Showing papers in "Journal of Materials Science in 2012"

Microstructure and Elevated Temperature Properties of a Refractory TaNbHfZrTi Alloy

Abstract: Compression properties of a refractory multi-component alloy, Ta20Nb20Hf20Zr20Ti20, were determined in the temperature range of 296–1473 K and strain rate range of 10−1–10−5 s−1. The properties were correlated with the microstructure developed during compression testing. The alloy was produced by vacuum arc melting, and it was hot isostatically pressed (HIPd) and homogenized at 1473 K for 24 h prior to testing. It had a single-phase body-centered cubic structure with the lattice parameter a = 340.4 pm. The grain size was in the range of 100–200 μm. During compression at a strain rate of έ = 10−3 s−1, the alloy had the yield strength of 929 MPa at 296 K, 790 MPa at 673 K, 675 MPa at 873 K, 535 MPa at 1073 K, 295 MPa at 1273 K and 92 MPa at 1473 K. Continuous strain hardening and good ductility (e ≥ 50%) were observed in the temperature range from 296 to 873 K. Deformation at T = 1073 K and έ ≥ 10−3 s−1 was accompanied by intergranular cracking and cavitation, which was explained by insufficient dislocation and diffusion mobility to accommodate grain boundary sliding activated at this temperature. The intergranular cracking and cavitation disappeared with an increase in the deformation temperature to 1273 and 1473 K or a decrease in the strain rate to ~10−5 s−1. At these high temperatures and/or low-strain rates the alloy deformed homogeneously and showed steady-state flow at a nearly constant flow stress. Partial dynamic recrystallization, leading to formation of fine equiaxed grains near grain boundaries, was observed in the specimens deformed at 1073 and 1273 K and completed dynamic recrystallization was observed at 1473 K.

Random-phase approximation and its applications in computational chemistry and materials science

Abstract: The random-phase approximation (RPA) as an approach for computing the electronic correlation energy is reviewed. After a brief account of its basic concept and historical development, the paper is devoted to the theoretical formulations of RPA, and its applications to realistic systems. With several illustrating applications, we discuss the implications of RPA for computational chemistry and materials science. The computational cost of RPA is also addressed which is critical for its widespread use in future applications. In addition, current correction schemes going beyond RPA and directions of further development will be discussed.

Effect of SiO2 and Al2O3 on the setting and hardening of high calcium fly ash-based geopolymer systems

Abstract: This study investigates the effect of silica and alumina contents on setting, phase development, and physical properties of high calcium fly ash (ASTM Class C) geopolymers. The characteristic rapid setting properties and, hence, limited workability range of high calcium fly ash geopolymers has restricted both development and potential application of these binder systems compared to conventional geopolymer binders derived from bituminous coal, i.e., (ASTM Class F) sources or from calcined kaolin feedstocks. For this study, control of setting and hardening properties were investigated by adjusting SiO2/Al2O3 ratio of the starting mix, via series of mixes formulated with varying SiO2 or Al2O3 contents to achieve SiO2/Al2O3 in the range 2.87–4.79. Foremost is the observation that the effect of varying silica and alumina in high calcium fly ash systems on setting and hardening properties is markedly different from that observed for traditional Class F geopolymer systems. Overall, increases in either silica or alumina content appear to shorten the setting time of high calcium-based systems unlike conventional geopolymer systems where increasing Al2O3 accelerates setting. The setting process was associated primarily with CSH or CASH formation. Furthermore, there appears to be a prevailing SiO2/Al2O3 ratio that prolongs setting, rather than Ca2+ ion content itself, while NASH primarily contributes to strength development. SiO2/Al2O3 ratios in the range of 3.20–3.70 resulted in products with highest strengths and longest setting times. These results suggest that initial predominance of Ca2+ ions and its reactions effectively help maintaining a SiO2/Al2O3 ratio at which amorphous geopolymer phase is stable to influence setting and initial strength development.

A critical review of all-cellulose composites

Abstract: Cellulose is a fascinating biopolymer of almost inexhaustible quantity. While being a lightweight material, it shows outstanding values of strength and stiffness when present in its native form. Unsurprisingly, cellulose fibre has been rigorously investigated as a reinforcing component in biocomposites. In recent years, however, a new class of monocomponent composites based on cellulosic materials, so-called all-cellulose composites (ACCs) have emerged. These new materials promise to overcome the critical problem of fibre–matrix adhesion in biocomposites by using chemically similar or identical cellulosic materials for both matrix and reinforcement. A number of papers scattered throughout the polymer, composites and biomolecular science literature have been published describing non-derivatized and derivatized ACCs. Exceptional mechanical properties of ACCs have been reported that easily exceed those of traditional biocomposites. Several different processing routes have been applied to the manufacture of ACCs using a broad range of different solvent systems and raw materials. This article aims to provide a comprehensive review of the background chemistry and various cellulosic sources investigated, various synthesis routes, phase transformations of the cellulose, and mechanical, viscoelastic and optical properties of ACCs. The current difficulties and challenges of ACCs are clearly outlined, pointing the way forward for further exploration of this interesting subcategory of biocomposites.

Graphene oxide: the mechanisms of oxidation and exfoliation

Abstract: Graphene oxides (GOs) with large sheets and more perfect aromatic structure were prepared by a novel modified Hummers method. We demonstrated that the graphite did not need to be oxidized to such a deep degree as described in Hummers method because the space distance increased little when the oxidation proceeded to a certain extent and the obtained graphite oxides (GTOs) could be fully exfoliated to single layers with high thermal stability. The oxidation mechanism and chemical structure model of GO were proposed by analyzing the evolution of the functional groups with oxidation proceeded based on thermogravimetric analysis, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy. The layer spacing calculated by molecular dynamics simulations coincided with the X-ray diffraction results. Furthermore, the size distribution and thickness of GOs were also studied. The results confirmed that the GOs prepared by the modified method were fully exfoliated to uniform single layers, and this method may be important for efficient exfoliation of GTO to GO and large-scale production of graphene.

Advanced titania nanostructures and composites for lithium ion battery

Abstract: Owing to the increasing demand of energy and shifting to the renewable energy resources, lithium ion batteries (LIBs) have been considered as the most promising alternative and green technology for energy storage applied in hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), and other electric utilities. Owing to its environmental benignity, availability, and stable structure, titanium dioxide (TiO2) is one of the most attractive anode materials of LIBs with high capability, long cycling life, high safety, and low cost. However, the poor electrical conductivity and low diffusion coefficient of Li-ions in TiO2 hamper the advancement of TiO2 as anode materials of LIBs. Therefore, intensive research study has been focused on designing the nanostructures of TiO2 and its composites to reduce the diffusion length of Li-ion insertion/extraction and improve the electrical conductivity of the electrode materials. In this article, the development of TiO2 and its composites in nano-scales including fabrication, characterization of TiO2 nanomaterials, TiO2/carbon composite, and TiO2/metal oxide composites to improve their properties (capacity, cycling performance, and energy density) for LIBs are reviewed. Meanwhile, the mechanisms for influences of the structure, surface morphology, and additives to TiO2 composites on the related properties of TiO2 and TiO2 composites to LIBs are discussed. The new directions of research on this field are proposed.

The influence of nano-silica on the hydration of ordinary Portland cement

Abstract: Nucleation seeding is a new approach to control the kinetics of cement hydration. It is known that nano-silica has an accelerating effect on cement hydration. It is assumed that the surface of these particles act as a nucleation site for C–S–H-seeds which then accelerate the cement hydration. In this case the acceleration should depend on the particles surface area. To verify this, nano-silica particles of different sizes and specific surface areas were synthesised. The acceleration of cement hydration clearly correlates with the total surface size of the added particles, which was varied by either using smaller particles or higher concentration of particles in the cement lime. Additional in situ-XRD experiments show that the consumption of C3S and the formation of portlandite are accelerated by the addition of nano-silica. In both cases the surface size is the major factor for the hydration kinetics.

Carbon fibres from cellulosic precursors: a review

Abstract: The focus of this review is primarily on the sequence of structural changes at micro and molecular level during carbonization of cellulosic fibres. The influence of various operational parameters such as the pyrolytic temperature and the stabilization agents also discussed as is the effect of the initial properties of the cellulose fibre on the final properties of the carbon fibre.

Room temperature elastic moduli and Vickers hardness of hot-pressed LLZO cubic garnet

Abstract: Cubic garnet Li6.24La3Zr2Al0.24O11.98 (LLZO) is a candidate material for use as an electrolyte in Li–Air and Li–S batteries. The use of LLZO in practical devices will require LLZO to have good mechanical integrity in terms of scratch resistance (hardness) and an adequate stiffness (elastic modulus). In this paper, the powders were fabricated by powder processing of cast ingots. All specimens were then densified via hot pressing. The room temperature elastic moduli (Young’s modulus, shear modulus, bulk modulus, and Poisson’s ratio) and hardness were measured by resonant ultrasound spectroscopy, and Vickers indentation, respectively. For volume fraction porosity, P, the Young’s modulus was 149.8 ± 0.4 GPa (P = 0.03) and 132.6 ± 0.2 GPa (P = 0.06). The mean Vickers hardness was 6.3 ± 0.3 GPa for P = 0.03 and 5.2 ± 0.4 for P = 0.06.

Effect of filler size and concentration on the structure and properties of poly(vinylidene fluoride)/BaTiO3 nanocomposites

Abstract: The effect of filler size and content in the thermal, mechanical, and electrical response of poly(vinylidene fluoride) (PVDF)/BaTiO3 nanocomposites has been investigated Dielectric constant increases significantly with increasing filler content and decreasing filler size Space charge effects at the interface between BaTiO3 and PVDF strongly influence the dielectric response The electroactive β-phase of PVDF is nucleated by the presence of the ceramic filler, the effect being strongly dependent on filler size and independent on filler content This filler/matrix interaction is also responsible for the variations observed in the activation energy of the thermal degradation of the polymer Smaller particles lead to larger relative contact areas and are responsible for the main variations observed in the thermal, mechanical, and electrical properties of the composites

Oxidation behavior of a refractory NbCrMo0.5Ta0.5TiZr alloy

Abstract: Isothermal oxidation behavior of a refractory high-entropy NbCrMo0.5Ta0.5TiZr alloy was studied during heating at 1273 K for 100 h in flowing air. Continuous weight gain occurred during oxidation, and the time dependence of the weight gain per unit surface area was described by a parabolic dependence with the time exponent n = 0.6. X-ray diffraction and scanning electron microscopy accompanied by energy-dispersive X-ray spectroscopy showed that the continuous oxide scale was made of complex oxides and only local (on the submicron levels) redistribution of the alloying elements occurred during oxidation. The alloy has a better combination of mechanical properties and oxidation resistance than commercial Nb alloys and earlier reported developmental Nb–Si–Al–Ti and Nb–Si–Mo alloys.

Phase and morphology evolution of calcium carbonate precipitated by carbonation of hydrated lime

Abstract: Phase and morphology evolution of CaCO3 precipitated during carbonation of lime pastes via the reaction Ca(OH)2 + CO2 → CaCO3 + H2O has been investigated under different conditions (pCO2 ≈ 10−3.5 atm at 60 % RH and 93 % RH; pCO2 = 1 atm at 93 % RH) using XRD, FTIR, TGA, and SEM. Simulations of the pore solution chemistry for different stages and conditions of carbonation were performed using the PHREEQC code to investigate the evolution of the chemistry of the system. Results indicate initial precipitation of amorphous calcium carbonate (ACC) which in turn transforms into scalenohedral calcite under excess Ca2+ ions. Because of their polar character, $$ \left\{ {21\bar{3}4} \right\} $$ scalenohedral faces (type S) interact more strongly with excess Ca2+ than non-polar $$ \left\{ {10\bar{1}4} \right\} $$ rhombohedral faces (type F), an effect that ultimately favors the stabilization of $$ \left\{ {21\bar{3}4} \right\} $$ faces. Following the full consumption of Ca2+ ions and further dissolution of CO2 leading to a pH drop of the pore solution, $$ \left\{ {21\bar{3}4} \right\} $$ scalenohedra are subjected to dissolution. This eventually results in re-precipitation of $$ \left\{ {10\bar{1}4} \right\} $$ rhombohedra at close-to-neutral pH. This crystallization sequence progresses through the carbonated depth with a strong dependence on the degree of exposure to CO2, which is controlled by the carbonated pore structure governing the diffusion of CO2. Both the carbonation process and the scalenohedral-to-rhombohedral transformation are kinetically favored under high RH and high pCO2. Supersaturation plays a critical role on the nucleation density and size of CaCO3 crystals. These results have important implications in understanding the behavior of ancient and modern lime mortars for applications in architectural heritage conservation.

The structure and mechanics of bone

Abstract: The four levels of hierarchy considered in this review are the nanoscale (the mineralised collagen fibre and the extrafibrillar mineral), the microscale (the structure as visible under the microscope), the mesoscale (particularly the relationship between cancellous and cortical bone) and the whole bone scale. The explosion of papers at the nanoscale precludes any settling on one best model. At the microscale the inadequacies of linear elastic fracture mechanics, the importance of R-curves for understanding what is happening to cracks in bone, and the effect of different histological types are emphasised. At the mesoscale the question of whether cancellous bone is anything but compact bone with a lot of holes in it, and the question of whether cancellous bone obeys Wolff’s ‘law’ is discussed. The problem of not damaging bone when examining it with X-rays is mentioned (though not solved). At the whole bone level the relative roles of genetics and the external forces and the question of the way in which bones are loaded, in bending or compression, is raised, and the question of size effects, long underestimated or ignored by the bone community, is discussed. Finally, the question of why there are hierarchies at all in bone is addressed

Effect of the LPSO volume fraction on the microstructure and mechanical properties of Mg–Y2X–ZnX alloys

Abstract: The influence of the volume fraction of long-period stacking ordered structure (LPSO) on the microstructure and mechanical properties in three extruded Mg100-3x Y2x Zn x alloys (x = 0.5, 1 and 1.5 at.%) has been studied. Two structures of LPSO phase coexist in these extruded alloys, 18R and 14H. The 18R structure transforms to 14H structure gradually in the course of the extrusion process. For the three alloys, the grain size in the vicinity of LPSO phase particles is refined because of a particle-stimulated nucleation (PSN) mechanism. The reinforcing effect of the LPSO phase is active up to 523 K. Above this temperature, grain size effect becomes important. Accordingly, MgY1Zn0,5 extruded alloy shows the Highest mechanical strength for temperatures greater than 523 K.

Properties of amorphous and crystalline titanium dioxide from first principles

Abstract: We used first-principles methods to generate amorphous TiO2 (a-TiO2) models and our simulations lead to chemically ordered amorphous networks. We analyzed the structural, electronic, and optical properties of the resulting structures and compared with crystalline phases. We propose that two peaks found in the Ti–Ti pair correlation correspond to edge-sharing and corner-sharing Ti–Ti pairs. Resulting coordination numbers for Ti (∼6) and O (∼3) and the corresponding angle distributions suggest that local structural features of bulk crystalline TiO2 are retained in a-TiO2. The electronic density of states and the inverse participation ratio reveal that highly localized tail states at the valence band edge are due to the displacement of O atoms from the plane containing three neighboring Ti atoms; whereas, the tail states at the conduction band edge are localized on over-coordinated Ti atoms. The $$\Upgamma$$ -point electronic gap of ∼2.2 eV is comparable to calculated results for bulk crystalline TiO2 despite the presence of topological disorder in the amorphous network. The calculated dielectric functions suggest that the amorphous phase of TiO2 has isotropic optical properties in contrast to those of tetragonal rutile and anatase phases. The average static dielectric constant and the fundamental absorption edge for a-TiO2 are comparable to those of the crystalline phases.

Glass–ceramic glazes for ceramic tiles: a review

Abstract: Glass–ceramics are ceramic materials produced through controlled crystallisation (nucleation and crystal growth) of a parent glass. The great variety of compositions and the possibility of developing special microstructures with specific technological properties have allowed glass–ceramic materials to be used in a wide range of applications. One field for which glass–ceramics have been developed over the past two decades is that of glazes for ceramic tiles. Ceramic tiles are the most common building material for floor and wall coverings in Mediterranean countries. Glazed tiles are produced from frits (glasses quenched in water) applied on the surface of green tiles and subjected to a firing process. In the 1990s, there was growing interest in the development of frits that are able to crystallise on firing because of the need for improvement in the mechanical and chemical properties of glazed tiles. This review offers an extensive evaluation of the research carried out on glass–ceramic glazes used for covering and pavement ceramic tile is accomplished. The main crystalline phases (silicates and oxides) developed in glass–ceramic glazes have been considered. In addition, a section focused on glazes with specific functionality (photocatalytic, antibacterial and antifungal activity, or aesthetic superficial effects) is also included.

From the computer to the laboratory: materials discovery and design using first-principles calculations

Abstract: The development of new technological materials has historically been a difficult and time-consuming task. The traditional role of computation in materials design has been to better understand existing materials. However, an emerging paradigm for accelerated materials discovery is to design new compounds in silico using first-principles calculations, and then perform experiments on the computationally designed candidates. In this paper, we provide a review of ab initio computational materials design, focusing on instances in which a computational approach has been successfully applied to propose new materials of technological interest in the laboratory. Our examples include applications in renewable energy, electronic, magnetic and multiferroic materials, and catalysis, demonstrating that computationally guided materials design is a broadly applicable technique. We then discuss some of the common features and limitations of successful theoretical predictions across fields, examining the different ways in which first-principles calculations can guide the final experimental result. Finally, we present a future outlook in which we expect that new models of computational search, such as high-throughput studies, will play a greater role in guiding materials advancements.

Diamond–metal interfaces in cutting tools: a review

Abstract: This article reviews studies undertaken on diamond cutting tools, with particular regard to the characteristics and performance of diamond/metal interfaces. The affinity of carbon to metals, as well as the wettability of diamond by molten metals, and the advantage of using coated diamonds under certain cutting conditions, are described. The choice of the appropriate metallic matrix in the field of both impregnated and brazed diamond tools is discussed in terms of the diamond/alloy interface, mechanical properties of the segment, diamond wear speed, and desired cutting performance. The effect of several principal elements and elements added in minor amounts to the metallic matrix is critically evaluated. Relevant open questions, related to the optimization of cutting tools performance, are outlined, with special attention directed toward the need for advanced fundamental studies on the functional link between work of adhesion and work of fracture.

The development of laminated composite plate theories: a review

Abstract: This study investigates and reviews approaches to modelling laminated composite plates. It explores theories that have been proposed and developed and assesses their suitability and functionality. The particular focus in this study has been on normal stresses and the through-thickness distributions of transverse shear. These are important for composite plates as stress-induced failures can occur in three different ways. Therefore, it is essential to understand and calculate transverse shear and normal stress through the thickness of the plate accurately. In this study, previous laminated composite plate theories are categorised and reviewed in a general sense, i.e. not problem specific, and the advantages and disadvantages of each model are discussed. This research mainly focuses on how accurate and efficient the models can predict the transverse shear. It starts with displacement-based theories from very basic models such as Classical laminate plate theory to more complicated and higher-order shear deformation theory. Models are furthermore categorised by how the models consider the overall laminate. In this article, the theories are divided into two parts: Single layer theory, where the whole plate is considered as one layer; and Layerwise theory, where each layer is treated separately. The models based on zig-zag and Discrete Theories are then reviewed, and finally the mixed (hybrid) plate theories are studied.

Defects in natural fibres: their origin, characteristics and implications for natural fibre-reinforced composites

Abstract: This article reviews defects in natural fibres and how, ultimately, they affect the properties of composite materials reinforced with such fibres. Under ideal circumstances, certain natural fibre like flax and hemp can display excellent tensile mechanical properties. However, the potential of the fibre is generally not realised in natural fibre-reinforced composites. Partly, this poor performance can be explained by the presence of defects in the fibres known variously as dislocations, kinks or microcompressions. After briefly considering the chemistry and structure of plant fibres, the properties of selected natural fibres are reviewed. The origin of defects and the impact that processing has on their presence is then considered. The effect that defects have on the mechanical properties of bast fibre and their susceptibility to chemical degradation is also reviewed. Finally, the effect that dislocations have on the properties of composites reinforced with natural fibres is discussed and areas of potential further research needed are highlighted.

Materials development for intermediate-temperature solid oxide electrochemical devices

Abstract: One of the major challenges in developing electrochemical devices for energy generation has been the identification and development of materials with outstanding performance at reduced (intermediate) temperatures (500–700 °C), increasing the durability and lowering the cost of the device. A solid-state electrochemical cell is in outline a simple device consisting of three components: anode, electrolyte and cathode. The function of each component is critical to cell performance, and as interest in fuel cells and electrolysers has gathered pace, many materials have been evaluated as functional components of these cells. Typically, the requirement for new materials development has been the drive to lower operation temperature, overcoming sluggish reaction kinetics in existing materials. Novel materials for the functional components of both electrolysers and fuel cells are introduced, with emphasis placed on the air electrode and electrolyte, with the potential of new classes of materials discussed, including layered materials, defect fluorites and tetrahedrally coordinated phases. Furthermore, the opportunity presented by thin film deposition to characterize anisotropic transport in materials and develop devices based on thin films is discussed.

New software tools for the calculation and display of isolated and attached interfacial-energy minimizing particle shapes

Abstract: Existing methods to rapidly compute interface-energy minimizing shapes with anisotropy are collected and clarified, and new methods are introduced. A description of freely available, platform-independent software for the computation and display of equilibrium geometries is provided. The software relies on a new computational method to rapidly find equilibrium geometries. It also features a graphical user interface and includes the 32 crystallographic point groups to simplify inputting interfacial energies and their associated orientations. When a particle is completely enclosed within a single interface (isolated), the software computes and provides visualization for Wulff shapes. When a particle is enclosed by two interfaces, such as a particle at a grain boundary, the software minimizes their collective interfacial energy; if one of the interfaces is planar, the computation reproduces the Winterbottom construction. When both interfaces are deformable, the software provides a new tool for calculating the particle shape and the distortions of boundaries that are attached to it, even for highly anisotropic interfaces. The properties of particles bounded by two deformable interfaces are discussed, and applications of the software are illustrated. In some cases, the software can be used as a method to infer values of relative interfacial energies from a microscopic observation.

Preparation and tribological properties of graphene oxide/nitrile rubber nanocomposites

Abstract: Graphene oxide (GO)/nitrile rubber (NBR) nanocomposites with various contents of GO were prepared by a solution-mixing method,in this study. The GO sheets were exfoliated from natural fake graphite by an improved Hummers method and could be further dispersed homogeneously in NBR matrix. The thickness and size of the GO sheets were observed by atomic force microscopy and transmission electron microscopy. The tribological properties of the GO/NBR nanocomposites were evaluated on a ring-block MRH-3 wear tester under dry sliding and water-lubricated conditions. The worn surface morphologies of the GO/NBR nanocomposites were observed by a scanning electron microscopy. It was found that under dry sliding, both the friction coefficient (COF) and specific wear rate of the nanocomposites decreased dramatically at first, then increased with increasing GO contents, while under water-lubricated condition, both the COF and specific wear rate of the nanocomposites decreased with increasing GO contents. Finally, the friction and wear mechanisms of the GO/NBR nanocomposites were tentatively proposed.

Properties of inorganic polymer (geopolymer) mortars made of glass cullet

Abstract: This study presents the results of experiments aiming to produce geopolymers from glass cullet, a non-traditional material compared to those usually found in the manufacture of geopolymers (e.g., metakaolin and fly ash). The study gives the principal formulation parameters affecting the behavior of glass cullet geopolymers. The glass used comes from recycled glass bottles. The parameters studied are the fineness of the glass (Blaine of 1000 to 4000 cm2/g), the temperature of synthesis (20, 40 and 60 °C), and the nature and concentration of the activation product (KOH, NaOH). The properties are evaluated in terms of compressive strength and durability. The results show that cullet of soda-glass can be used as a base material for the production of geopolymers and, contrary to metakaolin-based geopolymers, no waterglass is necessary for its setting and hardening since cullet glass already contains a high proportion of alkalis. Thermal activation at 40 or 60 °C is necessary but sufficient to obtain strength of more than 50 MPa, especially for the finer glass (4000 cm2/g). The durability of glass cullet geopolymers is affected by water conservation.

Synthesis of nanostructured materials using supercritical CO2: Part I. Physical transformations

Abstract: Nanostructured materials have been attracting increased attention for a wide variety of applications due to their superior properties compared to their bulk counterparts. Current methods to synthesize nanostructured materials have various drawbacks such as difficulties in control of the nanostructure and morphology, excessive use of solvents, abundant energy consumption, and costly purification steps. Supercritical fluids especially supercritical carbon dioxide (scCO2) is an attractive medium for the synthesis of nanostructured materials due to its favorable properties such as being abundant, inexpensive, non-flammable, non-toxic, and environmentally benign. Furthermore, the thermophysical properties of scCO2 can be adjusted by changing the processing temperature and pressure. The synthesis of nanostructured materials in scCO2 can be classified as physical and chemical transformations. In this article, Part I of our review series, synthesis of nanostructured materials using physical transformations is described where scCO2 functions as a solvent, an anti-solvent or as a solute. The nanostructured materials, which can be synthesized by these techniques include nanoparticles, nanowires, nanofibers, foams, aerogels, and polymer nanocomposites. scCO2 based processes can also be utilized in the intensification of the conventional processes by elimination of some of the costly purification or separation steps. The fundamental aspects of the processes, which would be beneficial for further development of the technologies, are also reviewed.

The water vapour sorption properties of thermally modified and densified wood

Abstract: The water vapour sorption behaviour of Scots pine (Pinus sylvestris L.) and Scots pine that was densified, thermally-modified, or subjected to a combination of thermal modification and densification has been investigated. It was found that all modifications resulted in a decrease in the equilibrium moisture content of the wood samples throughout the hygroscopic range. The water vapour sorption isotherms were reproducible for the unmodified wood samples, but changed between the first and subsequent sorption cycles for the densified, thermally-modified and for wood subjected to a combination of the two treatments. This is the first time that changes in the sorption isotherm between the first and subsequent cycles have been reported for thermally-modified wood. Irrespective of the wood treatment the difference between the adsorption and desorption isotherm loops (sorption hysteresis) was the same and greater than that observed for the unmodified wood sample. After the first sorption cycle, the hysteresis decreased to the values observed for the unmodified wood, even though the isotherms were different. The sorption kinetic behaviour was also investigated and found to be accurately described using the parallel exponential kinetics (PEK) model. The PEK model describes the dynamic sorption behaviour in terms of a fast and slow kinetic process and this has been interpreted in terms of two Kelvin-Voigt elements coupled in series (i.e. relaxation-limited kinetics).

The diversity of combustion synthesis processing: a review

Abstract: The harnessing of heat emanating from powder-based exothermic reactions to produce advanced materials has been around for many decades, and is manifested in the process of combustion synthesis (CS) A plethora of work has been published on the topic covering fundamental aspects of the process for a large number of material systems Over time, CS has been combined with other processes and effects to potentially improve on conventionally produced CS products and alleviate some of the inherent disadvantages of CS This article discusses processing aspects of CS, and provides a review of CS-related hybrid processes with the intent to exemplify the diversity of CS processing Approaches such as reactant microstructural design, reactive bulk deformation/compaction processes, reactive casting, laser-assisted CS, activation techniques (field/current, mechanical, microwave), and unconventional heat treatments are discussed together with other methods

Silicon nitride: the engineering material of the future

Abstract: The purpose of this review is to present the recent developments in silicon nitride (Si3N4) ceramics and to examine the achievements regarding our understanding of the relationship between processing conditions, chemical composition, microstructure and mechanical properties of Si3N4. Si3N4 is one of the most important structural ceramics because it possesses a combination of advanced properties such as good wear and corrosive resistance, high flexural strength, good fracture resistance, good creep resistance and relatively high hardness. These properties are obtained through the processing method involving liquid phase sintering in which a tailored microstructure, with high aspect ratio grains and chemistry of intergranular phase, triggers the toughening and strengthening mechanisms leading to the development of high fracture toughness and fracture strength. However, despite high fracture toughness and strength, Si3N4 ceramic materials still break catastrophically, and the fracture behaviour of this ceramic is considered to be the major obstacle for its wider use as a structural material. In addition to the macrostructure–mechanical properties relationship, this paper also reviews new designs involving laminates possessing no plane of weakness and some theoretical developments involving crack opening displacement. Proposals of how to improve the fracture resistance were also discussed.

In situ synthesis and thermal, tribological properties of thermosetting polyimide/graphene oxide nanocomposites

Abstract: The full exfoliation graphene oxide (GO) nanosheets were synthesized by an improved Hummers’ method. The phenylethynyl terminated thermosetting polyimide (PI) and PI/GO nanocomposites were prepared via a polymerization of monomer reactants process. Thermogravimetric analysis indicated that the incorporation of GO increased the thermal stability of the PI at low filling content. The friction and wear testing results of the PI and PI/GO nanocomposites under dry sliding condition against GCr15 steel showed that the addition of GO evidently improved the friction and wear properties of PI, which were considered to be the result of the formation of uniform transfer film and the increasing of load-carrying capacity. The friction and wear properties of the PI and PI/GO nanocomposites were investigated on a model ring-on-block test rig under dry sliding conditions against the GCr15 steel. Experimental results showed that the addition of GO evidently improved the friction and wear properties of PI, which were considered to be the result of the formation of uniform transfer film and the increasing of load-carrying capacity. The optimum GO content of nanocomposite for tribological properties is 3 wt%, which could be a potential candidate for tribo-material under dry sliding condition against GCr15 steel.

Physico-chemical and mechanical properties of nanocomposites prepared using cellulose nanowhiskers and poly(lactic acid)

Abstract: A range of nanocomposites were prepared using cellulose nanowhiskers (CNWs) and poly(lactic acid) (PLA) via a solvent casting process. Acid hydrolysis process was used to produce CNWs from bleached cotton. Structural morphology and surface topography of the CNWs and nanocomposites were examined using transmission (TEM) and scanning electron microscopy. TEM images revealed rod-like whiskers in the nano-scale region which were dispersed within the PLA matrix. The presence of the functional groups of CNWs and PLA were confirmed via FTIR analysis. Tensile tests were conducted on thin films and the nanocomposites containing 1 wt% CNWs showed a 34 and 31% increase in tensile strength and modulus, respectively, compared to pure PLA. The dynamic mechanical analysis showed that the tensile storage modulus also increased in the visco-elastic temperature region with increasing CNWs content in the nanocomposites. Thermogravimetric analysis showed that all the materials investigated were thermally stable from room temperature to 210 °C. A positive effect of CNWs on the crystal nucleation of PLA polymer in the nanocomposites was observed using differential scanning calorimetry and X-ray diffraction analysis. The degradation profiles of the nanocomposites in deionised water over 1 week revealed a mass loss of 1.5–5.6% at alternate temperatures (25, 37 and 50 °C) and at the same conditions the swelling ratio and water uptake were seen to increase with CNWs content in the nanocomposites, which was strongly influenced by the presence of crystalline CNWs.