明：再生混凝土的碳化深度随水灰比、再生骨料掺量的增加而减小,随原始混凝土强度的增大和水泥用量的增加而增大,适量添加矿物掺和料能降低再生混凝土的碳化深度,提升其抗碳化性能。在已有的普通混凝土碳化模型研究基础上,结合本试验和中国其他学者的试验数据,建立了再生混凝土碳化深度预测模型,模型预测结果与试验值吻合较好。     

Carbonation of low heat portland cement paste procured in water for different time

The carbonation technique was applied to accelerate the hydration of low heat portland cement (LHC). Before carbonation, the demoulded pastes were precured in water for 0, 2, 7, and 21 d, respectively. The results show that procuring time in water strongly influences the carbonation process. The phenolphthalein test indicates that the paste precured in water for a shorter time is more quickly carbonated than that for a longer time. The content of calcium hydroxide increases with increasing the procuring time in water, whereas, the amount of absorbed carbon dioxide changes contrarily. Scanning electron microscope (SEM) observation shows that portlandite always fills up big air bubbles in the paste during precuring in water, and the mercury intrusion porosimetry (MIP) results show that there are less large capillary pores in the paste precured in water for a longer time. It is found that the paste without precuring in water has more carbon dioxide absorption during curing in carbon dioxide atmosphere, and its total pore volume decreases remarkably with an increase in the carbonation time than that precured in water. X-ray diffraction (XRD) and Brunauer-Emmett-Teller (BET) surface area analyses indicate that the carbonate products are vaterite and calcite; CxSHy,, formed from carbonation has low BET surface area in comparison with that of C-S-H formed from curing in water.     

Carbonation of low heat portland cement paste precured in water for different time

The carbonation technique was applied to accelerate the hydration of low heat portland cement （LHC）. Before carbonation, the demoulded pastes were precured in water for 0, 2, 7, and 21 d, respectively. The results show that precuring time in water strongly influences the carbonation process. The phenolphthalein test indicates that the paste precured in water for a shorter time is more quickly carbonated than that for a longer time. The content of calcium hydroxide increases with increasing the precuring time in water, whereas, the amount of absorbed carbon dioxide changes contrarily. Scanning electron microscope （SEM） observation shows that portlandite always fills up big air bubbles in the paste during precuring in water, and the mercury intrusion porosimetry （MIP） results show that there are less large capillary pores in the paste precured in water for a longer time. It is found that the paste without precuring in water has more carbon dioxide absorption during curing in carbon dioxide atmosphere, and its total pore volume decreases remarkably with an increase in the carbonation time than that precured in water. X-ray diffraction （XRD） and Brunauer-Emmett-Teller （BET） surface area analyses indicate that the carbonate products are vaterite and calcite; CxSHy formed from carbonation has low BET surface area in comparison with that of C-S-H formed from curing in water.     

Determination of the apparent activation energy of concrete carbonation

Accelerated carbonation experiments about the development of carbonation rates of ordinary Portland cement concrete under different artificial climates were carried out. Six water cement ratios and six climate condition combinations of temperature and relative humidity were used. Results indicate that changes of concrete carbonation rate with environmental temperature agree the Arrhenius law well, which suggests concrete carbonation rate has obvious dependence on temperature. The higher the temperature is, the more quickly the concrete carbonates, and at the same time it is also affected by environmental relative humidity. Thereafter, the apparent activation energy E _a of concrete carbonation reaction was obtained, ranging from 16.8 to 20.6 kJ/mol corresponding 0.35–0.74 water cement ratio, and lower water cement ratio will cause the apparent activation energy increase. Concrete carbonation rates will increase 1.1–1.69 times as temperature increase every 10 °C at the temperature range of 10 to 60 °C.     

Modelling of time dependency of chloride diffusion coefficient in cement paste

A computer-based model and method was presented to predict the time dependency of chloride diffusion coefficients in cement paste. The HYMOSTRUC3D model was applied to generate a 3D representative elementary volume (REV) of cement paste. In the simulation of microstructure, both of cement hydration and chloride binding were considered. With the simulated microstructure of cement paste, the finite element method was applied to simulate the diffusion process of chloride through the saturated cement paste. Based on the Fick’s first law, the chloride diffusion coefficient can be calculated. In this method, the influences of age and w/c ratio on the chloride diffusion coefficient were evaluated. The simulated chloride diffusivities with various w/c at different time were compared to experimental data obtained from the literature. The experimental results indicate that the chloride diffusion coefficient decreases with the increase of time and the decrease of w/c ratio. The trend of simulated relationship (diffusion coefficient vs time, diffusion coefficient vs w/c ratio) fits very well with the experiments.     

Effect of Isobutyl-triethoxy-silane Penetrative Protective Agent on the Carbonation Resistance of Concrete

Effect of isobutyl-triethoxy-silane penetrative protective agent on the carbonation resistance of the concrete was studied.The concrete specimens for the 28 d accelerated carbonation process were manufactured with w/c of 0.49 and 0.64,both in the presence and absence of silane and mineral admixture.The penetration of isobutyl-triethoxy-silane and the carbonation of concrete were investigated by penetration depth,carbonation depth,XRD,SEM,and pore size distribution.The results showed that concrete compactness played an important role in the silane penetration and carbonation resistance.Penetration depth of silane-treated concrete mainly depended on the compactness of the concrete,and could not remarkably change through the accelerated carbonation process.In the accelerated carbonation process,penetrative protective agent improved the carbonation resistance of the higher compactness concretes but accelerated the carbonization process of the lower compactness concretes.As penetrative protective agent penetrated along the external connectivity pores into concrete not filling the entire surface area,the inorganic film could not fully protect the Ca(OH)_2 phase from carbonation.After 28 d accelerated carbonation,fibrous hydration products disappeared and the surface holes decreased.Due to the formation of carbonized products,the porosity of the concrete surface decreased,especially in high-strength concrete.     

Durability of lining concrete of subsea tunnel under combined action of freeze-thaw cycle and carbonation

Through the fast freeze-thaw cycle test,accelerated carbonation test,and natural carbonation test,the durability performance of lining concrete under combined action of freeze-thaw cycle and carbonation were studied.The experimental results indicate that freeze-thaw cycle apparently accelerates the process of concrete carbonation and carbonation deteriorates the freeze resistance of concrete.Under the combined action of freeze-thaw cycle and carbonation,the durability of lining concrete decreases.The carbonation depth of lining concrete at tunnel openings under freeze-thaw cycles and tunnel condition was predicted.For the high performance concrete with proposed mix ratio,the lining concrete tends to be unsafe because predicted carbonation depth exceeds the thickness of reinforced concrete protective coating.Adopting other measurements simultaneously to improve the durability of lining concrete at the tunnel openings is essential.     

Mechanical properties and microstructure of Portland cement concrete prepared with coral reef sand

The feasibility of using coral reef sand (CRS) in Portland cement concrete is investigated by testing the mechanical property and microstructure of concrete. The composition, structure and properties of the CRS are analyzed. Mechanical properties and microstructure of concrete with CRS are studied and compared to concrete with natural river sand. The relationship between the microstructure and performance of CRS concrete is established. The CRS has a porous surface with high water intake capacity, which contributes to the mechanical properties of concrete. The interfacial transition zone between the cement paste and CRS is densified compared to normal concrete with river sand. Hydration products form in the pore space of CRS and interlock with the matrix of cement paste, which increases the strength. The total porosity of concrete prepared with CRS is higher than that with natural sand. The main difference in pore size distribution is the fraction of fine pores in the range of 100 nm.     

粉煤灰水泥石碳化反应机理的研究

本文应用SEM、EDXA和MIP等手段对碳化前后水尼石结构进行了对比分析。揭示了水泥石碳化后大孔增加原理,并通过碳化收缩裂缝分析说明了粉煤灰水泥石抗碳化性能劣化的原因。     

混凝土自然碳化及其与人工加速碳化的相关性研究

在实验室研究了普通水泥混凝土和掺粉煤灰水泥混凝土在自然条件下的碳化规律,历时10年。提出了混凝土的碳化方程及其参数。通过自然碳化及相应的人工加速碳化试验和微观测试方法,对混凝土的碳化进程、孔结构和物相变化规律进行了分析。发现了自然碳化与人工加速碳化之间存在的相关性。得出的相关公式可用于碳化速率系数的计算和碳化进程的预测。     

Research of Neural Network Based on Improved PSO Algorithm for Carbonation Depth Prediction of Concrete

Firstly,neural network based on improved particle swarm optimization (PSO)algorithm is introduced in this paper. Based on the data collected from projects in typical areas,the concrete carbonation depth is assessed with consideration of various factors such as unit cement consumption (C),unit water consumption (W),binder material content (B),water binder ratio (W/B ),concrete strength (MPa),rapid carbonization days (D),fly ash consumption of unit volume concrete(FA),fly ash percentage of total cementitious materials (FA%),expansion agent consumption of unit volume concrete(EA),expansion agent percentage of total cementitious materials (FA%).Gaining the data from project-experiment,a model is presented to calculate and forecast carbonation depth using neural network based on improved PSO algorithm. The calculation results indicate that this algorithm accord with the prediction carbonation depth of concrete accuracy requirements and has a better convergence and generalization,worth being popularized.     

数字图像系统水泥水化计算机模拟(Ⅱ)

以CEMHYD3D为背景,阐述在完成水泥颗粒的三维重构后,根据元胞自动机理论,水泥水化的反应规则运用到水泥浆体的三维结构中。模拟水泥水化演变过程中水泥主要物相之间的化学反应,以实现水泥水化的水泥浆体的微结构的演变,并对水泥水化计算机模拟问题进行讨论。     

UFA水泥基材料早期自干燥及自收缩研究

基于水泥石孔隙理论对超细粉煤灰（Ultra-fine fly ash，简称UFA）水泥基材料的早期自干燥效应进行了理论分析及试验研究。在此基础上，采用改进的混凝土自收缩试验装置对UFA混凝土的早期自收缩变形进行了测试。结果表明，相比于基准水泥石，UFA水泥石内部自干燥程度大大降低；且随着UFA的掺入，混凝土早期水化反应的有效水灰比增大，自收缩变形随之减小，进一步证明水泥基材料早期内部孔隙的自干燥效应与混凝土的早期自收缩变形具有较好的相关性。     

复掺矿物掺合料混凝土碳化深度预测模型

在深入分析水泥水化、矿物掺合料二次水化以及混凝土碳化机理的基础上,对混凝土碳化理论模型中的重要参数——完全碳化时单位体积混凝土吸收二氧化碳的量m0进行了分析,提出了以水胶比、胶凝材料用量、粉煤灰、矿渣、硅灰掺量等为主要参数的计算公式,建立了复掺矿物掺合料混凝土碳化深度预测模型,经验证模型计算值与试验结果吻合较好.     

Application of X-ray computed tomography in characterization microstructure changes of cement pastes in carbonation process

The microstructure characteristics and meso-defect volume changes of hardened cement paste before and after carbonation were investigated by three-dimensional(3D)X-ray computed tomography(XCT),where three types water-to-cement ratio of 0.53,0.35 and 0.23 were considered.The high-resolution 3D images of microstructure and filtered defects were reconstructed by an XCT VG Studio MAX 2.0 software.The meso-defect volume fractions and size distribution were analyzed based on 3D images through add-on modules of 3D defect analysis.The 3D meso-defects volume fractions before carbonation were 0.79%,0.38% and 0.05% corresponding to w/c ratio=0.53,0.35 and 0.23,respectively.The 3D meso-defects volume fractions after carbonation were 2.44%,0.91% and 0.14% corresponding to w/c ratio=0.53,0.35 and 0.23,respectively.The experimental results suggest that 3D meso-defects volume fractions after carbonation for above three w/c ratio increased significantly.At the same time,meso-cracks distribution of the carbonation shrinkage and gray values changes of the different w/c ratio and carbonation reactions were also investigated.