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To obtain high strength often suggests inorganic and non-metallic materials where hardness provides resistance against high thermal or mechanical loads. In a book concerned with dynamic extremes, these stimuli include materials propelled to impact at high velocity. The design paradigm requires a material to deliver an easily formed structural component capable of resisting impulsive loads of high amplitude and arbitrary duration. At the present time the reality is that these aspirations are only partially met. The response of these materials to idealised one-dimensional loading under shock is not yet understood in full detail and fully three-dimensional loading is only described empirically. Nevertheless the response of glasses and ceramics to dynamic loading has been investigated by the impact community over the past 30 years so that at least a library of data exists. In that time much has been learnt but vital questions remain unresolved, particularly understanding contact, penetration, fragmentation, inelastic behaviour and failure that are encountered in the response of a brittle material to impulsive loading.
Even the qualitative understanding of the response of brittle materials to dynamic loading has not been reflected in advances in constitutive models for them. This results from an incomplete knowledge of operating mechanisms that are consequently not reflected in global models. Further, there is a wide range of microstructures represented in this grouping, ranging from amorphous silicate glasses to polycrystalline ceramics containing both crystalline and amorphous phases. Clearly to construct adequate models for such heterogeneous materials to work on numerical platforms requires a macroscale description of behaviour, yet at present even subscale approaches have not described the processes operating in these heterogeneous media where the phases interact at the mesoscale. It is scale that remains the key frontier that bridges the continuum to microscale behaviour, and it is the mesoscale where the defects that control failure in the bulk are found.
Understanding the physical origin of threshold switching and resistance drift phenomena is necessary for making a breakthrough in the performance of low-cost nanoscale technologies related to nonvolatile phase-change memories. Even though both phenomena of threshold switching and resistance drift are often attributed to localized states in the band gap, the distribution of defect states in amorphous phase-change materials (PCMs) has not received so far, the level of attention that it merits. This work presents an experimental study of defects in amorphous PCMs using modulated photocurrent experiments and photothermal deflection spectroscopy. This study of electrically switching alloys involving germanium (Ge), antimony (Sb) and tellurium (Te) such as amorphous germanium telluride (a-GeTe), a-Ge15Te85 and a-Ge2Sb2Te5 demonstrates that those compositions showing a high electrical threshold field also show a high defect density. This result supports a mechanism of recombination and field-induced generation driving threshold switching in amorphous chalcogenides. Furthermore, this work provides strong experimental evidence for complex trap kinetics during resistance drift. This work reports annihilation of deep states and an increase in shallow defect density accompanied by band gap widening in aged a-GeTe thin films.
A computer program, Dysnomia, for the maximum-entropy method (MEM) has been tested for the evaluation and advancement of MEM-based pattern fitting (MPF). Dysnomia is a successor to PRIMA, which was the only program integrated with RIETAN-FP for MPF. Two types of MEM algorithms, i.e., 0th-order single-pixel approximation and a variant of the Cambridge algorithm, were implemented in Dysnomia in combination with a linear combination of the “generalized F constraints” and arbitrary weighting factors for them. Dysnomia excels PRIMA in computation speed, memory efficiency, and scalability owing to parallel processing and automatic switching of discrete Fourier transform and fast Fourier transform depending on sizes of grids and observed reflections. These features of Dysnomia were evaluated for MPF analyses from X-ray powder diffraction data of three different types of compounds: taurine, Cu2CO3(OH)2 (malachite), and Sr9In(PO4)7. Reliability indices in MPF analyses proved to have been improved by using multiple F constraints and weighting factors based on lattice-plane spacings, d, in comparison with those obtained with PRIMA.
The man-made and the natural environment surrounds man with a wide array of plastics and polymers both natural and man-made. A polymer is a molecule which contains repeated units of a particular chemical base segment, and there are many types found across organic chemistry. A plastic is a term that covers a wide range of mostly synthetic but also some natural organic products that can be moulded or extruded. Thus while all plastics are organic polymers, not all polymers are plastics and in general may need to be modified with other additives to form useful materials. In everyday parlance plastic and polymer are terms often used interchangeably but in fact there are many other types of molecules, both biological and inorganic, that are also polymeric.
The word polymer has ancient Greek roots, compounded from poly (meaning many) and meros (meaning parts or units), whilst plastic has a root that indicates a solid that is malleable being easily shaped or moulded. Natural plastics may originate in biological systems such as tar and shellac, tortoise shell and horns, as well as tree saps that produce amber and latex. These plastics may be processed with heat and pressure into a host of different products. If natural polymers are chemically modified then other plastics result and during the 1800s these processes produced such materials as vulcanised rubber and celluloid. In 1909 a semi-synthetic polymer was produced called Bakelite, soon followed by fibres such as rayon (1911). The ability to work and particularly to cast or mould them to component shapes made plastics increasingly dominant for manufacturing. However, restrictions on supply of natural materials during the Second World War led to the modern predominance of synthetic plastics. This time period saw development of nylon, acrylic, neoprene, polyethylene and many more to replace the natural products that could no longer be imported. Post-war the plastics business has developed into one of the fastest growing industries in the world.
In the next chapters, four groups of materials will be introduced and discussed. These will embrace metals, brittle solids, polymers and energetic materials. Some of these will be pure elements in various microstructures, others will be composites of several in different conformations. A lot of what follows has been described and studied by materials science and much terminology and commonplace understanding will be borrowed from there. Appendix A at the end of the book summarises some key concepts for those trained in other disciplines. At the most basic level, materials can be classified as metals or non-metals according to their ability to conduct electricity. The metals consist of cations in a delocalised electron cloud with structure determined by electrostatic bonds formed between the ions and the electron cloud. As pressure increases this bonding changes nature and above the finis extremis localisation of the electron density away from the nucleus occurs leading to new states.
Metals are the most common class of elements in the periodic table (Figure 5.1). Atomic stacking rules define a lattice of ions surrounded by a delocalised cloud of electrons, but from the point of view of the electronic states, one may equally consider them as materials where conduction and valence bands overlap. This definition opens the descriptor to metallic polymers and other organic metals and, considering the context within this book, one must consider the behaviour of materials that change their characteristics under high pressures and cause them to achieve metallic states (to conduct) at pressures below the finis extremis. A diagonal line drawn from aluminium (Al) to polonium (Po) separates the metals from the non-metals, and within that region the elements order themselves into subgroups defined by their electronic structures.
This chapter will detail the response of a class of materials dubbed energetic to signify that they can break bonds and react under load. These substances contain a large amount of stored chemical energy that can be released if appropriate thermal thresholds are exceeded. Such materials combine a fuel and an oxidiser; fuels are typically carbon or hydrogen, oxidisers are oxygen or a halogen like chlorine, for example. Combining hydrogen and oxygen to form water liberates 13 260 J kg–1 and burning petrol with oxygen (air) 30000 J kg–1. Yet the high explosive TNT liberates only 4080 J kg–1, less than 15% of the amount liberated by petrol. The difference is that fuel alone burns only where oxygen is present; a spillage will burn for minutes with oxygen from air, for example. Yet a TNT molecule contains oxygen within it and can liberate energy in the microseconds the reaction front takes to transit the molecule and break bonds. Therefore the difference between these fuels lies in the power that the molecule supplies in the form in which the material exists on ignition. Energetic materials may be solids, liquids or gases, but condensed-phase materials will be followed here as earlier in the book. Further, they need not necessarily be organic. There is increasing need for higher performance, lighter weight and safer composites which use reacting metals as well as more conventional materials and using new material morphologies which have increased surface areas, such as mixtures of nano-materials or designed nano-composites. However, the principal energetics used at the present time include a range of elements that react with oxygen and these will be discussed in what follows.
Ordered arrays of titania nanotubes (NTs) are considered as good candidates for photocatalytic applications including water splitting. Considering that the functionality of these nanostructures is influenced by their morphology, electronic and the crystallographic structure, fundamental understanding of these properties and their possible correlations can clarify the approaches toward enhanced photocatalytic efficiency. In this work, ordered arrays of titania NTs are synthesized electrochemically and are subjected to isochronal annealing treatments in various atmospheres (oxygen-rich, oxygen-deficient and reducing) to modify their morphology, crystal and electronic structure. Upon characterization of these NTs, direct correlations are found between the annealing atmosphere and the corresponding unit cell volume and the crystallite size. Furthermore, correlations between the NTs’ structure and magnetic response are observed, revealing changes in the electronic structure such as the density of states, that are in turn relevant to the functional catalytic properties of titania.
Matter in the universe exists in a series of states; three that are well known from standard experience, solid, liquid and gas, and the plasma state in which gas is ionised. Other more esoteric states are possible but the four above occupy the main thrust of this book. This volume has confined itself to pressures in the range up to a megabar and temperatures below 10000 K in which solids exhibit strength that is based upon the interaction of valence electrons. Beyond a critical energy density bonding is determined by further interactions of inner orbital electrons and concepts from the ambient cannot be extended.
Equally the forces acting on matter applicable to this work are electrostatic or gravitational. Electrostatic forces may act over great distance but as length scale increases there is sufficient matter that substances behave as neutral. The long-range attractions at the microscale are due to Van de Waals’ forces that might operate over distances of the order of 10 nm between polymer chains and are important in binding matter at the mesoscale. Components on a scale of centimetres are naturally held under gravity in stacks or compressed under lateral forces by some restraint. The strength of such an interface in tension is determined by that of the pin or joint that constrains the interface between the two components. At this scale, flow occurs by hinging around pivots under load or by slip along the fracture line with frictional heating at the interface. At the planetary scale forces are gravitational and slip occurs down faults that allow flow under shear.
I cannot explain my curiosity about extreme phenomena in nature; nevertheless I have been drawn to the science that surrounds them – from those occurring on the scale of solar systems to those at work at the smallest regimes within matter. Extreme forces surround us; they govern our weather, the cores of planets, components of engineering structures and the ordering of particles within atoms. At the scales of interest in this book they are either gravitational or electrostatic in origin. Forces drive mechanical routes to impose change and materials are forced to respond to these pressures in non-linear, counter-intuitive and utterly fascinating manners; frequently more quickly than not only the senses, but the recording media that exist today can track. Nothing that changes does so instantaneously; every mechanism takes some time, however small. This mean that the integrated response follows a delicate framework of competing pathways that reorder as the driver for the forces changes. As with many processes, one can only see patterns apparent in retrospect. Furthermore, the difficulties encountered achieving these states mean that there are many untracked routes that matter can take to respond about which we know little. Thus despite the years this book has taken to come to this point, it can only provide a snapshot of behaviour as I see it.
Nevertheless, matter allows the nature of its bonding to be probed by subjecting it to load and the reader will learn to appreciate the variety of materials behaviours and their causes that allow the design of structures or even new materials to withstand the environments considered. The behaviours observed are complex and seemingly counter-intuitive, and quantifying them has frequently filled books in the past with extended solid mechanics. This has made texts rich in analysis and specialised in application and required the reader to be expert in the mathematics of non-linear behaviour. However, it seemed that a reader with an appreciation of the physical sciences and elementary algebra required an open text to emphasise behaviours not analytical subtleties. Thus this book unites principles covering a broad canvas at a level accessible to graduate students.Further, it addresses the regime in which the strength of matter may be described with extensions of solid mechanics at the continuum rather than extrapolation of atomic theory and quantum mechanics at the atomic scale.
The quality of interface between ultrathin silicon dioxide films and their silicon (Si) wafers was characterized using room-temperature photoluminescence (RTPL) and Raman spectroscopy. Three types of low-temperature (350 °C or room temperature) oxide films on Si grown by different techniques were measured and compared with Si wafers having native oxide and high-temperature thermally grown oxide films. Significant RTPL spectra and intensity variations were measured among low-temperature oxide films. Very strong excitation wave length dependence of RTPL spectra and intensity was observed from the low-temperature oxide films on Si whereas the RTPL spectra and intensity from Si with native oxide and thermally grown oxide films were consistent. Stress in the Si lattice, with different low-temperature oxide layers, showed noticeable differences depending on the oxidation technique used. Key device performance parameters of image sensor devices fabricated using three different low-temperature oxide films showed good correlation with the RTPL and Raman measurement results. The RTPL spectra and Raman shifts are very sensitive to the quality of the oxide/Si interface and can be used as an interface quality monitoring technique.
In the previous chapter, a series of examples was given to illustrate a range of material responses that stem from impact or explosion and result from a transient loading pulse within the material. These drivers propel waves travelling through solids, liquids and gases and place the material they have swept through into a state of compression, tension or shear. This chapter will describe these disturbances in more detail and attempt to give simple mathematical descriptions of the phenomena and the material's response. This basic approach is really a development of solid (a branch of continuum) mechanics to embrace additional features of loading at higher speeds and amplitudes; there are many, more complete texts available on the basics of solid mechanics that the reader may consult. The strategy here is to keep the derivations as simple as possible; again there are texts that derive relations with more generality than here but it is vital that the reader realises the assumptions, and more importantly their limits, in what follows. Particularly, it should be noted that solid mechanics assumes material behaviour based upon observations made in ambient states. Electronic bonding itself changes nature at around 300 GPa, so it is unrealistic to expect theory extended from the elastic state to apply in these regimes. Thus assumptions made and their limitations in the loading states the reader wishes to consider must be fully understood before using the formulae below. The basic laws of conservation of mass, momentum and energy, and classical mechanics will drive the descriptions of the thermodynamic states. To that will be added the concepts of elastic and inelastic (in metals, plastic) deformation bounded by a yield surface. To focus on material response, it is generally the simplest loading that is applied experimentally. Thus these states will be mentioned below to highlight particular relations to which the text will return.
The dynamic processes operating around us are often treated as transients that are not important when compared with the fixed states they precede. However, an ever-increasing knowledge base has illuminated this view of the operating physics and confirmed that extreme regimes can be accessed for engineering materials and structures. Matter is ever-changing, its form developing in a series of nested processes which complete on the timescales on which mechanisms operate; processes that occur on ever smaller timescales as length scales decrease. This book is concerned with the response that occurs when loads exceed the elastic limit. This affects behaviour in the regime beyond yield which encompasses a range of amplitudes and responses. However, it concerns condensed materials and loading, eventually taking them to a state where they bond in a different manner such that strength is not defined; this limit represents the highest amplitude of loading considered here. Nonetheless the driving forces are vast and awe-inspiring, while the different rates of change observed in operating processes are on scales that span many orders of magnitude. The following pages will highlight prime examples from the physical world and then provide a set of tools that classify mechanisms in order to analyse significant effects of these processes on the materials involved. The wide range of observations and applications create simple but powerful principles that are outlined in what follows.
Materials are central to the technologies required for future needs. Such platforms will place increasing demands on component performance in a range of extremes: stress, strain, temperature, pressure, chemical reactivity, photon or radiation flux, and electric or magnetic fields. For example, future vehicles will demand lighter-weight parts with increased strength and damage tolerance and next-generation fission reactors will require materials capable of withstanding higher temperatures and radiation fluxes. To counter security threats, defence agencies must protect their populations against terrorist attack and design critical facilities and buildings against atmospheric extremes.
We have developed a reactive force field within the ReaxFF framework to accurately describe reactions involving aluminum–molybdenum alloy, which are part parameters of Al–O–Mo ternary system metastable intermolecular composites. The parameters are optimized from a training set, whose data come from density functional theory (DFT) calculations and experimental value, such as heat of formation, geometry data, and equation of states, which are reproduced well by ReaxFF. Body-centered cubic molybdenum’s surface energy, vacancy formation, and two transformational paths, Bain and trigonal paths are calculated to validate the ReaxFF ability describing the defects and deformations. Some structures’ elastic constant and phonon are calculated by DFT and ReaxFF to predict the structures’ mechanics and kinetic stability. All those results indicate that the fitted parameters can describe the energy difference of various structures under various circumstances and generally represent the diffusion property but cannot reproduce the elasticity and phonon spectra so well.