Lightweight expanded clay aggregates (LWAs) are porous materials with low density and high strength (EN-13055-1), and they are important in sustainable construction through their lightweight nature and ability to provide thermal or acoustic insulation. The objective of this work was therefore to evaluate the preparation of LWAs using a smectite clay (M1 formulation), whose application in common ceramic production is difficult. An alternative approach was proposed for the valorization of phosphate sludge and a palygorskite-rich sediment by mixing them with expanded clay (M2 formulation) for LWA production. This could result in economically cost-effective products with significant environmental benefits. Pellets were prepared and fired at various temperatures (1100°C, 1125°C and 1150°C), and relevant properties such as bloating index, density, water absorption and compressive strength were determined. Additionally, the microstructure, mineralogical transformations and phase compositions under various sintering temperatures were investigated. Increasing the temperature from 1000°C to 1150°C significantly improved the expansion properties of LWAs, and 1150°C seemed to be the optimal firing temperature at which the best expansion properties were achieved. In addition, the incorporation of the selected waste improved the properties of the final products, leading to lower density, greater strength and greater bloating with the development of the internal pore structure as compared to the LWAs without this addition. Because of their low density (0.6 g cm–3) and sufficient compressive strength (0.86 MPa), the manufactured LWAs can be used in construction (as insulating panels or in lightweight concrete) and in green roofs.

The interface performance between clay–sand mixtures and concrete structures is governed by the mixture's composition and its physical properties. Moisture content and particle-size distribution play important roles in deciding the mixture's arrangement of soil particles, porosity, hydraulic conductivity and behaviour under various mechanical loadings. Application of a polymer interfacial coating can improve the bond performance between soils and concrete mainly via interfacial friction/mechanical interlocking. The present work analyses the development of interfacial strength between clay–sand mixtures and a polymer coating with changes in particle gradation. The multi-scale mechanisms at the interface are investigated, giving primary attention to soil porosity. A 50:50 clay–sand mixture exhibited a greater interfacial adhesive performance compared to other soil mixtures. In addition, the moisture-controlled pores and gradation-controlled pores demonstrated differences in macroscale interfacial strength. Both mercury intrusion porosimetry (MIP) and 129Xe nuclear magnetic resonance (NMR) were utilized to detect the pore structure of the mixtures. 129Xe-NMR revealed the pore distribution of the mixtures as ranging from macropores to nanopores, and MIP complemented the pore information by determining the critical pore entry diameter in the macropore regime. Mesopores dominated with increasing fine sand content until a threshold value was reached; thereafter, merging of pores occurred and macropores dominated.

Recent pedological evidence of the widespread distribution of beidellites in soils indicates the need for a greater knowledge of the effect of charge location on the microstructural organization of Na+ smectite in gels. After equilibration at a suction pressure of 3.2 kPa before and after desiccation, TEM observations showed large differences between a beidellite and both a low and high charge montmorillonite. Monolayers were rare; individual layers were instead organized in particles with larger interparticle distances. This has implication for theories relating swelling pressures to interlayer distances or surface areas and implies the need for a geometrical approach to the study of swelling in smectites. Location of isomorphous substitution in the tetrahedral sheet of smectites results in an increased lateral extension of overlapping layers. This was reflected in a greater capacity to rehydrate after desiccation. Increased number of layers in particles were found with increasing surface charge density. The geometric organization of the particles is critical to the understanding of the ability of Na+ smectite to hold water against an applied suction.

Clay samples of greenish colour were collected from submarine hydrothermal chimneys of the Galapagos Rift and Mariana Trough. Mineralogical and chemical investigations of the clay by scanning and transmission electron microscopy, X-ray diffraction, differential thermal analysis, infrared-spectros-copy, X-ray fluorescence, and determination of specific surface area, and oxygen isotope composition identify it as a well crystallized nontronite. This nontronite of hydrothermal origin has a nearly monomineralic character, a low Al-content, and a formation temperature of 21.5 to 67.3°C. The most remarkable characteristic, however, of the nontronite deposit is its microstructure, a network of microtubes composed of fine frequently folded clay sheets. These delicate filaments show close similarity in size and form to sheath forming bacteria. The correlation between clay mineral and chemical characteristics, as well as biological conditions at marine hydrothermal smoker chimneys, let us suggest that Fe oxidizing, sheath forming bacteria are playing a decisive role in nontronite formation at these sites.

Homoionic Ca-saturated clay pastes were prepared and drying curves were obtained by applying suction pressures from 1 kPa to 100 MPa, A transmission device was used to study particle orientation by placing the clay in a cell specially designed to obtain diagrams corresponding to different sample orientations. The 00l and hk0 reflections were compared to determine the best reflections for studying clay-particle orientation. Depending on the clay, 00/ reflections or the 020 reflection and/or hkl bands can be used to analyze orientation. In many cases the 020 reflection is preferred because the intensity of the peak is high and appears to be independent of the H2O content and the degree of stacking order of layers along the [001] direction.

For interstratified clays, the conditions required to obtain 00l reflections depended on several factors, the most important of which is the water content. Also, the intensity relating to particie orientation depends on (1) particle extension (size) in the (001) plane and (2) the crystal structure. Illite crystals of <1000 A gave a poorly oriented clay matrix. In contrast, large aggregates of illite, smectite, and kaolinite particles (>10,000 Å) showed a strongly oriented system. The particles of smectites may be curved and the dry material was poorly oriented owing to weak cohesion forces between the layers in comparison to illite.

The study of the orientation of particles by X-ray diffraction on hydrated samples may be affected by sample mounting techniques. Any change in the content or the way the sample is mounted may modify the microstructure of a material.

Clay containing a high water content affects the disorientation of particles, whereas, for the dry samples, pore size, pore volume, and solid continuity are associated with the geometry and crystal structure of the clay matrix.

This paper aims at characterizing the morphology, texture, and microstructure of three hydrated kaolin rich clays (f < 0.2 μm) from volcanic soils. These clays represent a weathering sequence in which CEC, halloysite content with respect to kaolinite, as well as smectite content in the halloysite-smectite mixed-layer clays decrease with increased weathering. The clay samples were made homoionic (K+ or Mg2+) and hydrated under a low suction pressure (3.2 kPa). After replacing water by a resin, ultrathin sections were cut and examined by TEM. Particle shape varies with increased weathering, as follows: spheroids → tubes → platelets. Higher aggregation and dispersion are observed by TEM after Mg2+ and K+ saturation, respectively, at two levels of the clay-water system organization: intraparticle and interparticle. The microstructure variations induced by the nature of the exchangeable cation become less pronounced with decreasing layer charge of the 2:1 layers. They are thus related here to the presence of smectite layers localized in the halloysite habitus, mostly at the particle periphery. These results show that small amounts of smectite largely affect the organization of clays rich in kaolins at a high water content, and that K+ behaves here as a dispersing ion.

Nontronite and microbes were detected in the surface layers of deep-sea sediments from Iheya Basin, Okinawa Trough, Japan. Nontronite, an Fe-rich smectite mineral, was embedded in acidic polysaccharides that were exuded by microbial cells and electron microscopy showed that the nontronite layers were apparently oriented in the polysaccharide materials. We propose that the formation of nontronite was induced by the accumulation of Si and Fe ions from the ambient seawater and that extracellular polymeric substances (EPS) served as a template for layer-silicate synthesis. Experimental evidence for this hypothesis was obtained by mixing a solution of polysaccharides (dextrin and pectin) with ferrosiliceous groundwater. After stirring the mixture in a sealed vessel for two days, and centrifuging, Fe-rich layer silicates were identified within the precipitate of both the dextrin and pectin aggregates, whereas rod-shaped or spheroidal Si-bearing iron hydroxides were found in the external solution. Microbial polysaccharides would appear to have affected layer-silicate formation.

The objective of this research was to study the cellulose addition effect on the geopolymerization of heated clay. The clay, composed of illite, plagioclase and kaolinite, was heated at 700°C for 2 h and mixed with cellulose (up to 10 mass%). The mixtures were NaOH-activated, and shaped samples were aged at 83°C for 30 days. The cured samples were investigated by using X-ray diffraction, Fourier-transform infrared spectroscopy and scanning electron microscopy. The influence of the cellulose addition on the mechanical/physical properties was also evaluated. The results showed that zeolite ZK-14, hydrosodalite, sodium carbonate and a geopolymer composed of poly(sialate) units were formed in all cured samples. The relative amounts of zeolite and metakaolin evolved antagonistically, whereas that of illite slightly decreased with increasing cellulose content. Metakaolin and illite were involved in the geopolymerization process. Cellulose addition led to the improvement of the flexural strength of the samples and to porosity reduction. By contrast, water absorption was increased. The positive effect of cellulose on sample performance is explained on the basis of hydrogen bonding between the functional moieties of cellulose and the active sites of sample constituents, namely zeolites, metakaolin, illite and the geopolymer. As a filler, zeolite probably contributed to sample strengthening, and the detrimental impact of Na-carbonate was insignificant. Based on the results obtained, the composites could be used as binders for brick manufacturing or as lightweight mortars.

The rheological properties of sepiolite gels in relation to solution chemistry, fiber charge, and microstructure are poorly understood. The purpose of this study was to bring more clarity to this topic by quantifying the effects of solution pH, ionic strength, and adsorbed tetrasodium pyrophosphate (TSPP) additive on rheological properties. The electrical charge on sepiolite fibers was investigated to explain the fiber interaction configuration observed in the microstructure. Fiber interaction forces and dynamics explained the ageing behavior of the gel. Sepiolite gels of only a few percent solids displayed long-time ageing behavior, which was manifested by an increasing yield stress with wait time and continued for weeks. The gel microstructure showed randomly orientated rigid fibers with cross configuration attraction. Each fiber experiences both attractive (van der Waals and heterogeneous charge) and repulsive (electric double layer) forces, and initially a net force. The repulsive force causes these fibers to orientate or move continually to achieve a state of force equilibrium and this process takes a long time. The Leong model describes this ageing behavior. For good fiber separation, high intensity probe sonication of the suspension was required. The yield stress increased with sonication time, solids loading, and temperature. The yield stress was absent at pH > 11 and increased to a maximum value at pH < 8. This maximum was insensitive to pH between 4 to 8, and ionic strength up to 1 M KCl. TSPP reduced this maximum and shifted the zero yield stress region to a lower pH, ~7. The zero yield stress state corresponded to a zeta potential with a minimum magnitude of 30 mV.

The elimination of Pb2+ and recovery of lead metal during the treatment of industrial sewage is an important research topic. Montmorillonite (Mnt) is a promising material in this regard. The purpose of the present study was to improve the Pb2+ adsorption ability of Na-containing Mnt (Na-Mnt) by pillaring titania (anatase) into its interlayer spaces using a sol-gel method. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The ratio of Ti to Mnt affected the crystal phase of titania-pillared Na-Mnt (Ti-Mnt), and changed the interlayer spacing of the (001) plane of Ti-Mnt and the growth of anatase. The Pb2+-adsorption capabilities of Ti-Mnt were tested using an aqueous solution of lead nitrate as a wastewater model. The Ti-Mnt prepared adsorbed >99.99% of the Pb2+; leached and activated Ti-Mnt adsorbed >95.7% of the Pb2+, indicating that Ti-Mnt could be recycled effectively. Furthermore, the Pb2+-adsorption capability of Ti- Mnt was related to the interlayer spacing of Mnt, the distribution of anatase particles pillared in Mnt, and the specific surface area, especially with respect to the relationship between the anatase particles and the interlayer spacing of the (001) plane.

The thermal maturity of samples of the Posidonia Shale collected from the Hils Syncline, northern Germany, varies significantly as a function of location indicating variations in local history. Synchrotron X-ray diffraction was used to document the composition and the preferred orientation of four samples of the Posidonia Shale with different degrees of maturity (0.68–1.45%, Ro) to determine possible effects on diagenesis and preferred orientation. Overall, the degree of preferred orientation of all clay minerals (illite-smectite, illite-mica, and kaolinite) and in all samples is similar, with (001) pole figure maxima ranging from 3.7 to 6.3 multiples of a random distribution (m.r.d.). Calcite displays weak preferred orientation, with c axes perpendicular to the bedding plane (1.1–1.3 m.r.d.). Other constituent phases such as quartz, feldspars, and pyrite have a random orientation distribution. The difference in thermal history, which causes significant changes in the maturity of organic matter, influenced the preferred orientation of clay minerals only marginally as most of the alignment seems to have evolved early in their history. Synchrotron X-ray microtomography was used to characterize the three-dimensional microstructure of a high-maturity sample. Low-density features, including porosity, fractures, and kerogen, were observed to be elongated and aligned roughly parallel to the bedding plane. The volume of low-density features was estimated to be ~7 vol.%, consistent with previous petrophysical measurements of porosity of 8–10 vol.%. Transmission electron microscopy analysis of samples with different degrees of maturity (0.74%Ro and 1.45%Ro) was used to document microstructures at the nanoscale as well as the presence of kerogen. In the high-maturity sample, pores were less abundant while minerals were more deformed as shown by fractured calcite and by kinked and folded illite. Some of the porosity was aligned with clay platelets.

Emanation thermal analysis (ETA), based on radon release measurements from previously labeled samples, was used for the first time in the characterization of the thermal behavior of natural Mg2+-vermiculite (Santa Olalla, Huelva, Spain) and of Na+- and ${\text{NH}}_4^{+}$-exchanged vermiculite samples. In addition, vermiculite samples subjected to a chemical treatment with an aqueous solution of (NH4)2SiF6 and partially or totally re-saturated with Na+ ions were also investigated by ETA. The ETA results of natural Mg2+-vermiculite, Na+-vermiculite and ${\text{NH}}_4^{+}$-vermiculite gave supplementary information about microstructure changes of the samples observed under dynamic heating conditions. The method has proved to be very useful for characterization of microstructure changes due to modification in the interlayer space of samples during the heat treatment. The crystallization of vermiculite into new phases, such as enstatite (for ${\text{NH}}_4^{+}$-vermiculite and Mg2+-vermiculite) and forsterite (for Na+-vermiculite) was also observed by ETA.

The results from mesoscale simulations of the formation and evolution of microstructure for assemblies of Na-smectite particles based on assumed size distributions of individual clay platelets are presented here. The analyses predicted particle arrangements and aggregation (i.e. platelets linked in face—face configurations) and are used to link geometric properties of the microstructure and mechanical properties of the particle assemblies. Interactions between individual ellipsoidal clay platelets are represented using the Gay-Berne potential based on atomistic simulations of the free energy between two Na-smectite clay-platelets in liquid water, following a novel coarse-graining method developed previously. The current study describes the geometric (aggregate thickness, orientation, and porosity) and elastic properties in the ‘jammed states’ from the mesoscale simulations for selected ranges of clay particle sizes and confining pressures. The thickness of clay aggregates for monodisperse assemblies increases (with average stack thickness consisting of n = 3–8 platelets) with the diameter of the individualclay platelets and with the level of confining pressure. Aggregates break down at high confining pressures (50–300 atm) due to slippage between the platelets. Polydisperse simulations generate smaller aggregates (n = 2) and show much smaller effects of confining pressure. All assemblies show increased order with confining pressure, implying more anisotropic microstructure. The mesoscale simulations are also in good agreement with macroscopic compression behavior measured in conventional 1-D laboratory compression tests. The mesoscale assemblies exhibit cubic symmetry in elastic properties. The results for larger platelets (D = 1000 Å) are in good agreement with nano-indentation measurements on natural clays and shale samples.

To further elucidate adsorption-to-partition transitional mechanisms which have been proposed previously for organo-bentonites with different surfactant loadings, the structural characteristics of interlayer surfactant aggregates on organo-bentonite with different surfactant cetyltrimethylammonium bromide loading levels (0.20–2.56 times cation exchange capacity, CEC) have been investigated by in situ X-ray diffraction (XRD) and Fourier TransformInfrared (FTIR) spectroscopy. The sorption properties and the structure of the clay interlayers changed according to the type of surfactant, the surfactant loading level, and the state of hydration in the clays. Based on the sorption of nitrobenzene, phenol, and aniline to organobentonites, the contaminant sorption coefficients (Ksf), normalized with the organic carbon content, show a remarkable dependence on surfactant loading levels. The Ksf values first increased with surfactant loading until reaching a maximum at 1.0 to 1.2 times the CEC, and then decreased. According to the theoretical calculation of the volume fractions relating to the interlamellar space, the interlamellar microenvironment became a more hydrophobic medium, contributing to the dissolution of organic contaminants, as the surfactant loading increased from 0.20 to 2.56 times the CEC. However, the increase in packing density (ρ) for the intercalates, and induced steric hindrances both affect the result in terms of a reduction in the accessible free space where the organic contaminants can be located, which might be a negative factor in the sorption capacity.

In Sweden and in many other countries, a bentonite barrier will be used in the repository for spent nuclear fuel. In the event of canister failure, colloidal diffusion is a potential, but scarcely studied mechanism of radionuclide migration through the bentonite barrier. Column and in situ experiments are vital in understanding colloid diffusion and in providing information about the micro structure of compacted bentonite and identifying cut-off limits for colloid filtration. This study examined diffusion of negatively charged 2-, 5-, and 15-nm gold colloids in 4-month diffusion experiments using MX-80 Wyoming bentonite compacted to dry densities of 0.6–2.0 g/cm3. Breakthrough of gold colloids was not observed in any of the three diffusion experiments. In a gold-concentration profile analysis, colloid diffusion was only observed for the smallest gold colloids at the lowest dry density used (estimated apparent diffusivity Da ≈ 5 × 10−13 m2/s). The results from a microstructure investigation using low-angle X-ray diffraction suggest that at the lowest dry density used, interlayer transport of the smallest colloids cannot be ruled out as a potential diffusion pathway, in addition to the expected interparticle transport. In all other cases, with either greater dry densities or larger gold colloids, compacted bentonite will effectively prevent diffusion of negatively charged colloids due to filtration.

Typical unconventional gas/liquid plays of China were studied using field-emission/focused ion beam scanning electron microscopy (SEM) for clay mineralogy and microstructural development. The SEM microstructural investigations of clay-rich shale and mudstone reservoirs provided significant information about clay mineral type, size, distribution and aggregates, which allows for interpretations regarding porosity preservation and petrophysical variability. The major clay-hosted porosity types are interparticle clay pores, intraparticle clay pores and aggregate pores. Interparticle clay pores occur in open spaces of the clay aggregates and include four subtypes: (1) elongated pores, (2) packed pores, (3) jagged pores and (4) card-house pores. Intraparticle clay pores are present within clay particles and have mostly secondary origin. These pores are diagenesis dependent and are restricted to secondary illite particles during the transformation of clay minerals from smectite to illite. Intraparticle clay pores constitute only isolated porosity and could not contribute to hydrocarbon molecule storage and migration. Aggregate pores were predominantly encountered in association with organic–clay and pyrite–clay aggregates. In places, organic–pyrite–clay aggregates can also display polymerization, but they do not contribute significantly to overall porosity and permeability. Combining SEM morphological analyses with the software ImageJ is critical in clay microstructure and porosity analyses via semi-quantitative characterization of the 3D pore surface, 2D pore profile, pore quantity, pore size, areal porosity, etc. These visual and semi-quantitative results highlight the significance of jagged pores and pyrite–clay aggregate pores in shale gas/liquid reservoirs because they may be important facilitators of gas storage and transmission.

Set yogurt's physical characteristics are greatly affected by the homogenization and heat treatment processes. In our previous study, set yogurt treated at 130°C and with the fat particle size reduced to ≤0.6 μm had equivalent curd strength, less syneresis and smoother texture than yogurt treated at 95°C. When investigating the mechanisms underlying yogurt's physical properties, it is important to evaluate the yogurt's microstructure. We conducted electron microscopy evaluations to investigate the mechanisms of changes in yogurt's physical properties caused by 130°C heat treatment and by a reduction in the fat globule size. We prepared yogurt mixtures by combining heat treatment at 95 and 130°C and homogenization pressure at 10 + 5 and 35 + 5 MPa and then fermented the mixtures in a common yogurt starter. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used for the structural observations. Fine particles were observed on the surface of the casein micelles of the yogurt treated at 95°C, and the coalescence density between micelles was high. The surface of the yogurt treated at 130°C had few fine particles, and the coalescence density between micelles was low. The yogurt treated at 130°C with 35 + 5 MPa homogenization had low coalescence density between casein micelles, but smaller-particle-size fat globules increased the network density. Approximately 30% of the fat globules were estimated to be incorporated into the yogurt networks compared to the volume of casein micelles. We speculate that 130°C heat treatment alters the structure of whey protein on the surface of casein micelles and interferes with network formation, but reducing the size of fat globules reinforces the network as a pseudoprotein.

Mollusk shells from archeological deposits are often exposed to high temperatures through human-caused or natural heating events. While heat exposure affects reliability of mollusk shells for environmental reconstructions based on geochemistry, it can provide a valuable source of information on past human behaviors and human–environment interactions. We analyzed burned and not-burned bivalve and gastropod specimens collected within two megalithic circular structures in the HAS1 settlement in Oman (Late Iron Age and Classical Period). Through a multi-methodological approach, we investigated shell microstructure using scanning electron microscopy (SEM), shell mineralogy using X-ray diffraction (XRD), and shell stable-isotopic composition (δ18O, δ13C) using isotope-ratio mass spectrometry (IRMS) to infer the temperatures these specimens were exposed to and to reconstruct the processes responsible for heating the shells. Thermal response of aragonite and calcite shells having different microstructures were also determined. We found that mollusk shells at this site were exposed to three temperature ranges: a) no exposure or <300°C, b) between 250°C and 500°C, and c) ≥500°C. The heat source was likely a fire which engulfed the entire settlement, which is also supported by evidence of carbonized wooden poles found in situ inside the circular structures.

Byronids are problematic fossils of possible cnidarian affinity, only rarely reported from the Devonian, but never previously studied in the Barrandian area, Czech Republic. Two new species Prestephanoscyphus branzovensis sp. nov. and Prestephanoscyphus robustus sp. nov. are erected from the Lochkovian and the Eifelian, respectively. Four poorly known species referred to Byronia are described in open nomenclature from the Emsian and Eifelian. The new genus Parabyronia gen. nov. with the type species Parabyronia elegans sp. nov. is closely related to other sphenothallids but is distinguished by transverse ridges on its theca and short spines at the apertural end of the theca. Definite identification of phosphatic rings as the attachment structure of byronids was proved by new material of the Lochkovian age. A dwarf conularia Pidiconularia gen. nov. with the type species Pidiconularia tubulata sp. nov. is remarkable by its minute size and very fine ornament; its conulariid affinity is proved by subrectangular cross-section and four internal carinae. Microstructure of theca of Prestephanoscyphus is characterised by alternation of compact laminae of aligned columnar microcrystallites and chambered laminae with isometric microcrystallites of apatite. Accretionary growth of byronid theca and structure of the holdfast with basal opening for the adhesive pedal disc support their cnidarian affinity although they likely display the bilateral instead of tetramerous symmetry. The protective function of bilaterally symmetrical whorls of internal apophyses in Prestephanoscyphus is suggested and their role in strengthening of thecal wall or supporting function of gastric septa are disputed. The byronids are regarded as epibionts rather than attached to the rocks. They are representatives of benthic groups with phosphatic shells that declined with decreasing availability of phosphorus in seas and oceans.