Reliable characterization of the pore structure is essentially important for transport-related durability studies of cementitious materials. Mercury intrusion porosimetry has been commonly used for pore structure measurement while the ink-bottle effect significantly affects the trustworthiness of pore size features of cementitious materials. Pressurization-depressurization cycling mercury intrusion porosimetry (PDC-MIP) is an alternative approach previously reported with the purpose to provide better estimates of pore size results. It is found however that the PDC-MIP greatly overestimates the ink-bottle pore volume owing to the incomplete extrusion of mercury in throat pores after the pressurization-depressurization cycle. Intrusion-extrusion cyclic mercury porosimetry (IEC-MIP), as a further improvement, is then described, which can reliably capture the ink-bottle effect and obtain a clear picture of the distribution of the ink-bottle pores in cementitious materials. The ink-bottle effect of cement pastes is observed being pore size-dependent and the role of critical pores is emphasized. Water-cement ratio primarily changes the effective porosity while plays a minor role in the ink-bottle porosity. The addition of reactive blends substantially enhances the ink-bottle effect during mercury penetration into small pores. IEC-MIP tests, together with a unique data analysis, enable to obtain a more truthful pore size distribution.

Metastructures consisting of planar arrangements of bi-stable snap-through beams are able to exhibit multiple stable configurations. Apart from the expected translational state transition, when all beam elements snap through, rotational states may exist as well. In this paper we explore the rotational properties of multi-stable metastructures on the basis of both experimental and theoretical investigations, and define the conditions for achieving rotational stable states. Results show that the metastructure is able to realize both translational and rotational states, while the rotational transitions require less energy as compared to their translational counterparts. The influence of geometric parameters on rotational stability is investigated via parametric studies. Furthermore, to determine the design criteria for rotational stability, a theoretical investigation based on mode superposition principle is performed to predict the nonlinear-deformation of a unit cell. The theoretical analysis predicts well the rotational snap-through transitions that are observed in finite element simulations. It is found that the rotational stability is determined by setting proper values for h/L and t/L (h, t, L represent apex height, thickness and span of the bi-stable beam structure, respectively). Finally, we experimentally demonstrate that the proposed metastructure with multiple layers is able to achieve large rotations and translations.

Durability of photocatalytic coatings is a major concern in engineering practice. Here, two types of novel visible light-responsive coatings, both consisting of vinyl chloride/vinyl ester/ethylene copolymer (as a binder) and graphitic carbon nitride (g-C₃N₄) but different in fabrication, are proposed and applied on the mortar surface. The first type is mono-layer coating (MC), where the g-C₃N₄ suspension containing the binder is directly sprayed on the mortar. The second type is double-layer coating (DC), where the binder layer is applied on mortar surface before spraying the g-C₃N₄ layer. Results show that the binder addition leads to a good anchorage of the coatings on both MC and DC mortar substrates, along with desirable resistance to peeling and washing, compared to the g-C₃N₄ coated mortar without the binder. The well-distributed binder in g-C₃N₄-based coating inevitably decreases the photocatalytic efficiency of the MC mortar due to masking effect of the binder on the coating surface. The DC mortar, on the contrary, takes full advantage of the binder adhesion by inserting a binder layer and therefore holds strong resistance to peeling and washing without compromising its photocatalytic efficiency. The proposed DC technique provides a promising strategy to fabricate highly cost-effective and durable photocatalytic coatings applied on cementitious materials.

Microstructure-property relationship has drawn strong attention in modern material science. The progress achieved in this field relies on a common basis that the material performance originates from the microstructure. This paper brings together new insights and facts from experiments regarding the pore size dependent connectivity and its relation to ionic transport property in saturated cementitious materials. An innovative measurement, i.e. intrusion-extrusion cyclic mercury porosimetry (IEC-MIP), is proposed to distinguish between the small capillary pores that are present within clusters of hydration products and the large capillary pores that are left out of hydration products. The distribution of connectivity as a function of pore size in cementitious materials is analyzed. A novel transport parameter, i.e. connectivity of small capillary pores, is introduced and quantified by IEC-MIP measurements. The ionic transport was measured by means of rapid chloride migration tests. A power relationship is established between connectivity of small capillary pores and chloride migration coefficient for cementitious materials irrespective of the binder type.

Rheological properties are of significant importance in successful placement and performance of self-compacting concrete (SCC). In this work, the rheological properties of SCC, combined with a powder-viscosity modifying admixture, were investigated based on a series of experimental studies. The modified Bingham model was applied to determine the rheological parameters and shear thickening behavior of SCC. The effects of mixing procedures, including charging sequence, mixing time and mixing speed, were analyzed. The results show that the shear thickening of SCC is reduced by first mixing the aggregate and water and then adding other raw materials. The direct contact between aggregate and water leads to a large amount of free water to be adsorbed by the aggregate system, resulting in an increase of the yield stress. In order to ensure an excellent fluidity and a low shear thickening behavior of SCC, the mixing time should be controlled at 4-5 min and the mixing speed at 30-45 r/min.

Pumping is the most common technique used to transport fresh concrete in construction sites. The large-scale use of concrete all over the world makes the pumping increasingly important. A wide variety of additives and admixtures are incorporated into modern concrete in order for sustainable development. The performance of modern concrete is rather complex and its pumping behavior differs significantly from that of conventional concrete, especially in the fresh stage. This paper presents a comprehensive overview on the state of the art of concrete pumping. The models and methods used for characterizing the concrete pumpability and lubrication layer are described. The factors influencing the pumping behavior are discussed. A couple of ultra-high pumping engineering of concrete conducted in China are introduced.

Conceptual analysis is performed to examine the effects of pore features on the water continuity in unsaturated porous systems. The roles of pore features in relative chloride diffusion coefficient (D_rc) of mortar specimens at various degrees of water saturation (S_w) were studied based on mercury intrusion porosimetry and resistivity tests. It is found that the role of pore structure in the D_rc-S_w relationship is a result of its effect on the water continuity. Porosity and tortuosity are not relevant to the D_rc-S_w relationship. A finer pore size distribution or lower pore connectivity tends to result in a lower D_rc. The pore size effect on the D_rc is pronounced primarily at high S_w, while the D_rc is dominated by the pore connectivity at low S_w. Cement mortar with a higher water-to-binder ratio shows larger chloride diffusion at high relative humidity levels but smaller chloride diffusion at low relative humidity levels.

Concrete is rarely saturated. Reliable durability design of marine concrete structures requires a solid understanding of the long-term chloride transport in unsaturated concretes. This paper presents a critical analysis of the time-dependent chloride diffusion coefficient in unsaturated cementitious materials exposed to marine environment. Evolutions of pore structure and chloride diffusion coefficient in saturated cementitious materials, along with the role of the degree of water saturation in long-term chloride diffusion, are analyzed. It is emphasized that the long-term sharp decrease of the chloride diffusion coefficient in marine cementitious materials is not primarily caused by densification of the microstructure due to hydration, but by the decreasing degree of water saturation with depth in the surface part of the materials. The effects of water/binder ratio and supplementary cementitious materials on chloride diffusion coefficient are different between saturated and unsaturated cementitious materials.

An analytical model for predicting the relative chloride diffusion coefficient in cementitious materials at different degrees of water saturation is presented in this paper. The model is developed based on the Nernst-Einstein equation and conductivity of cementitious electrolyte, as well as on moisture distribution in the pore structure. Good agreement is found between the model and the experimental data. With the help of the model, the chloride diffusion coefficient of cementitious material at unsaturated state can be determined according to the chloride diffusion coefficient at saturated state, the degree of water saturation and the average pore diameter of the material. A detailed discussion about the inputs and outputs of the model is given in order to facilitate its application for engineering practice.

Lagged settlement is a typical accident induced by shield construction in sandy cobble strata. This paper analyzed the process and mechanism of lagged settlement, results show that all phases are in accord with the characteristics of ellipsoid theory of particle flows. Based on this theory, a method for calculating coefficient of lateral earth pressure and loosened earth pressure is proposed in this research. For the coefficient of lateral earth pressure, the boundary of loosened ellipsoid is divided into two parts, the arch zone and the excavation zone, and the lateral pressure coefficients are derived respectively according to the stress state. For loosened earth pressure on tunnel, the Terzaghi earth pressure theory and Protodyakonov earth pressure theory are adapted in different conditions according to the state of loosened cobble soil. Theories developed in this study can be applied on determination of shield excavation parameters, as well as calculation of loosened earth pressure and control of tunnel support.

An "on water" organocatalytic cyanoarylmethylation of aryl acetonitrile to isatins is developed, giving products in high yields and up to excellent diastereoselectivities. A remarkable enhancement of reaction rates and diastereoselectivities by water was observed under mild conditions. Moreover, this approach provides a highly efficient and environmentally benign access to thermodynamic 3-hydroxy-3-cyanomethyl oxindoles.

The combination of photocatalyst with cementitious materials for air pollution abatement and self-cleaning has gained considerable attention. However, the most popularly used photocatalytic cementitious composites based on TiO₂ achieve the purification function under ultraviolet sunlight, significantly impeding a broader application of photocatalytic cementitious composites. Here, the photocatalytic cementitious composites were prepared by incorporating g-C₃N₄ nanosheets (CNNs) in Portland cement. With the increase of CNNs content, the photocatalytic NO_x abatement and self-cleaning performance was notably improved, while the micro-hardness of cementitious composites increased first and then decreased. Among the three mixing dosages (0.5%, 1% and 2% by weight of cement), the cementitious composite admixed with 2% CNNs showed the highest photocatalytic NO_x abatement efficiency of 227.3 μmol m⁻² h⁻¹, and could degrade the rhodamine B within 40 min under visible light. Additionally, its microscopic hardness was 5.4% higher than the one without CNNs, suggesting that a moderate amount of CNNs (below 2%) in cementitious composites was effective in achieving an improved photocatalytic depollution performance.

The internal relative humidity (RH) plays a crucial role in most of the concrete properties. Self-desiccation caused by continuous cement hydration is a major factor affecting the RH of concrete. This paper investigates the relationship between RH and microstructure for cementitious systems in the case of self-desiccation. A series of paste specimens prepared with different binder and water-binder-ratio (w/b) were cured under sealed conditions from 1 day to 1.5 years. The RH and microstructure of the paste specimens were measured. The microstructure characteristics under study include porosity, pore size, evaporable and non-evaporable water content. The results reveal that the RH of cementitious system drops to a great extent in the first 105 days' hydration and decreases slowly afterwards. The blended materials such as fly ash, slag or limestone powder have different influences on the RH. A mathematical model between RH and the average pore diameter is proposed for cementitious systems under self-desiccation, regardless of age, w/b or cement type.

The production of cement leads to a large amount of CO₂ emission. Using industrial waste slag, such as ceramic polishing powder (PP), to replace part of Portland cement can reduce the pollution caused by the cement industry and solid waste disposal. In order to use PP as a replacement for cement, its effects on the properties of cement paste need to be clarified. In this study, the effect of PP on the nucleation and growth of hydrates in cement paste at very early ages was investigated. Quartz was used as a reference. The interactions of their surface with various ions in cement paste solution, which has an important effect on the nucleation and growth of hydrates, were studied by using the zeta potential test. The morphology of the nucleus and crystal of hydrates was investigated by using SEM. The zeta potential measurements showed that the affinity of the surface of PP and quartz to ions in the pore solution of cement paste is similar. The image of SEM indicated that there is also not much difference in the crystallization of hydrates on the surfaces of PP and quartz. These evidences suggested that PP has similar surface charge properties as quartz, and its effects on the properties of cement paste are the same as that of quartz. From the viewpoint of the effect on very early hydration, PP can be used in cement paste, similar to quartz power.

Experiments have been carried out to study the influence of moisture condition, including moisture content and its distribution, on the chloride diffusion in partially saturated ordinary Portland cement mortar. The mortar samples with water-to-cement (w/c) ratios of 0.4, 0.5 and 0.6, cured for 1 year, were preconditioned to uniform water saturations ranging from 18 to 100%. The interior relative humidities of these partially saturated cement mortars, i.e. water vapour desorption isotherm (WVDI), were measured. The WVDI results in relation to the pore structures obtained from the mercury intrusion porosimetry tests of paste samples with the same w/c ratios were analyzed, which provided a basic insight into the moisture distribution in the non-saturated cement mortars. The relative chloride diffusion coefficients of cement mortars at various water saturations were determined based on the Nernst-Einstein equation and conductivity technique. It is found that the relative chloride diffusion coefficient D_rc depends on the degree of water saturation S_w and WVDI. At a given S_w level, the D_rc is larger for a higher w/c ratio. The role of the w/c ratio in the D_rc–S_w relation, however, becomes less pronounced with increasing w/c ratio. There exists a critical saturation, below which the water-filled capillary pores are discontinuous and the D_rc-value tends towards infinitely small. An increase of the w/c ratio results in a decrease of the critical saturation level.