The traps in characterisation of PAN and carbon fibers by the mercury porosimetry method

The mechanical properties of a fiber relate to an average pore size or the pore size distribution in the fiber. In this study, the effects of testing sample preparation, crystallization rate, humidity, sizing agent, composition and processing conditions on the pore size distribution measurements were analyzed and discussed.     

Porosity, pore size distribution and in situ strength of concrete

In this study, in situ strength of concrete was determined through compression test of cores drilled out from laboratory cast beams. The apparent porosity and pore size distribution of the same concrete were determined through mercury intrusion porosimetry, performed on small-drilled cores. The normal-strength concrete mixes used in the experimental investigation were designed to exhibit a wide variation in their strengths. To ensure further variation in porosity, pore size distribution and strength, two modes of compaction, two varieties of coarse aggregates, different levels of age, curing period and exposure condition of concrete were also introduced in experimental scheme. With the data so generated, an appraisal of the most frequently referred relationships involving strength, porosity and pore size of cement-based materials was carried out. Finally, a new empirical model relating the in situ strength of concrete with porosity, pore size characteristics, cement content, aggregate type, exposure conditions, etc., is presented.     

Assessment of permeation quality of concrete through mercury intrusion porosimetry

Permeation quality of laboratory cast concrete beams was determined through initial surface absorption test (ISAT). The pore system characteristics of the same concrete beam specimens were determined through mercury intrusion porosimetry (MIP). Data so obtained on the measured initial surface absorption rate of water by concrete and characteristics of pore system of concrete estimated from porosimetry results were used to develop correlations between them. Through these correlations, potential of MIP in assessing the durability quality of concrete in actual structure is demonstrated.     

Three-dimensional visualization of pore structure in hardened cement paste by the gallium intrusion technique

It is widely known that the pore structure of concrete strongly influences its physical properties. Therefore, we developed a technique for the visualization of the pore structure because of clearing it correctly. However, this visualization is limited to two-dimensional imaging for sections of the specimen. As a result, in this study, we developed a technique for reconstructing the acquired 2D images of the pore structure into 3D form by stacking them. By using this image, the relationship between water permeability and pore connectivity was clarified, and it was shown clearly that the pore connectivity strongly affects the water permeability.     

Porosity and specific surface area of Roman cement pastes

Mercury porosimetry, water vapour and nitrogen adsorption were used to follow the hydration of Roman cements — belite cements calcined at low temperature. Generally, unimodal distribution of pore sizes was observed, with the threshold pore width decreasing considerably with increasing curing time. An open porous structure with the threshold pore diameter between 0.2 and 0.8 μm and the specific surface area not exceeding 20 m²/g was produced at early ages when quick growth of the C–A–H phases is observed. The surface area reached up to 120 m²/g and the threshold pore width shifted to around 0.02 μm when the subsequent formation of C–S–H gel filled the larger pores. Both mercury porosimetry and water vapour adsorption were found to be capable of following the progress of hydration of the Roman cements with high reliability at least for a comparative evaluation of historic Roman cement mortars and repair materials used in restoration projects.     

Influence of superplasticizers on the hydration of cement and the pore structure of hardened cement

This paper describes the influence of various types of superplasticizers such as naphthalene type (β-NS), refined lignin sulfonate type (LS) and polycarboxylate types (P34, S34) on the hydration of cement and the pore structure of hardened cement. Other superplasticizers except β-NS delayed the initial hydration of cement. In any case, it hardly influences the hydration reaction at late stage of cement. The retardation by the addition of superplasticizers is not observed after 28 days of curing. Large pores of 0.1 μm or more for hardened cement with LS or β-NS are larger than those of hardened samples with P34 or S34 cured for 28, 56 and 91 days. This is related to the coagulated structures of fresh cement pastes with various types of superplasticizers. It was presumed that the size of the cluster of aggregated particles became small when S34 or P34 that has a high dispersing ability was added compared to LS or β-NS that has a lower dispersing ability.     

Change in pore structure and composition of hardened cement paste during the process of dissolution

An understanding about the dissolution phenomena of cement hydrates is important to assess changes in the long-term performance of radioactive waste disposal facilities. To investigate the alteration associated with dissolution, dissolution tests of ordinary Portland cement (OPC) hydrates were performed.Through observation of the samples after leaching, it was confirmed that ettringite precipitation increased as the dissolution of the portlandite and the C-S-H gel progressed. EPMA performed on cross-sections of the solid phase showed a clear difference between the altered and unaltered parts. The boundary between the two parts was termed the portlandite (CH) dissolution front. As the leaching period became longer, the CH dissolution front shifted toward the inner part of the sample. A linear relationship was derived by plotting the distance moved by the CH dissolution front against the square root of the leaching time. This indicated Ca ion movement by diffusion.     

The pore solution phase of carbonated cement pastes

Samples of hydrated cement pastes were exposed to atmospheres with various carbon dioxide concentrations at relative humidities controlled by different saturated salt solutions. When carbonated throughout their thickness, as indicated by the phenolphthalein test, they were resaturated with water and subjected to pore solution expression and analysis. The effects of the various carbonating environments on the pore solution composition and on aspects of the pore structure and mineralogy of the carbonated products are reported. Implications regarding the likely effects of different accelerated carbonation regimes on the corrosion behaviour of steel in concrete are discussed. In particular, it is shown that the use of saturated sodium nitrite solution to control the relative humidity of atmospheres with high concentrations of carbon dioxide may cause an evolution of gaseous oxides of nitrogen, which can result in the contamination of the pore solution with nitrite and nitrate salts.     

NMR studies of pore formation and water diffusion in self-hardening cut-off wall materials

Cut-off walls for the containment of polluted sites are vertical in-ground barriers of low hydraulic conductivity. To construct these barriers, self-hardening watery suspensions of a special cement-based hydraulic binder and a cement-stable bentonite are used. The formation of the pore structure during hardening of suspensions with different solid contents and the water self-diffusion in the resulting cut-off wall materials were studied by non-destructive ¹H NMR techniques. It was found that an increased amount of hydrating solids in the suspension leads to a decrease in NMR relaxation times and self-diffusion coefficients of the pore water, indicating a reduction of the pore sizes and an enhancement of the diffusion resistance. The self-diffusion coefficients of the water in the hardened cut-off wall materials were determined to be about four orders of magnitude smaller than in bulk liquid water and two orders of magnitude smaller than in pure bentonite-water suspensions confirming the excellent diffusive resistance of the cut-off wall materials.     

Activation of fly ash cementitious systems in the presence of quicklime. Part II: Nature of hydration products, porosity and microstructure development

Following the first paper of a two-part series study on the activating effect of industrial quicklime upon different fly ashes, the current paper concludes on its beneficial role by focusing on the nature of hydration products, pore size and microstructure evolution of each system that was investigated. By looking into the development of these properties, the exact effect of the chemical activator could be elucidated, but furthermore a first approximation of the durability efficiency of the examined systems could be obtained. In the frame of this second part, it was demonstrated that, apart from portlandite, calcium sulphoaluminates (ettringite and monosulfoaluminate) along with some gismondine and gehlenite hydrate (C₂ASH₈) crystals are formed in activated fly ash-cement pastes from the first week of hydration. Mercury intrusion porosimetry data confirmed the beneficial action of quicklime, towards decreasing the total pore volume (and concurrent increase in the volume occupied by fine pores) in high-lime ash blends. Gel/space ratios were estimated for each blended paste, and fine, almost linear, correlation was established with total porosity values. Microscopical observations revealed that the critical contribution of quicklime in the production of secondary C–S–H nearby the ash particles. The flocculent-like gel collaborates smoothly with needle-like products and finely-dispersed crystals towards the gradual impletion of the pores and strengthening of the paste.     

On the relationship between pore structure and chloride diffusivity from accelerated chloride migration test in cement-based materials

In this study the electrochemical technique is applied to accelerate chloride ion migration in concrete to determine the chloride ions in anode cell, and the pore characteristic of the same mortars in concrete was obtained from the mercury intrusion porosimetry (MIP). The plain ordinary Portland cement and the constant aggregate with eight w/c ratios ranging from 0.3 to 0.65 were used. A good linear relationship between the steady-state migration coefficient and non-steady-state migration coefficient based on the same experimental setup and specimens was obtained. Both of the steady-state migration coefficient and non-steady-state migration coefficient were linearly related to the capillary pore volume and the critical pore diameter.     

Pore size and shape in mortar by thermoporometry

The pore structure of mortar (w/c = 0.55) was examined using thermoporometry (TPM), nitrogen adsorption/desorption (NAD), and mercury intrusion porosimetry (MIP). The TPM measurements were calibrated by comparison to NAD and MIP measurements on porous glass; similar comparisons were made on dried and resaturated mortars. For undried mortars, TPM provides the size of pore entries (from the freezing cycle) and interiors (from the melting cycle). In keeping with previous studies, we find that there is an unfrozen layer of water between the ice and the pore wall in porous glass that is about 0.8 nm thick; when lime-saturated water is used, the thickness of that layer increases by about 10%. In mortar, the unfrozen layer is about 1.0-1.2 nm thick, so no freezing occurs in pores with diameters ≤ 4.5 nm, at least down to − 40 °C (where the radius of the crystal/liquid interface is ∼ 1.5 nm). Based on the hysteresis in the freezing and melting curves, the larger mesopores in mortar were found to be rather spheroidal, while the smaller ones were more cylindrical.     

An ESEM investigation of latex film formation in cement pore solution

Environmental scanning electron microscopy (ESEM) and complementary methods were employed to study the time dependent film formation of a latex dispersion in water and cement pore solution. First, a model carboxylated styrene/n-butyl acrylate latex dispersion possessing a minimum film forming temperature (MFFT) of 18 °C was synthesized in aqueous media via emulsion polymerization. Its film forming property was at a temperature of 40 °C, studied under an ESEM. The analysis revealed that upon removal of water, film formation occurs as a result of particle packing, particle deformation and finally particle coalescence. Film formation is significantly retarded when the latex dispersion is present in cement pore solution. This effect can be ascribed to adsorption of Ca²⁺ ions onto the surface of the anionic latex particles and to interfacial secondary phases. This layer of adsorbed Ca²⁺ ions hinders interdiffusion of the macromolecules and subsequent film formation of the latex polymer.     

Experimental determination of the effective anionic charge density of polycarboxylate superplasticizers in cement pore solution

The specific anionic charge density of polycarboxylate superplasticizers can be determined experimentally by titration with a cationic polyelectrolyte. In this study, the anionic charge densities of several polycarboxylates based on methacrylate ester chemistry were measured in aqueous solution at pH 7 and 12.6, resp., and in cement pore solution. The anionic charge of the polycarboxylates increases with increasing pH value as a result of deprotonation of the carboxylate groups in the polymer backbone. Addition of Ca²⁺ ions generally causes a decrease of the anionic charge density. The reduction in anionic charge varies and depends on the architecture of the polycarboxylate. The effect results from the binding of calcium ions by the carboxylate groups, both through complexation and counter-ion condensation. Consequently, the effective anionic charge density of polycarboxylates in cement pore solution can differ significantly from the charge density which is calculated based on the chemical composition. Generally the -COO⁻ functionality may coordinate Ca²⁺ as a monodentate or bidentate ligand. The type of coordination depends on the steric accessibility of the carboxyl group. In PC molecules possessing high side chain density, the -COO⁻ group is shielded by the side chains and coordinates as bidentate ligand, producing a neutral Ca²⁺-PC complex. Accordingly, this type of PC shows almost no anionic charge anymore in cement pore solution. In PCs possessing high amount of -COO⁻, Ca²⁺ is coordinated monodentate, resulting in an anionic complex. Consequently, this type of PC shows significant anionic character in pore solution. Its adsorption behaviour is determined by a gain in enthalpy which derives from the electrostatic attraction between the PC and the surface of cement. This way, by utilizing the relatively simple method of charge titration, it is possible to assess the electrostatic attraction which, besides entropy gains, is the driving force behind the adsorption of polycarboxylates on the cement surface and thus determines their effectiveness as dispersing agent. The findings are generally applicable to other anionic admixtures used in cement.     

Magnetic resonance studies of cement based materials in inhomogeneous magnetic fields

Single-sided magnets give hope that Nuclear Magnetic Resonance (NMR) might in future be used for in situ characterisation of hydration and water transport in the surface layers of concrete slabs. Towards that end, a portable NMR-MOUSE (MObile Universal Surface Explorer) has been used to follow the hydration of gypsum based plaster, a Portland cement paste and concrete mortar. The results compare favourably to those obtained using a standard laboratory bench-top spectrometer. Further, stray field imaging (STRAFI) based methods have been used with embedded NMR detector coils to study water transport across a mortar/topping interface. The measured signal amplitudes are found to correlate with varying sample conditions.     

Early-age behavior of materials with a cement matrix

Materials with a cement matrix classically present early-age volume variations (shrinkage and/or swelling). This intrinsic early-age behavior strongly influences the length of time the buildings and structures will last because of the micro-cracking and cracking that results from it. One explanation for the macroscopic shrinkage is the presence of pore pressure in the porous medium. In this study, fine modeling of the coupling mechanism behind these internal strains is proposed. The chemical reaction associated with hydration is considered as the main force behind the hydric and mechanical evolutions in an endogenous configuration. Thus, the influence of chemical contraction, porosity, pore-size distribution and pore pressure are central to the study in the light of the numerical and experimental results obtained. A self-leveling layer of mortar of sulfo-aluminous concrete base was used.     

Study on some factors affecting the results in the use of MIP method in concrete research

Effects of rate of pressure application and forms and type of sample on porosity and pore size distribution of concrete estimated through mercury intrusion porosimetry (MIP) are presented in this experimental work. Two different forms of concrete sample, namely, crushed chunks of concrete and small core drilled out from the concrete beam specimens, were used for this study. The results exhibit that the rate of pressure application in mercury porosimetry has little effect on porosity and pore size distribution of concrete. It is also demonstrated that small cores drilled out from large concrete specimens are preferable as samples for performing porosimetry test on concrete.     

Characterization of partially densified 3D Cf/SiC composites by using mercury intrusion porosimetry and nitrogen sorption

The microstructure of partially densified three-dimensional carbon fiber fabrics reinforced silicon carbide (C_f/SiC) composites are characterized by both mercury intrusion porosimetry (MIP) and isothermal nitrogen sorption (INS). By comparison, MIP is preferable to the characterization for its wide effective probing ranges. Based upon multiple measurements, in the C_f/SiC composite, exists a complicated three-dimensional porous network formed by the interconnecting pores and necks with various sizes, diverse shapes and rough surfaces.     

Influence of heat curing on the pore structure and compressive strength of self-compacting concrete (SCC)

The mechanical properties of self-compacting concrete (SCC) are well understood. But there are no scientific investigations available on the influence of a heat treatment on the properties of SCC. To evaluate the influence on the compressive strength, SCCs as powder type, combination type and viscosity-agent type in the strength classes between C20/25 and C70/85 were designed and exposed to heat treatment with different maximum temperatures. It has been found that there is an influence of the composition of the concrete, especially the (w/c)_eq ratio, on the compressive strength after heat treatment. The reason for the substantial loss of strength in some cases compared to the strength of the concrete, which was stored under standard conditions, is a change of the pore size distribution. An empirical formula is presented to calculate the influence of the heat treatment on the compressive strength of the SCCs.     

Characterization of multi-scale porosity in cement paste by advanced ultrasonic techniques

The effectiveness of advanced ultrasonic techniques to quantitatively characterize the capillary porosity and entrained air content in hardened cement paste is examined. Direct measurements of ultrasonic attenuation are used to measure the volume fraction and average size of entrained air voids and to assess variations in intrinsic porosity - as influenced by water-to-cement ratio (w/c) - in hardened cement paste samples. For the air entrained specimens, an inversion procedure based on a theoretical attenuation model is used to predict the average size and volume fraction of entrained air voids in each specimen, producing results in very good agreement with results obtained by standard petrographic methods and by gravimetric analysis. In addition, ultrasonic attenuation measurements are related to w/c to quantify the relationship between increasing porosity (with increasing w/c) and ultrasonic wave characteristics.