Properties of polymer-modified cement mortar using pre-enveloping method

A new method, pre-enveloping sand with polymer, was adopted to make polymer-modified cement mortar (PCM). In the research, two kinds of latex, i.e., styrene acrylate rubber and styrene butadiene rubber, were used. The experimental results of physical and mechanical tests showed that, at the same level of polymer cement ratio, pre-enveloping method was better than normal method regarding the performance of the resulted composite. Moreover, in the condition of relatively low addition of polymer, the improvement of physical and mechanical properties, especially the resistance to cycling of freezing-thawing, by the pre-enveloping method was more significant. Additionally, it was found that styrene butadiene rubber can improve the fluidity of the mortar, and mortar with styrene acrylate rubber can maintain the same fluidity as the control sample by adding small quantities of a superplasticizer. Styrene acrylate rubber had no water-reducing ability by itself.     

The interface between polymer-modified cement paste and aggregates

The effects of polymer dispersions on the structure of the interfacial zone between portland cement paste and aggregates (limestone and granite) have been investigated. EDAX analyses of the polymer modified composites showed that a relatively high polymer content is present at the paste-aggregate interface. Scanning electron microscope (SEM) observations of fractured surfaces of the plain cement paste-aggregate interface revealed large calcium hydroxide crystals which are orientated with their c-axes perpendicular to the interface. With increasing polymer content cement hydration products become indistinct, and microcracks appeared to be bridged-up by the polymer film.     

Chemistry of cement hydration in polymer-modified pastes containing lead compounds

The role of polymeric additives on the hydration process of cement pastes admixed with a lead compound (Pb₃O₄) was investigated. Three series of pastes were prepared: the reference series, mixing water with Ordinary Portland Cement (OPC), and two series in which whether a styrene–butadiene rubber latex or a superplasticiser based on acrylic-modified polymer was added to the pastes. For each series, 5 and 10 wt% of Pb were mixed with the pastes. Phase analysis and microstructural characterisation were carried out by means of X-ray powder diffraction and SEM–EDX. Thermogravimetric analysis was performed to monitor the hydration degree of the three pastes; indeed, quantitative determination of portlandite and calcite was performed.Dynamic leach tests were performed on solidified monoliths to evaluate the effective immobilisation of Pb₃O₄. After 384 h leaching, excellent results were obtained by pastes mixed with superplasticiser that showed a cumulative release of Pb equal to 0.62 mg/l for samples containing 5 wt% of Pb, and equal to 0.84 mg/l for samples bearing 10 wt% of Pb.     

Experimental study on properties of polymer-modified cement mortars with silica fume

This paper discussed the flexural and the compressive strengths of polyacrylic ester (PAE) emulsion and silica fume (SF)-modified mortar. The chloride ion permeability in cement mortar and the interfacial microhardness between aggregates and matrix were measured. The chemical reactions between polymer and cement-hydrated product were investigated by the infrared spectral technology. The results show that the decrease of porosity and increase of density of cement mortars can be achieved by the pozzolanic effect of SF, the water-reducing and -filling effect of polymer. Lower porosity and higher density can give cement mortars such properties as higher flexural and compressive strength, higher microhardness value in interfacial zone and lower effective diffusion coefficient of chloride ion in matrix.     

Mechanical and adhesion properties of polymer-modified cement mortars in relation with their microstructure

In this study, cement mortars were modified with a commercial polymer admixture. The aim of this study is to investigate the influence of the polymer content on the mechanical and adhesion properties of the mortars and to relate these properties with mortars’ microstructure. A series of mortars were produced with various polymer/cement/water/aggregate ratios. The adhesion properties of the mortars to clay bricks were tested with a simplified tensile testing measurement. The microstructure of mortars, as well as interfaces, were evaluated by Scanning Electron Microscopy (SEM). It was found that with high polymer content, large size hardened particles are formed, reducing the compressive strength of the mortars. Polymer addition enhances the adhesion between the mortar and brick. The mortar microstructure at the interface affects the adhesion properties and the mode of failure.     

Microstructural aspects of failure in semicrystalline polymers

Microstructural features of semicrystalline polymers are reviewed, as are the roles of chain properties and thermal history in their development. Experimental results relating failure properties to microstructural detail are described. General models to explain inter- and intra-spherulitic failure behavior are proposed. Important are (a) the role of spherulite size in boundary incompatibility, (b) competition between spherulite boundary cracking and intraspherulitic yielding, (c) competition between localized (interspherulitic) fracture and dispersed (intraspherulitic) fracture.     

Microstructural evolution and texture analysis of magnesium phosphate cement

Three-dimensional quantitative image analysis from synchrotron X-ray microcomputed tomography indicated a coarsening of the microstructure of magnesium potassium phosphate cements driven by crystallization of K-struvite from the first amorphous product. Porosity and pore surface area increased because of the progressive build-up of a network of elongated/tabular crystal domains, with density higher than the amorphous. The known increase in strength with time is thought to occur thanks to the overwhelming contribution of a developing interlocked lath-shaped microstructure. Combined X-ray and neutron diffraction texture analysis indicated that at least a fraction of K-struvite nucleates at the surface of MgO grains, suggesting the intervention of more than one crystallization mechanism. The detected weak texture, compatible with a nearly random orientation of crystallites, and the isotropic pore fabric, are beneficial with respect to crack propagation.     

Microstructural study of gypsum activated fly ash hydration in cement paste

The addition of 3 to 6% gypsum to a low alkali, low C₃A cement blended with low (30 %) and high (60%) volume of a Class F fly ash (FA) led to a distinct increase in strength in comparision to the blends without additional gypsum. This is discussed in terms of the reaction of the FA with cement and gypsum. The role of FA alkalies is also described. The investigation included scanning electron microscopy/energy dispersive X-ray analysis (SEM/EDXA) to study the microstructural development of FA replacement pastes with progressive hydration, and X-ray diffraction (XRD) for mineralogical identification of hydrated phases.     

Microstructural development of early age hydration shells around cement grains

An important microstructural aspect of the early hydration of Portland cement (PC) is the formation of a shell of hydration products around cement grains. There is, at present, limited information on the mechanism of formation of the shell and of the chemistry of the phases that constitute the shells. Through the use of STEM imaging of early age hydrated cement pastes as early as 2 h, the present work shows that the shells correspond to the first C-S-H type product formed which has a distinct morphology compared to C-S-H formed later when the main reaction occurs (nucleation and growth stage at setting time). The shells form only around the silicate part of the grain and are not empty but filled with a fragile fibrous C-S-H which appears to have a lower (packing) density than the rest of the hydration products. The cement grains underneath the shells are seen to react unevenly and the hydration seems to follow a reaction front, leaving striations up to 1 µm deep on the grains. Over the long term, the original fragile product seems to densify and gives rise to the usual inner C-S-H. High resolution EDS chemical analysis and mappings were used to get insight into the chemistry associated with the formation of these early age products. The C/S ratio of all C-S-H (inner and outer shell) is the same (within the limits of the analysis accuracy) and evolves insignificantly over the first 24 h of hydration. High concentrations of sulfate are associated with the C-S-H formed during the early development of the microstructure, but these decrease later, the sulfate being mainly incorporated into ettringite.     

Microstructural aspects of the flow behaviour in a liquid—solids circulating fluidized bed

The local instantaneous and time‐average suspension densities were determined in a 76 mm diameter by 3 m tall liquid‐solids circulating fluidized bed riser using a fibre‐optic probe. Attempts were made to qualify the microflow structure through statistical analysis of the local bed voidage fluctuations obtained under different operating conditions for the first time. The results show that local microflow structure is uniform in the axial direction but non‐uniform in the radial direction with more flow fluctuation near the wall than in the core of the column for a given axial position. The standard deviation and intermittency index tend to increase with increasing solids circulating rates. Comparing with the gas—solids CFB, the liquid—solids CFB shows much more homogeneous flow structure in both the axial and radial microscopic flow behaviours. The microflow behaviours in the conventional liquid—solids fluidization, liquid—solids circulating fluidization and dilute‐phase liquid transport regimes are also characterized by examining the probability distribution and the intermittency index of the solids holdup.     

Oil well cement slurries I. Microstructural approach of their rheology

Oil Well Cement (OWC) slurries were studied for their rheological behaviour and sedimentation tendency as a function of dispersant concentration. Adsorption isotherms, zeta potential and sedimentation data indicate that saturation of the surface of cement particles by dispersant molecules suppresses attractive interparticle forces and therefore leads to sedimentation. This and the maximum yield value observed at low dispersant concentration can be explained by the patch model well known in colloidal chemistry.     

Hydrogarnet-type cubic crystals in polymer-modified mortars

Polymer-modified mortars (PMMs) using recently developed redispersible polymer powders and aqueous polymer dispersions have become popular construction materials in the world, particularly for finishing and repairing works, because of their excellent performance and durability. In order to develop usable models of structure-property relationships for such systems, the authors have focussed their studies on the microscopic level because such aspects still need more information. In this context, they have already reported their detailed observations on the formation of Ca(OH)₂, AFt, AFm, hollow tubules, and hollow crystals in PMMs (1–5). However, studies on hydrogarnet-type cubic crystals in PMMs were not available by that time.

The purpose of this paper is to establish morphologically the formation of hydrogarnet-type cubic crystals in PMMs.     

Microstructural and chemical aspects of working-temperature aged Ca-doped CeO2

Aging behavior investigation can provide a necessary basis for evaluating the suitability of doped ceria as the electrolyte material for intermediate temperature solid oxide fuel cells under working circumstances. In the current study, the microstructural and chemical variations of Ca-doped CeO₂ with various aging conditions have been systematically investigated by means of transmission electron microscopy (TEM), electron energy-loss spectroscopy (EELS), X-ray photoemission spectroscopy (XPS) and X-ray diffractometry (XRD). TEM shows that crystal defects in terms of microdomain and superstructure are alleviated by the aging processing. Reduction of the tetravalent Ce can be induced by high temperature aging, and the reduction fraction has been quantitatively determined within a broad temperature range. A new cerium oxide phase with a crystal structure of primitive monoclinic (a = 1.31 ± 0.013 nm, b = 0.38 ± 0.004 nm, c = 3.52 ± 0.035 nm, and β = 94.7 ± 0.3°) has been determined in the high temperature aged specimens. The possible effects of the evolutions in the microstructure and material chemistry on the ionic conductivity are discussed.     

Microstructural analysis of the bond mechanism between polyolefin fibers and cement pastes

This paper presents an investigation of polyolefin bond mechanisms in shotcrete. Polyolefin fibers were characterized in terms of their mechanical properties and microstructure. Effects of hydration reaction and of the mixing of fibers on the bond between the fiber and the paste were investigated in both the concrete mixture and its pore solution. Three cement types commonly used in the field were tested. Test results using scanning electron microscopy (SEM) analysis showed that the morphology of the fiber changes with cement hydration and mixing.     

Microstructural and bulk property changes in hardened cement paste during the first drying process

This paper reports the microstructural changes and resultant bulk physical property changes in hardened cement paste (hcp) during the first desorption process. The microstructural changes and solid-phase changes were evaluated by water vapor sorption, nitrogen sorption, ultrasonic velocity, and ²⁹Si and ²⁷Al nuclear magnetic resonance. Strength, Young's modulus, and drying shrinkage were also examined. The first drying process increased the volume of macropores and decreased the volume of mesopores and interlayer spaces. Furthermore, in the first drying process globule clusters were interconnected. During the first desorption, the strength increased for samples cured at 100% to 90% RH, decreased for 90% to 40% RH, and increased again for 40% to 11% RH. This behavior is explained by both microstructural changes in hcp and C–S–H globule densification. The drying shrinkage strains during rapid drying and slow drying were compared and the effects of the microstructural changes and evaporation were separated.     

Interphase effects in polymer-modified hydraulic cements

Earlier work has indicated the importance of interphase adhesion within these systems. The work here reported shows that, with reactive polymers, substantial chemical modification occurs at the surface of the polymer latex particle. With certain polymer types, such as polyethylene and polystyrene homopolymers, no evidence is found of such reactions; with others, such as poly(vinylidene chloride, vinyl chloride) and poly(ethyl acrylate, methyl methacrylate), substantial reaction occurs. Crosslinking and insolubilization frequently accompany these reactions, and the nature of the polymer is significantly altered.     

Ceramic-reinforced polymers and polymer-modified ceramics

The composites discussed in this review are prepared using techniques similar to those used in the new sol-gel approach to ceramics. Organometallis such as silicates, titanates, and aluminates are hydrolyzed in the presence of polymer chains (for example polysiloxanes and polyimides) that typically contain hydroxyl or amino groups. The functional groups are used to bond the polymer chains onto the silica, titania, or alumina being formed in the hydrolysis, thus forming organic-inorganic composites. When the polymer chains are present in excess, they constitute the continuous phase, with the ceramic-type material appearing as reinforcing particles. When present in smaller amounts, the polymer is dispersed in the continuous ceramic phase, to give a polymer-modified ceramic. Under some conditions, bicontinuous systems are obtained. The composites thus prepared are characterized by electron microscopy, X ray, and neutron scattering intensities, density determinations, and stress-strain and impact-strength measurements.     

Microstructural characterization of ITZ in blended cement concretes and its relation to transport properties

The improvements in the overall performances of concrete with blended materials were often ascribed to the modification of its hardened paste in general. In this paper, the effects of limestone filler (LF) and slag (GGBS) on chloride migration and water absorption of concretes with systematically varied aggregate properties were evaluated from the view point of ITZ by using BSE image, EDS, and MIP analysis. It was found that the incorporation of moderate amount of LF and GGBS would compact the microstructure of both ITZ and bulk cement matrix. The reduction in the pore volume (> 100 nm) contributes to the largest decrease in total porosity. Additionally, incorporating GGBS avoids the build-up of Ca(OH)₂ within ITZ and provides a more uniform microstructure. The mechanism for the improvement in limiting water and ions penetration was found to be mainly related to the densification of bulk cement matrix rather than the modification of ITZ.     

Reagentless recycling of pyruvate oxidase on a conducting polymer-modified electrode

The enzyme pyruvate oxidase (PyOD) covalently immobilized on an original conducting copolymer poly(5-hydroxy-1,4-naphthoquinone-co-5-hydroxy-3-thioacetic-1,4-naphthoquinone acid) can be recycled under anaerobic conditions, at +0.1 V versus SCE. It is first demonstrated that the quinone group is an efficient co-substrate for PyOD in homogeneous conditions, then this efficiency is preserved when the quinone group is embedded in the polymer structure. The copolymer remains efficient even in aerated media. The low working potential avoids side-oxidations of interfering species as ascorbic acid or salycilate.     

Critical aspects of nano-indentation technique in application to hardened cement paste

Several open questions related to the experimental protocol and processing of data acquired by the nano-indentation (NI) technique are investigated. The volume fractions of mechanically different phases obtained from statistical NI (SNI) analysis are shown to be different from those obtained by back-scattered electron (BSE) image analysis and X-ray diffraction (XRD) method on the same paste. Judging from transmission electron microscope (TEM) images, the representative volume element of low-density calcium-silicate hydrates (C–S–H) can be considered to be around 500 nm, whereas for high-density C–S–H it is about 100 nm. This raises the question how the appropriate penetration depth for NI experiments should be selected. Changing the maximum load from 1 mN to 5 mN, the effect of penetration depth on the experimental results is studied. As an alternative to the SNI method, a “manual” indentation method is proposed, which combines information from BSE and atomic-force microscopy (AFM), coupled to the NI machine. The AFM allows to precisely indent a high-density C–S–H rim around unhydrated clinkers in cement paste. Yet the results from that technique still show a big scatter.