Ce0.67Cr0.33O2.11: A New Low-Temperature O-2 Evolution Material and H-2 Generation Catalyst by Thermochemical Splitting of Water

Ce0.67Cr0.33O2.11 was synthesized by hydrothermal method using diethylenetriamine as complexing agent (Chem. Mater. 2008, 20, 7268). Ce0.67Cr0.33O2.11 being the only compound likes UO2+delta to have excess oxygen, it releases a large proportion of its lattice oxygen (0.167 M [O]/mole of compound) at relatively low temperature (465 degrees C) directly and it has been utilized for generation of H-2 by thermo-splitting of water. An almost stoichiometric amount of H-2 (0.152 M/Mole of compound) is generated at much lower temperature (65 degrees C). There is an almost comparable amount of oxygen release and hydrogen generation over this material at very low temperature comparedto other CeO2-MOx (Mn, Fe, Cu, and Ni) mixed-oxide solid solutions (O-2 evolution >= 1300 degrees C and H-2 generation at 1000 degrees C). The reversible nature of oxygen release and intake of this material is attributed to its fluorite Structure and coupling between the Ce4+/Ce3+ and Cr4+/6+/Cr3+ redox couples. Compound shows reversible oxygen release and intake by H2O absorption and subsequent hydrogen release to gain parent structure and hence this material can be utilized for generation of H-2 at very low temperature by thermo-chemical splitting of water.

Evaluation of the Biocompatibility of Poly (ortho ester), Copolymer of ε-caprolactone/D,L-lactide and the Composite of Copolymer of ε-caprolactone/D,L-lactide and Tricalciumphosphate as Bone Filling Material

The purpose of this series of studies was to evaluate the biocompatibility of poly (ortho) ester (POE), copolymer of ε-caprolactone and D,L-lactide [P (ε-CL/DL-LA)] and the composite of P(ε-CL/DL-LA) and tricalciumphosphate (TCP) as bone filling material in bone defects. Tissue reactions and resorption times of two solid POE-implants (POE 140 and POE 46) with different methods of sterilization (gamma- and ethylene oxide sterilization), P(ε-CL/DL-LA)(40/60 w/w) in paste form and 50/50 w/w composite of 40/60 w/w P(ε-CL/DL-LA) and TCP and 27/73 w/w composite of 60/40 w/w P(ε-CL/DL-LA) and TCP were examined in experimental animals. The follow-up times were from one week to 52 weeks. The bone samples were evaluated histologically and the soft tissue samples histologically, immunohistochemically and electronmicroscopically. The results showed that the resorption time of gamma sterilized POE 140 was eight weeks and ethylene oxide sterilized POE 140 13 weeks in bone. The resorption time of POE 46 was more than 24 weeks. The gamma sterilized rods started to erode from the surface faster than ethylene oxide sterilized rods for both POEs. Inflammation in bone was from slight to moderate with POE 140 and moderate with POE 46. No highly fluorescent layer of tenascin or fibronectin was found in the soft tissue. Bone healing at the sites of implantation was slower than at control sites with the copolymer in small bone defects. The resorption time for the copolymer was over one year. Inflammation in bone was mostly moderate. Bone healing at the sites of implantation was also slower than at the control sites with the composite in small and large mandibular bone defects. Bone formation had ceased at both sites by the end of follow-up in large mandibular bone defects. The ultrastructure of the connective tissue was normal during the period of observation. It can be concluded that the method of sterilization influenced the resorption time of both POEs. Gamma sterilized POE 140 could have been suitable material for filling small bone defects, whereas the degradation times of solid EO-sterilized POE 140 and POE 46 were too slow to be considered as bone filling material. Solid material is difficult to contour, which can be considered as a disadvantage. The composites were excellent to handle, but the degradation time of the polymer and the composites were too slow. Therefore, the copolymer and the composite can not be recommended as bone filling material.

In-situ one-step hydrothermal synthesis of a lead germanate-graphene composite as a novel anode material for lithium-ion batteries

Lead germanate-graphene nanosheets (PbGeO3-GNS) composites have been prepared by an efficient one-step, in-situ hydrothermal method and were used as anode materials for Li-ion batteries (LIBs). The PbGeO3 nanowires, around 100–200 nm in diameter, are highly encapsulated in a graphene matrix. The lithiation and de-lithiation reaction mechanisms of the PbGeO3 anode during the charge-discharge processes have been investigated by X-ray diffraction and electrochemical characterization. Compared with pure PbGeO3 anode, dramatic improvements in the electrochemical performance of the composite anodes have been obtained. In the voltage window of 0.01–1.50 V, the composite anode with 20 wt.% GNS delivers a discharge capacity of 607 mAh g−1 at 100 mA g−1 after 50 cycles. Even at a high current density of 1600 mA g−1, a capacity of 406 mAh g−1 can be achieved. Therefore, the PbGeO3-GNS composite can be considered as a potential anode material for lithium ion batteries.

Cyclic-oxidation behavior of Ti3SiC2-base material at 1100°c

The cyclic-oxidation behavior of Ti3SiC2-base material was studied at 1100°C in air. Scale spallation and weight loss were not observed in the present tests and the weight gain would just continue if the experiments were not interrupted. The present results demonstrated that the scale growth on Ti3SiC2-base material obeyed a parabolic rate law up to 20 cycles. It then changed to a linear rate with further increasing cycles. The scales formed on the Ti3SiC2base material were composed of an inward-growing, fine-grain mixture of Ti022 + SiO2 and an outward-growing, coarse-grain TiO2. Theoretical calculations show that the mismatch in thermal expansion coefficients between the inner scale and Ti3SiC2-base matrix is small. The outer TiO2 layer was under very low compressive stress, while the inner TiO2 + SiO2 layer was under tensile stress during cooling. Scale spaliation is, therefore, not expected and the scale formed on Ti3SiC2-base material is adherent and resistant to cyclic oxidation.

Evaluation of material crack using acoustic emission technique

Cracks in civil structures can result in premature failure due to material degradation and can result in both financial loss and environmental consequences. This thesis reports an effective technique using Acoustic Emission (AE) technique to assess the severity of the crack propagation in steel structures. The outcome of this work confirms that combination of AE parametric analysis and signal processing techniques can be used to evaluate crack propagation under different loading configurations. The technique has potential application to assess and monitor the condition of civil structures.

Organic–inorganic bismuth (III)-based material: A lead-free, air-stable and solution-processable light-absorber beyond organolead perovskites

Methylammonium bismuth (III) iodide single crystals and films have been developed and investigated. We have further presented the first demonstration of using this organic–inorganic bismuth-based material to replace lead/tin-based perovskite materials in solution-processable solar cells. The organic–inorganic bismuth-based material has advantages of non-toxicity, ambient stability, and low-temperature solution-processability, which provides a promising solution to address the toxicity and stability challenges in organolead- and organotin-based perovskite solar cells. We also demonstrated that trivalent metal cation-based organic–inorganic hybrid materials can exhibit photovoltaic effect, which may inspire more research work on developing and applying organic-inorganic hybrid materials beyond divalent metal cations (Pb (II) and Sn (II)) for solar energy applications.

Effect of residual stresses and metallographic stability on the over all performance of integral diaphragm material

The integral diaphragm pressure transducer consists of a diaphragm machined from precipitation hardened martensitic (APX4) steel. Its performance is quite significant as it depends upon various factors such as mechanical properties including induced residual stress levels, metallurgical and physical parameters due to different stages of processing involved. Hence, the measurement and analysis of residual stress becomes very important from the point of in-service assessment of a component. In the present work, the stress measurements have been done using the X-ray diffraction (XRD) technique, which is a non-destructive test (NDT). This method is more reliable and widely used compared to the other NDT techniques. The metallurgical aspects have been studied by adopting the conventional metallographic practices including examination of microstructure using light microscope. The dimensional measurements have been carried out using dimensional gauge. The results of the present investigation reveals that the diaphragm material after undergoing series of realization processes has yielded good amount of retained austenite in it. Also, the presence of higher compressive stresses induced in the transducer results in non-linearity, zero shift and dimensional instability. The problem of higher retained austenite content and higher compressive stress have been overcome by adopting a new realization process involving machining and cold and hot stabilization soak which has brought down the retained austenite content to about 5–6% and acceptable level of compressive stress in the range −100 to −150 MPa with fine tempered martensitic phase structure and good dimensional stability. The new realization process seems to be quite effective in terms of controlling retained austenite content, residual stress, metallurgical phase as well as dimensional stability and this may result in minimum zero shift of the diaphragm system.

Behaviour of Bi-material interface cracks in the presence of material nonlinearity of adherends

The well known features of crack face interpenetration/contact at the tip of an interface crack is re-examined using finite element analysis and assuming material nonlinear properties for the adherends. It was assumed in literature that the crack tips are fully open at all load levels in the presence of material nonlinearity of the adherends. Analysis for the case of remote tension shows that even in the presence of material nonlinearity, crack tip closes at small load levels and opens above a certain load level. Mixed-mode fracture parameters are evaluated for the situation when the crack tips are fully open. Due to the presence of nonlinearity, the mixed-mode fracture parameters are measured with the symmetric and anti-symmetric components of J-integral. The present analysis explains the sequence of events at the interface crack tip with progressively increasing remote tension load for the case of adherends with material nonlinear behaviour.

Efficient computation of volume fractions for multi-material cell complexes in a grid by slicing

The paper presents a novel slicing based method for computation of volume fractions in multi-material solids given as a B-rep whose faces are triangulated and shared by either one or two materials. Such objects occur naturally in geoscience applications and the said computation is necessary for property estimation problems and iterative forward modeling. Each facet in the model is cut by the planes delineating the given grid structure or grid cells. The method, instead of classifying the points or cells with respect to the solid, exploits the convexity of triangles and the simple axis-oriented disposition of the cutting surfaces to construct a novel intermediate space enumeration representation called slice-representation, from which both the cell containment test and the volume-fraction computation are done easily. Cartesian and cylindrical grids with uniform and non-uniform spacings have been dealt with in this paper. After slicing, each triangle contributes polygonal facets, with potential elliptical edges, to the grid cells through which it passes. The volume fractions of different materials in a grid cell that is in interaction with the material interfaces are obtained by accumulating the volume contributions computed from each facet in the grid cell. The method is fast, accurate, robust and memory efficient. Examples illustrating the method and performance are included in the paper.

Nano-confined synthesis of highly ordered mesoporous carbon and its performance as electrode material for electrochemical behavior of riboflavin (vitamin B2) and dopamine

Highly ordered mesoporous carbon (MC) has been synthesized from sucrose, a non-toxic and costeffective source of carbon. X-ray diffraction, N2 adsorption–desorption isotherm and transmission electron micrograph (TEM) were used to characterize the MC. The XRD patterns show the formation of highly ordered mesoporous structures of SBA15 and mesoporous carbon. The N2 adsorptiondesorption isotherms suggest that the MC exhibits a narrow pore-size distribution with high surface area of 1559 m2/g. The potential application of MC as a novel electrode material was investigated using cyclic voltammetry for riboflavin (vitamin B2) and dopamine. MC-modified glassy carbon electrode (MC/GC) shows increase in peak current compared to GC electrode in potassium ferricyanide which clearly suggest that MC/GC possesses larger electrode area (1.8 fold) compared with bare GC electrode. The electrocatalytic behavior of MC/GC was investigated towards the oxidation of riboflavin (vitamin B2) and dopamine using cyclic voltammetry which show larger oxidation current compared to unmodified electrode and thus MC/GC may have the potential to be used as a chemically modified electrode.

Effect of the addition of B2O3 and BaO-B2O3-SiO2 glasses on the microstructure and dielectric properties of giant dielectric constant material CaCu3Ti4O12

The effect of the addition of glassy phases on the microstructure and dielectric properties of CaCu3Ti4O12 (CCTO) ceramics was investigated. Both single-component (B2O3) and multi-cornponent (30wt% BaO-60wt% B2O3-10wt% SiO2 (BBS)) glass systems were chosen to study their effect on the density, microstructure and dielectric properties of CCTO. Addition of an optimum amount of B2O3 glass facilitated grain growth and an increase in dielectric constant. However, further increase in the B2O3 content resulted in its segregation at the grain boundaries associated with a reduction in the grain size. In contrast, BBS glass addition resulted in well-faceted grains and increase in the dielectric constant and decrease in the dielectric loss. An internal barrier layer capacitance (IBLC) model was invoked to correlate the dielectric constant with the grain size in these samples. (c) 2007 Elsevier Inc. All rights reserved.

Simultaneous material selection and geometry design of statically determinate trusses using continuous optimization

In this work, we explore simultaneous geometry design and material selection for statically determinate trusses by posing it as a continuous optimization problem. The underlying principles of our approach are structural optimization and Ashby’s procedure for material selection from a database. For simplicity and ease of initial implementation, only static loads are considered in this work with the intent of maximum stiffness, minimum weight/cost, and safety against failure. Safety of tensile and compression members in the truss is treated differently to prevent yield and buckling failures, respectively. Geometry variables such as lengths and orientations of members are taken to be the design variables in an assumed layout. Areas of cross-section of the members are determined to satisfy the failure constraints in each member. Along the lines of Ashby’s material indices, a new design index is derived for trusses. The design index helps in choosing the most suitable material for any geometry of the truss. Using the design index, both the design space and the material database are searched simultaneously using gradient-based optimization algorithms. The important feature of our approach is that the formulated optimization problem is continuous, although the material selection from a database is an inherently discrete problem. A few illustrative examples are included. It is observed that the method is capable of determining the optimal topology in addition to optimal geometry when the assumed layout contains more links than are necessary for optimality.

Interatomic potentials for fusion reactor material simulations

Fusion energy is a clean and safe solution for the intricate question of how to produce non-polluting and sustainable energy for the constantly growing population. The fusion process does not result in any harmful waste or green-house gases, since small amounts of helium is the only bi-product that is produced when using the hydrogen isotopes deuterium and tritium as fuel. Moreover, deuterium is abundant in seawater and tritium can be bred from lithium, a common metal in the Earth's crust, rendering the fuel reservoirs practically bottomless. Due to its enormous mass, the Sun has been able to utilize fusion as its main energy source ever since it was born. But here on Earth, we must find other means to achieve the same. Inertial fusion involving powerful lasers and thermonuclear fusion employing extreme temperatures are examples of successful methods. However, these have yet to produce more energy than they consume. In thermonuclear fusion, the fuel is held inside a tokamak, which is a doughnut-shaped chamber with strong magnets wrapped around it. Once the fuel is heated up, it is controlled with the help of these magnets, since the required temperatures (over 100 million degrees C) will separate the electrons from the nuclei, forming a plasma. Once the fusion reactions occur, excess binding energy is released as energetic neutrons, which are absorbed in water in order to produce steam that runs turbines. Keeping the power losses from the plasma low, thus allowing for a high number of reactions, is a challenge. Another challenge is related to the reactor materials, since the confinement of the plasma particles is not perfect, resulting in particle bombardment of the reactor walls and structures. Material erosion and activation as well as plasma contamination are expected. Adding to this, the high energy neutrons will cause radiation damage in the materials, causing, for instance, swelling and embrittlement. In this thesis, the behaviour of a material situated in a fusion reactor was studied using molecular dynamics simulations. Simulations of processes in the next generation fusion reactor ITER include the reactor materials beryllium, carbon and tungsten as well as the plasma hydrogen isotopes. This means that interaction models, {\it i.e. interatomic potentials}, for this complicated quaternary system are needed. The task of finding such potentials is nonetheless nearly at its end, since models for the beryllium-carbon-hydrogen interactions were constructed in this thesis and as a continuation of that work, a beryllium-tungsten model is under development. These potentials are combinable with the earlier tungsten-carbon-hydrogen ones. The potentials were used to explain the chemical sputtering of beryllium due to deuterium plasma exposure. During experiments, a large fraction of the sputtered beryllium atoms were observed to be released as BeD molecules, and the simulations identified the swift chemical sputtering mechanism, previously not believed to be important in metals, as the underlying mechanism. Radiation damage in the reactor structural materials vanadium, iron and iron chromium, as well as in the wall material tungsten and the mixed alloy tungsten carbide, was also studied in this thesis. Interatomic potentials for vanadium, tungsten and iron were modified to be better suited for simulating collision cascades that are formed during particle irradiation, and the potential features affecting the resulting primary damage were identified. Including the often neglected electronic effects in the simulations was also shown to have an impact on the damage. With proper tuning of the electron-phonon interaction strength, experimentally measured quantities related to ion-beam mixing in iron could be reproduced. The damage in tungsten carbide alloys showed elemental asymmetry, as the major part of the damage consisted of carbon defects. On the other hand, modelling the damage in the iron chromium alloy, essentially representing steel, showed that small additions of chromium do not noticeably affect the primary damage in iron. Since a complete assessment of the response of a material in a future full-scale fusion reactor is not achievable using only experimental techniques, molecular dynamics simulations are of vital help. This thesis has not only provided insight into complicated reactor processes and improved current methods, but also offered tools for further simulations. It is therefore an important step towards making fusion energy more than a future goal.

Multiscale study on hydrogen mobility in metallic fusion divertor material

For achieving efficient fusion energy production, the plasma-facing wall materials of the fusion reactor should ensure long time operation. In the next step fusion device, ITER, the first wall region facing the highest heat and particle load, i.e. the divertor area, will mainly consist of tiles based on tungsten. During the reactor operation, the tungsten material is slowly but inevitably saturated with tritium. Tritium is the relatively short-lived hydrogen isotope used in the fusion reaction. The amount of tritium retained in the wall materials should be minimized and its recycling back to the plasma must be unrestrained, otherwise it cannot be used for fueling the plasma. A very expensive and thus economically not viable solution is to replace the first walls quite often. A better solution is to heat the walls to temperatures where tritium is released. Unfortunately, the exact mechanisms of hydrogen release in tungsten are not known. In this thesis both experimental and computational methods have been used for studying the release and retention of hydrogen in tungsten. The experimental work consists of hydrogen implantations into pure polycrystalline tungsten, the determination of the hydrogen concentrations using ion beam analyses (IBA) and monitoring the out-diffused hydrogen gas with thermodesorption spectrometry (TDS) as the tungsten samples are heated at elevated temperatures. Combining IBA methods with TDS, the retained amount of hydrogen is obtained as well as the temperatures needed for the hydrogen release. With computational methods the hydrogen-defect interactions and implantation-induced irradiation damage can be examined at the atomic level. The method of multiscale modelling combines the results obtained from computational methodologies applicable at different length and time scales. Electron density functional theory calculations were used for determining the energetics of the elementary processes of hydrogen in tungsten, such as diffusivity and trapping to vacancies and surfaces. Results from the energetics of pure tungsten defects were used in the development of an classical bond-order potential for describing the tungsten defects to be used in molecular dynamics simulations. The developed potential was utilized in determination of the defect clustering and annihilation properties. These results were further employed in binary collision and rate theory calculations to determine the evolution of large defect clusters that trap hydrogen in the course of implantation. The computational results for the defect and trapped hydrogen concentrations were successfully compared with the experimental results. With the aforedescribed multiscale analysis the experimental results within this thesis and found in the literature were explained both quantitatively and qualitatively.

Characterisation of head-hardened rail steel in terms of cyclic plasticity response and microstructure for improved material modelling

Stress- and strain-controlled tests of heat treated high-strength rail steel (Australian Standard AS1085.1) have been performed in order to improve the characterisation of the said material׳s ratcheting and fatigue wear behaviour. The hardness of the rail head material has also been studied and it has been found that hardness reduces considerably below four-millimetres from the rail top surface. Historically, researchers have used test coupons with circular cross-sections to conduct cyclic load tests. Such test coupons, typically five-millimetres in gauge diameter and ten‐millimetres in grip diameter, are usually taken from the rail head sample. When there is considerable variation of material properties over the cross-section it becomes likely that localised properties of the rail material will be missed. In another case from the literature, disks 47 mm in diameter for a twin-disk rolling contact test machine were obtained directly from the rail sample and used to validate ratcheting and rolling contact fatigue wear models. The question arises: How accurate are such tests, especially when large material property gradients exist? In this research paper, the effects of rail sampling location on the ratcheting behaviour of AS1085.1 rail steel were investigated using rectangular-shaped specimens obtained at four different depths to observe their respective cyclic plasticity behaviour. The microstructural features of the test coupons were also analysed, especially the pearlite inter-lamellar spacing which showed strong correlation with both hardness and cyclic plasticity behaviour of the material. This work ultimately provides new data and testing methodology to aid the selection of valid parameters for material constitutive models to better understand rail surface ratcheting and wear.