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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.
The present chapter gives an overview of experimental platforms showing how they may be used to populate models for materials behaviour. The condensed phase defines the pressure and temperature range of interest, which may be approximately fixed at less than 1 TPa and below 10000 K. Indeed pressure has one of the largest ranges of all physical parameters in the universe (the pressure in a neutron star is c. 1033 Pa), so that most of the materials in nature are under conditions very different from those on Earth. The goal of shock experiments is to track response and mechanisms across the realms of stress and volume that are experienced by condensed-phase matter across the universe. At the highest pressures and temperatures, materials move from the solid to the liquid and then to plasma states as new correlations and bonding are formed. These high-density states have been termed warm dense matter (WDM) and lie beyond the finis extremis – outside the regime of extreme behaviour considered here. A summary of the phase space occupied by matter in these regions is shown in Figure 3.1.
The goal of experimental work is to provide adequate knowledge of the response of matter over the operating regimes of the relevant plasticity mechanisms. By this means, analytical descriptions can be constructed to try and capture the fundamental relationships between the independent variables – stress and stress state, strain and strain rate, and temperature – that determine the constitutive, damage and failure behaviour of materials. A shock impulse provides a pump to drive materials deformation and control of that impulse also allows a window into the operative mechanisms that lead to plasticity and damage evolution. This includes determining dynamic strength as a function of pressure as well as determining equation of state over the range of interest for particular applications.
This article reviews the use of x-ray computed tomography (XRCT) to investigate the structure and properties of cellular solids. In the first section, the possibilities offered by XRCT are presented. Examples of tomographic images are shown for the three classes of material (polymers, metals, and ceramics). Different characterizations of cellular solids performed thanks to XRCT images are shown: calculation of morphological parameters, in situ and ex situ mechanical tests, and use of the tomographic images to perform finite element (FE) modeling. The second part of the paper presents the existing methods to create the meshes from tomographic images and highlights some interesting results from the FE simulations.
In this paper, a process to introduce nanoscale cells in homogeneous polyetherimide (PEI) is presented. The nanofoams produced have a bulk porosity (void fraction) in the range of 25–64%, with the average cell sizes in the range of 40–100 nm. Uniform nucleation of cells throughout the volume of the PEI specimen was observed. Supercritical CO2 at 20 MPa was used as the blowing agent and the specimens were foamed in a hot press to ensure flatness for further processing and characterization. Sorption studies showed that at 20 MPa, PEI can absorb about 10% CO2 by weight and that a 1-mm thick specimen can reach an equilibrium concentration in approximately 100 h at 45 °C. The effects of desorption time, foaming temperature, clamping pressure, and foaming time were investigated. Several nanoscale morphologies were observed through changes in the foaming temperature, which ranged from 165 to 210 °C. In one experiment, it was found that when the clamping force is increased from 1 to 10 tons, the average cell size increased from 40 to 4000 nm or by a factor of 100. This points to the clamping force as an important process variable to control the nanostructure introduced in PEI. Optimal processing conditions for the production of defect-free nanofoams are presented.
Confined synthesis of three-dimensionally ordered mesoporous-imprinted (3DOm-i) zeolites within three-dimensionally ordered mesoporous (3DOm) carbons prepared from silica colloidal crystals was achieved through multiple hydrothermal (MHT) synthesis and steam-assisted crystallization (SAC). The transition of ordered mesoporous structures, starting from silica colloidal crystal to resulting 3DOm-i zeolites including the intermediate 3DOm carbon templates, and the correlations among the confined synthesis methods, crystal growth nature of different zeolites, and the sintering of the templates were studied. An imperfect replication was found in 3DOm-i zeolite when it compared to silica colloidal crystals regardless the synthesis methods (MHT or SAC), which might be originated from combination effects of sintering of the silica colloidal crystals and partial filling of cavities of the 3DOm carbon template during the confined synthesis, and the degree of the structure replication was notably influenced by microstructures of zeolite as well. A thorough investigation of the growth development of 3DOm-i BEA zeolites with various Si/Al ratios ranging from 14 to 27 through the MHT method confirmed that the crystallization takes place in the carbon template by a cage-to-cage propagation growth process.
Gold surfaces exhibit most interesting frictional properties on the nanometer scale. They can be studied in detail by means of friction force microscopy. Atomic-scale variations of the lateral force allow investigation of microscopic mechanisms of sliding. Friction force microscopy even reveals surface reconstruction of the gold surface as a modulation of the lateral force signal. Experiments indicate that the mobility of surface atoms at room temperature and plastic deformation mechanisms give rise to neck formation between gold and microscopic asperities in sliding contact. The frictional properties of gold surfaces change dramatically at temperatures below 150 K, where the surface diffusion is greatly reduced. Insight into the lubrication properties of self-assembled monolayers is provided by molecular-scale modulations of frictional forces. Molecular-scale maps of the friction force also allow identification of the relevant surface structure in experiments on electrochemically modified gold surfaces. Variation of the electrochemical potential is a means to reversibly switch between low and high friction states on gold surfaces.
This unified guide brings together the underlying principles, and predictable material responses, that connect metals, polymers, brittle solids and energetic materials as they respond to extreme external stresses. Previously disparate scientific principles, concepts and terminology are combined within a single theoretical framework, across different materials and scales, to provide all the tools necessary to understand, and calculate, the responses of materials and structures to extreme static and dynamic loading. Real-world examples illustrate how material behaviours produce a component response, enabling recognition – and avoidance – of the deformation mechanisms that contribute to mechanical failure. A final synoptic chapter presents a case study of extreme conditions brought about by the infamous Chicxulub impact event. Bringing together simple concepts from diverse fields into a single, accessible, rigorous text, this is an indispensable reference for all researchers and practitioners in materials science, mechanical engineering, physics, physical chemistry and geophysics.
Presenting a unique perspective on state-of-the-art physical gels, this interdisciplinary guide provides a complete, critical analysis of the field and highlights recent developments. It shows the interconnections between the key aspects of gels, from molecules and structure through to rheological and functional properties, with each chapter focusing on a different class of gel. There is also a final chapter covering innovative systems and applications, providing the information needed to understand current and future practical applications of gels in the pharmaceutical, agricultural, cosmetic, chemical and food industries. Many research teams are involved in the field of gels, including theoreticians, experimentalists and chemical engineers, but this interdisciplinary book collates and rationalises the many different points of view to provide a clear understanding of these complex systems for researchers and graduate students.
Grain boundary engineering (GBE) has been carried out in nickel-based Alloy 690 with different initial grain sizes. The microstructure evolution during GBE-processing is characterized using electron backscatter diffraction to study the initial grain size effects on the grain boundary network (GBN). The microstructures of the partially recrystallized samples revealed that the GBE-processing is a strain-recrystallization process, during which each grain-cluster is formed by “multiple twinning” starting from a single recrystallization nucleus. Taking into consideration the coincidence site lattices (CSLs) and ∑, which is defined as the reciprocal density of coincidence sites, a high proportion of low-∑ CSL grain boundaries (GBs) and large grain-clusters are found to be the features of GBE-processed GBN. The initial grain size has a combined effect on the low-∑ CSL GBs proportion. A large initial grain size reduces the number of recrystallization nuclei that form, increasing the cluster size, but decreasing twin boundary density. On the other hand, smaller initial grain sizes increase the density of twin boundary after recrystallization, while decreasing grain-cluster size. Neither the grain-cluster size nor the twin boundary density is the sole factor influencing the proportion of low-∑ CSL GBs. The ratio of the grain cluster size over the grain size governs the proportion of low-∑ CSL GBs.
Materiomics is growing. In this book, we have discussed and reviewed how one side of the materiomics coin, the screening of libraries of biomaterials, is developing, but the future of screening will go hand in hand with the other side of the coin – modelling. Materiomics is growing and is, one could say, still in its infancy. Currently, most materiomics research is performed by academic research groups, although a small but increasing number of companies are active in this area. It will be helpful to understand how fast this field will grow, and how it might develop.
To sketch a potential scenario perhaps it is worth looking at recent developments in the field of molecular biology. In the mid-1990s, there were specialized machines in the lab to produce oligonucleotides, so-called primers, used in the polymerase chain reaction, a specialist job which gave the lab a scientific head start. These days, however, a primer can be ordered online and be at your bench in days, for the cost of a few dozen Euros. By the late 1990s, we saw cDNAs arrayed on nitrocellulose, which allowed simultaneous quantification of expression for dozens to hundreds of genes. No more tedious northern blotting one gene at a time! Driven by these early successes, many institutes started investing in arraying equipment and software development, as DNA microarray analysis became increasingly popular. But the real breakthrough in the use of this technology came when companies such as Affymetrix invested not only in standardization and professionalization of the technology, but importantly also in the work flow of a DNA microarray experiment. These companies provided a full package with not only arrays but also the incubators, washing, data analysis, detailed work protocols, image analysis software and a customer service platform. In both cases, the new technological possibilities of oligonucleotide synthesis and DNA microarray production paved the way for breakthroughs in science. We think that this will also be possible for materiomics.
This chapter deals with an overview of basic microfabrication techniques. The goal is to explain to the reader how such techniques can be utilized in the field of materiomics. The basic processes used in microfabrication including photolithography, etching, electron beam lithography and micromoulding are explained. Some classic examples of these techniques as applied to materiomics are also shown. Furthermore, possible uses of such techniques, and the development and application of hybrid techniques to be able to answer fundamental questions about biological behaviour of materials, are also suggested.
Basic principles of microfabrication
Introduction
Techniques used to fabricate structures or devices smaller than 100 µm are commonly referred to as microfabrication techniques. Initially meant for the electronics industry, they have found a wide range of applications in diverse fields such as chemical engineering and the life sciences. Since the early 1990s, the application of microfabrication technologies in the area of chemical and biological analysis has been termed ‘micro total analysis systems’ (µTAS) (1). Microfabricated devices meant for µTAS initially offered the advantage of sample analysis on the microscale, but over the years, the evolution of these technologies has led to the facilitation of sample preparation, fluid handling, separation systems, cell handling and cell culturing in an integrated manner (1). The application of microtechnologies for the fabrication of devices or systems to study material properties benefits from cost efficiency, high performance, precision-based design flexibility, miniaturization and automated analysis. Miniaturization involves the convergence of multiple disciplines, such as fluid dynamics, material sciences, engineering and the life sciences, that need to join expertise in order to design functional systems. Moreover, these devices can be used to evaluate biological behaviour in vitro and can help us to test thousands of different biomaterials and surface properties without the complexity related to in vivo assays.
Given the demographic challenges of an ageing population combined with rising patient expectation and the growing emphasis placed on cost containment by healthcare providers, economic regenerative medicine approaches for regeneration of damaged and diseased organs and tissues are a major clinical and socio-economic need. The scope of this chapter is to use skeletal regeneration as the exemplar to discuss classical and high-throughput screening approaches to biomaterials development for regenerative medicine, including choice and design of materials based on clinical need, biological assessment and regulatory issues.
Basic principles: development of materials for regenerative medicine
The increase in an ageing population in developed countries is accompanied by a growing need for replacement and repair of damaged organs and tissues. Transplantation of the patient’s own tissue is still considered the gold standard in many applications, but limited availability, and complications associated with harvesting of the so-called autograft, are becoming an important drawback. Tissues and organs from human or animal donors present issues of disease transmission and functional failure. Alternative strategies, based on biological growth factors, cell therapy and tissue-engineered constructs, are being explored as alternatives to the patient’s own tissue, but their use is hampered by biological instability and high costs. These issues demonstrate the need for strategies based on biomaterials, which are often synthetic, and thus less prone to instability problems. In addition, the fact that (synthetic) biomaterials can often be produced in large quantities and thus be available off-the-shelf is an important advantage when coping with an increasing need for regenerative approaches.