Modeling of ionic diffusivity in non-saturated cement-based materials using lattice Boltzmann method

The ionic diffusivity in non-saturated cement-based materials is quantitatively studied using lattice Boltzmann method. The Shan–Chen multi-phase lattice Boltzmann model modified by incorporating the Carnahan–Starling equation of state into the model is used to simulate the equilibrium distribution of water and gas phases with density ratio as high as 775 in the three-dimensional microstructure of cement paste at various degrees of water saturation. The lattice Boltzmann diffusion model is subsequently applied to simulate the diffusion process of the ionic species through the partially saturated cement paste. Before the application of the modified Shan–Chen model, the benchmark tests including bubble test and contact angle test are carried out to validate it. It is shown that the ionic diffusivity is greatly influenced by the degree of water saturation. The simulated relative ionic diffusivity as a function degree of water saturation is in good agreement with the experimental data obtained from literature. In addition, the effect of w/c ratio on the ionic diffusivity through cement paste under non-saturated conditions is investigated. It indicates that there is a significant difference between the relative diffusivity for cement paste with w/c ratios of 0.4 and 0.5 over the whole range of water saturation degree. However, the difference of relative diffusivity for cement paste with w/c ratios of 0.5 and 0.6 is not obvious.     

Molecular dynamics of 4-n-octyl-4′-cyanobiphenyl in partially filled nanoporous SBA-type molecular sieves

The molecular dynamics of 4-n-octyl-4′-cyanobiphenyl (8CB) confined to the nanopores of new SBA-type molecular sieves was investigated in a wide temperature range using broadband dielectric spectroscopy (10⁻²–10⁹ Hz). One molecular sieve has a hexagonal structure of the pores while the other is a cellular nanoporous material. To explore the extent of surface interaction effects a high and a low filling degree were considered.

For the molecular sieves with a high filling degree two relaxation regions were observed: a bulk-like relaxation process related to molecules, which behave as mesophase, located in the centre of the pores. The second relaxation process has a much lower relaxation rate than the former and is assigned to molecules located in a surface layer. The temperature dependence of its relaxation rates follows the Vogel–Fulcher–Tammann law, characteristic for glassy dynamics.

For samples with a low filling degree only one relaxation process due to the surface layer was observed. Moreover, especially at the temperatures lower than the melting point of bulk 8CB, its relaxation rate is situated between the characteristic frequencies of the two relaxation processes observed for the pores with a high filling degree. This behaviour gives a measure of the extension of the influence of the wall on the neighbouring 8CB molecules. In addition, the differences revealed by the molecule dynamics inside the two types of nanoporous materials are related to both surface interactions and geometrical constraints.     

Thermal Expansion Kinetics: Method to Measure Permeability of Cementitious Materials: II, Application to Hardened Cement Pastes

A new approach to determine the permeability of cementitious materials is presented in this paper. The method involves the measurement of the thermal dilatation of thin slabs of saturated cement paste. On heating and subsequent isothermal holding, the sample first expands, then gradually contracts over time. The paste is treated as a porous solid with low permeability in which the initial expansion is partly due to the liquid expanding within the pores, putting both solid and liquid under stress. The time-dependent contraction is due to the liquid flowing out of the pores to restore the pressure to equilibrium. By analyzing the kinetics of the thermal expansion and contraction, the liquid permeability of the porous solid can be calculated. The theoretical analysis (presented in a previous paper) is applied to determine the water permeability coefficients of selected cement pastes modified with silica fume and made with different water/solid ratios.     

Fluid distribution and pore wettability of monolithic carbon xerogels measured by 1H NMR relaxation

The pore wettability of two types of carbon xerogels exhibiting micro- and mesopores with different sizes was investigated using ¹H NMR relaxation. These nanomaterials are great candidates as active material for gas diffusion electrodes in mobile energy storage devices. The distribution of fluids in these electrodes is a critical parameter determining the electrode performance. Using ¹H NMR relaxation information about the wettability of micro- as well as mesopores is determined simultaneously. Two important solvents for electrolytes, water and dimethyl sulfoxide (DMSO), were studied for different filling states inside the porous structure. While for water no discrimination between micro- and mesopores could be achieved because of its fast exchange rate between the pores, the measurements with DMSO allow for discriminating between solvent in micro- and mesopores. Thus, the wettability of DMSO in both pore regimes was determined by calculating the surface relaxation strength. It turned out that the wettability of the porous structure is dependent on the differences in the pore sizes between micro- and mesopores. At low filling states both pore regimes compete for the remaining fluid leading to a nonuniform distribution. The pores with the better wettability keep the complete surface in contact with the bulk fluid.     

缓凝剂对水泥浆中自由水状态演变的影响

用低场核磁共振技术考察了HN-1型缓凝剂对水泥浆体中可蒸发水的横向弛豫时间(T2)及状态演变过程的影响。结果表明:在初始水化阶段的150 min内,水泥浆GR(添加缓凝剂HN-1的水泥净浆)的弛豫峰峰形和峰顶位置均无明显变化,水泥浆G(纯水泥净浆)的弛豫峰峰形变窄且峰顶位置从2.15 ms迁移至0.95 ms,说明缓凝剂HN-1主要通过改变水泥浆体中不同状态水的存留时间来改变其水化进程。随养护时间的延长,硬化水泥石W0.44和WR0.5中可挥发水弛豫峰分布范围分别从0.11~4.75 ms变为0.08~0.58 ms、0.24~4.23 ms变为0.11~2.35 ms,总体趋向于短弛豫时间,表明水泥石中毛细水逐渐向凝胶水和物理结合水转化,水泥石养护龄期延长至25 d时,其内部凝胶结构水含量超过90%。利用XRD考察了缓凝剂对水泥浆水化产物的影响,结果表明:缓凝剂只改变水泥浆水化过程,对最终水化产物晶型及晶型结构不存在任何影响。     

硫酸盐侵蚀下硬化水泥浆体微结构演变及膨胀过程的数值模拟

根据硫酸盐侵蚀机理,利用改进的CEMHYD3D水化模型和随机概率方法,建立了硫酸盐侵蚀下硬化水泥浆体的微结构演变模型。在微观层次上,模拟了浆体孔溶液中硫酸根离子的自由扩散、随机碰撞和转化反应,分析了膨胀性侵蚀产物生长导致的微结构损伤和体积膨胀,计算了侵蚀过程中石膏和钙矾石的生成量及浆体的膨胀应变,并与已有试验结果对比分析验证了模型的合理性。在此基础上,数值模拟了硫酸盐侵蚀下不同水灰比水泥浆体的微结构演变及膨胀过程。结果表明：同一硫酸盐浓度下,硬化水泥浆体中氢氧化钙和含铝物相与孔隙的接触面积越小,浆体的膨胀应变越低;水灰比为0.25、0.30和0.35的硬化水泥浆体的孔隙填充程度分别达到9.09%、9.27%和9.41%时,浆体膨胀应变开始快速增大;硫酸盐侵蚀溶液浓度增大,浆体体积快速膨胀的时间提前。     

Impedance spectroscopy study of hardened Portland cement paste

In this paper, the differential impedance analysis (DIA) has been applied to the study of the dielectric properties of hardened Portland cement paste. Two time constants are found in the impedance spectra obtained in the frequency region form 100 kHz to 15 MHz. One time constant has been attributed to the solid matrix and the other one to the liquid phase filling the pores. The effect of the cement paste-electrodes interface has been quantified using two different experimental set-ups. Measurements using direct contact between electrodes and cement paste have been compared with measurements using an air gap technique in which the specimen “floats” between the electrodes. The two referred time constants have been found in both types of measurements. The influence of drying on the dielectric parameters is also studied.     

1H驰豫时间谱在水泥基材料研究中的应用

水泥水化、硬化体结构的形成及演化、水泥基材料内部不同水分之间的转化、吸水、干燥、水分在水泥基材料内部的扩散过程引起水分化学状态或所处环境物理状态的变化.这种变化可用1H核磁共振驰豫时间进行表征.已有的研究表明,1H驰豫时间谱可用于水泥水化过程、硬化体结构形成、孔结构、水分在水泥基材料内的传输过程等的表征,所得结果与其它方法所得结果有较好的一致性.且磁共振成像可直接观察水分在水泥基材料中的分布及传输,这是其它现代测试方法难以达到的.     

Creep and relaxation of cement paste caused by stress‐induced dissolution of hydrated solid components

The creep and relaxation of cement paste caused by dissolving solid hydration products is evaluated in this work. According to the second law of thermodynamics, dissolution or precipitation of solid constituents may be altered by the change in stress/strain fields inside cement paste via alteration of the stress power or strain energy. Thus, it is hypothesized that stress‐induced dissolution can affect the overall creep/relaxation behavior of cement composites. A novel, fully coupled thermodynamic, mechanical, and microstructural model (TM²) that uses the finite element method was developed to predict the time‐evolving properties of cement paste under prescribed strains and to test the hypothesis. In the model, the strain energy was incorporated to accurately predict the effect of stress and strain fields on cement microstructure change. From the simulation results, depending on the stress/strain levels and the choice of the domain (over which the thermodynamic equilibrium is enforced), stress‐induced dissolution of solid constituents can lead to significant creep/relaxation.     

Influence of Cement Particle-Size Distribution on Early Age Autogenous Strains and Stresses in Cement-Based Materials

The influence of cement particle-size distribution on autogenous strains and stresses in cement pastes of identical water-to-cement ratios is examined for cement powders of four different finenesses. Experimental measurements include chemical shrinkage, to quantify degree of hydration; internal relative humidity development; autogenous deformation; and eigenstress development, using a novel embedded spherical stress sensor. Because the latter three measurements are conducted under sealed conditions, whereas chemical-shrinkage measurements are made under "saturated" conditions, the National Institute of Standards and Technology cement hydration and microstructure development model is used to separate the effects of differences in hydration rates (kinetics) from those caused by the different initial spatial arrangement of the cement particles. The initial arrangement of the cement particles controls the initial pore-size distribution of the cement paste, which, in turn, regulates the magnitude of the induced autogenous shrinkage stresses produced by the water/air menisci in the air-filled pores formed throughout the hydration process. The experimental results indicate that a small autogenous expansion (probably the result of ettringite formation), as opposed to a shrinkage, may be produced and early age cracking possibly avoided through the use of coarser cements.     

Modelling relationships between permeability and cement paste pore microstructures

Pore size distribution and the interconnectivity of cement paste pores have a strong influence on permeability. A computer network model has been developed to simulate flow through the pore microstructure cement paste. Network models have been successfully applied to predicting permeabilities of geological materials including rocks and soils but have not been specifically developed in the area of cement and concrete. The network model presented in this paper is used to obtain further insight into how pore size distributions of cement paste microstructures influences permeability. The model accounts for variations in pore microstructure by using a two-dimensional network of tubes with different log-normal size distributions.     

Characterisation of intra- and inter-C–S–H gel pore water in white cement based on an analysis of NMR signal amplitudes as a function of water content

¹H nuclear magnetic resonance (NMR) relaxation analysis of water in progressively dried white cement paste is used to estimate the width and relative specific area of intra-C–S–H sheet pores and inter-C–S–H particle gel pores. The measurement is based on the ratio of solid echo to free induction decay signal amplitudes and the observation that as water is removed, so the surface fraction contributing to the solid echo increases. The intra- and inter-C–S–H pores are found to be 1.5 nm and 4.1 nm thick respectively. The total specific area and volume ratio is 2.4 and 0.88 respectively. The volume ratio of readily evaporable water within the pore types is 0.63. Hence, the sheet porosity is 47% of the total or 38% if based solely on evaporable water. The method is distinct from NMR analyses based on the relaxation time. There is good agreement between the measured widths by the two methods.     

缓凝剂SN-3的制备及其对水泥浆横向弛豫时间T2分布的影响

首先合成了一种新型两性聚合物缓凝剂SN-3,然后采用红外光谱和元素分析等测试手段对其进行结构表征。其次,对其应用性能作了进一步研究,主要包括稠化时间、加量和温度敏感性等,实验结果表明应用性能满足现场施工要求。利用低场核磁共振测试技术重点研究了缓凝剂SN-3对油井水泥浆水化过程中横向弛豫时间T₂分布的影响,在相同的水灰比、温度和水化时间下,对纯水泥浆C和掺有缓凝剂SN-3的水泥浆CHN的横向弛豫时间进行测试和分析,借助迁移速率和峰形指数两个参数表征水泥浆T₂分布曲线的变化过程。最后,结合X衍射和扫描电镜（SEM）进一步探讨缓凝剂SN-3的缓凝作用原理。实验结果表明,缓凝剂使水泥浆中填充于絮凝结构之间的水的受缚程度减小,存在时间变长,转化为化学结合水所经历时间变长;缓凝剂SN-3主要通过沉淀和络合作用达到缓凝效果的。     

Effect of Heat Treatment on the Pore Structure and Drying Shrinkage Behavior of Hydrated Cement Paste

The effect of a short heat treatment on hydrated cement paste has been investigated by measuring the weight and length changes of specimens as they undergo various combinations of heating, drying, and resaturation. Heating a cement paste to 60°C coarsens the capillary pore system, decreases the volume of mesopores, and increases the degree of polymerization of the silicates. In addition, the saturated weight of the paste is permanently decreased by a heat treatment. This weight loss can be explained by conversion of bound hydroxyl groups into liquid water during polymerization of the C-S-H gel phase. These experiments help reconcile and interpret published results describing the properties of cement cured at various temperatures, the effects of a short heat treatment on cement paste, and the thermal expansion behavior of saturated and dry cement paste.     

NMR Line Shape-Spin-Lattice Relaxation Correlation Study of Portland Cement Hydration

The proton free induction decay of a portland cement paste in an advanced stage of hydration can be roughly divided into three main components: (1) a component with a very short spin-spin relaxation time, T², representing the protons of the solid OH groups and the water of crystallization, (2) a component with an intermediate T, representing the bonded water in the gel phase, and (3) a third component with a relatively long T² representing the water in the micropores and layers. The dependences of the intensities, T²'s, and spin-lattice relaxation times (T¹'s) of these three components on the cement hardening time have been determined. The proton spin-lattice relaxation time of the "solid" component increases with hardening time whereas T¹ decreases for the other two components. The observed time dependence of the diffusion coefficient, D, of water in a tricalcium silicate paste supports the findings of the above correlation study.     

Nonexponential Dynamics in Porous Glasses

The dielectric relaxation properties of porous glasses prepared from sodium borosilicate glasses are studied by dielectric spectroscopy over a wide range of frequencies (20 Hz–1 MHz) and temperatures (–100–300°C). The dielectric behavior reflecting the geometric disorder is analyzed within the models describing the non-Debye slowly damped dynamics. It is found that the dielectric response is very sensitive to microstructural and mesostructural features of the porous matrix and the properties of a material filling pores. The response contains information on the dynamics of water molecules in pores, which accounts for the interaction of these molecules with the pore surface.     

The influence of water removal techniques on the composition and microstructure of hardened cement pastes

The removal of water from hardened cement paste for analysis or to arrest ongoing hydration has been reported to affect the composition of hydrated phases and microstructure. The effect that arresting the hydration of hardened cement paste by replacing the pore water with acetone before drying, and by removing the water by freeze, vacuum and oven drying has on the hardened cement paste has been investigated. Two pastes were studied, a cemented iron hydroxide floc where a high proportion of ordinary Portland cement (OPC) had been replaced by pulverised fuel ash, and a pure hydrated OPC. The results showed that none of the water removal techniques caused any major deterioration in the composition and microstructure of the hardened cement pastes studied, but the pores appeared better preserved after arresting hydration using acetone quenching. Freeze drying appeared to cause more cracking of the microstructure than the other water removal techniques.     

Water dynamics in cement paste at early age prepared with pozzolanic volcanic ash and Ordinary Portland Cement using quasielastic neutron scattering

Early age hydration kinetics of Portland cement with pozzolanic volcanic ash was examined using quasielastic neutron scattering. Volcanic ash consisting of two different particle sizes was used to prepare cement pastes with different ratios of Portland cement to volcanic ash. The concentration of the volcanic ash played a major role in the bound water index and self-diffusion coefficients of hydration water confined in the cement paste. An increase in the particle size of the volcanic ash affected the degree of hydration by allowing more free and mobile water in the gel pores, suggesting that volcanic ash may not have completely reacted during the experimental time frame. This study shows that the particle size along with variation in volcanic ash composition governs the early age hydration process in volcanic ash cements.     

硫酸腐蚀后油井水泥石的性能及微观结构

研究了硫酸对油井水泥石强度及微观结构的影响。结果表明：水泥石被硫酸腐蚀后,强度明显下降,硬化浆体中100 nm以上有害孔的数量显著增多,水化产物变得疏松多孔,硬化水泥浆体的物相组成发生变化,有新的腐蚀产物CaSO4·2H2O生成;水泥石抵抗酸性介质腐蚀的能力不仅与其致密程度有关,还与其硬化浆体的矿物组成密切相关;不同水化产物抵抗腐蚀的能力不同,Ca（OH）2比C-S-H凝胶更容易受到酸性介质的腐蚀;C-S-H凝胶被腐蚀后产生的孔隙主要是细小孔隙,而Ca（OH）2被腐蚀后产生的孔隙主要是100 nm以上有害孔,降低硬化浆体中Ca（OH）2的含量是提高水泥石抗腐蚀性能的关键。     

Measuring permeability and stress relaxation of young cement paste by beam bending

When a saturated rod of a porous material is deflected in three-point bending, two types of time-dependent relaxation processes occur simultaneously: hydrodynamic relaxation, caused by the flow of liquid in the porous body, and viscoelastic (VE) relaxation of the solid network. By measuring the decrease in the force required to sustain a constant deflection, it is possible to obtain the permeability from the hydrodynamic relaxation function, in addition to the VE stress relaxation function of the sample. We report the early-age evolution of permeability, elastic modulus, and stress relaxation function for Type III Portland cement paste with water–cement (w/c) ratios of 0.45, 0.50, and 0.55. The stress relaxation function is shown to preserve its shape during aging; that function is numerically transformed into the creep function.