Handbook of Materials Structures, Properties, Processing and Performance

This initial chapter briefly reviews the principal ages of materials and metals: the Stone Age, the Copper Age, the Bronze Age, and the Iron Age, spanning some ten millennia. Incidental to these major materials ages, gold and silver are noted as these were initially utilized in native forms, along with copper and iron, which has been identified throughout antiquity in meteoric forms along with nickel. There were ideally eight metals employed in civilizations in antiquity: copper, gold, silver, iron, tin (which when alloyed with copper heralded the Bronze Age), zinc, lead, and mercury.

In this chapter we present a few examples of materials science and engineering and nanomaterials and nanotechnology represented in antiquity. These examples may seem to represent contemporary materials science and engineering concepts but also point up that they are historically pervasive. While ancient metallurgists and materials-related artisans and technologists may not have purposefully devised or designed a materials system, millennia of anecdotal evidence or observations provide compelling support. The examples begin with prospects for concrete casting of some core blocks in the pyramids rather than transporting them from quarries. Asbestos in antiquity illustrates possibly the most multifunctional material ever developed. Carbon nanotubes and related carbonaceous materials are also observed in antiquity along with applications of carbon block and soot derivatives in inks. Nanofibers also play a role in Mayan blue paintings, and colloidal silver and copper are shown to exhibit antibacterial and antifungal action over several millennia linking to contemporary applications involving silver nanoparticles in fiber weaves for socks as a simple example.

Following a brief overview or review of the history of electricity, electromagnetic waves and related phenomena are discussed in the context of Maxwell’s equations and the development of the so-called wave-optics equation which was the precursor to the Schrödinger equation as will be discussed in the chapter “A Brief Introduction to Quantum Mechanics.” The important issues to be illustrated in this chapter (chapter “Electromagnetic Fundamentals”) are the identification and evolution of fundamental materials properties: permittivity (ε), permeability (μ), index of refraction (n), conductivity and resistivity (σ and ρ), Ohm’s law, and the interrelationship of these materials properties as well as their measurement. This provides a context for materials properties historically and illustrates the role that Maxwell and his mathematical contributions have had in establishing quantum mechanics and its fundamental role in the behavior of materials, particularly nanomaterials.

It can be noted in Fig. 9 of chapter “Examples of Materials Science and Engineering in Antiquity” that color, represented by dyes and pigments (representing organic and inorganic materials, respectively), represents a sweeping application of materials fundamentals throughout human history. Even before Mayan blue (Fig. 9a of chapter “Examples of Materials Science and Engineering in Antiquity”), Egyptian blue and Chinese blue were discovered and developed as will be described in chapter “Serendipitous Nanotechnology in Antiquity.” In this chapter, color in glass (an amorphous structure) is discussed in contrast to color in crystalline materials. Color in crystals often indicates some features of electrical behavior: conductors versus semiconductors for transparent crystals. Structural color arising from the diffraction or interference of electromagnetic waves in the visible portion of the spectrum is described in the context of the so-called photonic crystals, providing a contrast between dye and pigment augmented absorption and electronic absorption by substitutional impurities in crystal structures, including the creation of color centers such as F-centers where an electron occupies a lattice site normally occupied by a negative ion or anion. Finally, the concept of negative index of refraction is briefly discussed as this relates to the so-called stealth materials or materials structures related to photonics or photonic crystal structures, the idea that creating intricate combinations of negative permeability and negative permittivity materials systems can exhibit invisibility.

Utilizing the wave-optics equation derived by Maxwell, E. Schröinger inserted the de Broglie relationship to derive a time-independent equation with an embedded wave-particle dualism and energy quantization. This chapter illustrates the Schrödinger equation and its application to electrons composing atoms, an equation of motion for an electron. Simple illustrations examine electron energy quantization in atoms as well as so-called “free” electrons in a volumetric confinement such as an electrical conductor. This brief introduction to quantum mechanical principles as these relate to atomic structure represented by electrons occupying quantized energy states serves as a precursor to understanding matter or materials at the atomic or ionic level.

Having illustrated symbolically and mathematically the wave-particle dualism applied to electrons in atoms in chapter “A Brief Introduction to Quantum Mechanics”, the symmetrical and asymmetrical behavior of quantized electron energy states in composing or characterizing atoms in the development and prediction of atomic chronology implicit in the periodic table of the elements is explored. The systematic or asystematic addition and subtraction of electrons from the quantum states or substates of atoms is discussed as this creates ions, both positive (cations) and negative (anions) valence states. This serves as a precursor to understanding change balance and atomic or ionic binding in the creation of solid or condensed matter to be discussed in chapter “Chemical Forces: Molecules” following.

The way atoms and ions are bound creates many of the properties of solid matter, including electrical, mechanical, and optical properties in particular. These chemical forces include ionic, covalent, metallic, and van der Waals binding, which are briefly but fundamentally described in this chapter.

Atoms can aggregate or cluster in simple arrangements without forming a unit cell. Silica tetrahedral (SiO₃) and other tetrahedral clusters, double tetrahedral containing five atoms, pyramids containing five atoms, as well as octahedral or double pyramids containing six atoms are among the more fundamental clusters. Eight atoms form a simple cubic unit cell, while nine characterize a body-centered cubic cell, becoming more complex with face-centered cubic unit cells which can be rendered as icosahedrons of 12 atoms or 13 atoms with a body-centered or cluster-centered atom. These form building blocks for nanoparticles which can continue to add layers or shells forming layered or shell structures, even nanotubes. Many clusters and shell structures are represented by the platonic solids and their regular-face, convex polyhedra. Carbon clusters such as fullerene-based multilayer or multiconcentric clusters form unique nanoparticles. Variances of these structures form aggregates representing carbon-based soots and related nanoclusters.

This chapter presents a short review or overview of point and space group symmetries and notations, and lattice systems and crystal structures and structure types.

Chapter “Lattice Directions and Planes, and Diffraction by Crystals” reviews Miller index notation for crystal planes and directions as a precursor to establishing simple principles for diffraction by crystals. Bragg’s law establishes diffraction geometry, while atomic scattering from specific atoms and structure factors determine the amplitudes of diffraction depending upon the atomic species and their crystal or lattice structure. The concept of the Ewald sphere and a reciprocal lattice as it relates to diffraction and diffraction amplitudes is also presented.

There are roughly 70 metallic and metallike elements with correspondingly 2,485 binary combinations or alloys. This chapter begins with a brief introduction followed by an overview of boron (Z = 5), a metalloid exhibiting unusual polymorphic structures, and a comparative overview of plutonium, another unusual polymorphic metal near the end of the periodic table (Z = 94). These two elements represent perhaps the most unusual ranges of polymorphic structures and properties in the periodic table.

It is remarkable that while the Platonic solids reflect 5-fold symmetry in both the icosahedra and the dodecahedron, crystal structures did not represent this symmetry until around 1983 when quasicrystals were discovered. This chapter presents a short overview of quasicrystals and 5-fold symmetric structures which have been described over the past three decades. Their relationship to the golden mean or the divine proportion is also briefly discussed. The concept of aperiodic or quasicrystals versus periodic or regular crystals is also described.

Electrovalent or ionic crystals, especially oxide crystals, exhibit interesting properties as a consequence of vacancy-based stoichiometry variations and related phenomena such as color center production described in chapter “Electromagnetic Color and Color in Materials”. In this chapter, metal oxides and sulfides are treated as AX and AX₂ compounds where X represents oxygen or sulfur, as well as perovskite and spinel structure oxides iABO₃ and AB₂O₄ structures, respectively. Oxide structures and crystal chemistry are particularly interesting because they are precursors to oxide superconductors which are treated in chapter “Structures and Properties of Oxide Superconductors” which follows.

Using chapter “Electrovalent Crystal Structures and Chemistry,” and especially the crystal chemistry of metal oxides as a platform, this chapter will examine basic structures and properties of oxide superconductors, particularly the so-called high-temperature (HT) superconductors. The two conditions for true superconductors, zero resistance (or resistivity), and a demonstrated Meissner effect (levitation of a magnet) are described, the latter as the exclusion of magnetic flux in the superconducting state. However, this chapter begins with a brief overview of more conventional metal or alloy superconductors in order to establish a relationship between these more conventional superconductors in contrast to oxide superconductors. It is pointed out that since the popular theory of superconductivity, the BCS theory, does not elucidate specific mechanisms which provide any predictability or avenues for guided exploration, future innovations may hinge on novel design strategies to improve existing systems.

In dealing with materials fundamentals, crystal imperfections or defects represent the most significant aspect of crystal structure or microstructure. Point defects or zero-dimensional imperfections have already been illustrated to determine the properties of extrinsic semiconductors (n-or-p type) (Fig. 8 of chapter “Electromagnetic Color and Color in Materials”), the color of crystals (Fig. 11 of chapter “Electromagnetic Color and Color in Materials”), and the superconductivity in oxide superconductors (Fig. 5 of chapter “Structures and Properties of Oxide Superconductors”). The role of line imperfections (dislocation lines) or one-dimensional defects was implicated in the enhancement of flux or vortex pinning and improved supercurrent density in superconductors, along with the implications of grain size or grain boundaries (planar defects or 2-dimensional defects) (Fig. 5 of chapter “Structures and Properties of Oxide Superconductors”). The formation of point defects and their agglomeration to create voids or 3-dimensional imperfections in the self-irradiation of plutonium and its alloys was also briefly described in Chapter “Structure of Metals and Alloys.” This chapter will summarize point defects as crystal imperfections and provide some additional and even unconventional examples of the role they play in determining material properties and performance, especially polycrystalline engineering materials, and with emphasis on metals and alloys.

Dislocation geometries, energetics, generation, interaction, dissociation, and multiplication are described as these relate to deformation and related properties in crystalline materials. Rotation-induced imperfections described as disclinations are also discussed.

Aspects already discussed of stacking faults on {111} planes in fcc crystals and the emission of dislocations from grain boundaries in fcc polycrystals discussed in chapter “Line Defects: Dislocations in Crystalline Materials” have shown the dissociation of dislocations forming varying extensions of stacking faults. In fcc materials, stacking faults are characterized by partial dislocations, and similar dislocation configurations are characteristic of twin boundaries on {111} planes. Grain boundaries can also be shown to be composed of dislocation arrays, and interfaces separating different crystal regimes (interphase boundaries) as well as the accommodation of misfit and misfit strains between different phases can also be viewed as misfit dislocation arrays. In this chapter, these planar arrays are discussed in terms of their fundamental structures or microstructures and the corresponding or associated interfacial free energies. In some cases, where applicable, disclination concepts are also applied.

Second-phase (solid-state) inclusions such as precipitates and dispersed phase particles are discussed briefly along with other clusters, voids, and bubbles, such as those which can arise by radiation effects. Other types of defects involving carbon aggregates forming various graphite inclusions are discussed in later chapters dealing with such features in iron and related carbides in steels.

Crystal imperfections affect the stress–strain diagram in a number of ways, often increasing the tensile strength as the density of imperfections increase or their geometry creates partitioning of the crystal structure. Work hardening and strain hardening are also dependent upon imperfections. Hardness and yield stress for many metals and alloys are related by a simple relationship, σ_y = H/3, while the yield stress is often expressed by a Hall–Petch-type relationship, dependent upon the reciprocal square root of the grain size. These issues are presented in this chapter.

Properties of single crystals in particular often differ with different crystal directions as a consequence of constraints imposed by atomic packing and arrangements as well as the placement of substitutional impurities or other defects. For polycrystalline materials with more random orientations of crystal grains, these properties usually average out, and measurements represent the same values in any direction. Such multi-directional or multi-vector properties are intrinsically connected, and these connected properties are represented by tensors or arrays of vectors represented crystallographically (as crystal directions). These tensors or vector arrays have a rank characteristic of their complexity, which manifests itself in the scalar coefficients characteristic of a property. Such notations are conveniently represented by matrix algebra which in the case of tensor properties represents a powerful mathematical tool to study or predict properties of crystals, particularly crystal orientations.

A novel matrix can execute a transformation from one set of Cartesian axes to another by systematic rotations through angles α, β, and γ or Euler angles: ϕ, θ, and ψ. In effect, this allows tensor coefficients representing a crystal property measured in a specific orientation to be mathematically transformed into any other orientation, thereby eliminating the necessity to remeasure the property coefficients.

In this short chapter, the ability to characterize textured polycrystalline materials using an averaging technique for elastic moduli is briefly described.

One of the most notable applications of single-crystal orientation to control elastic modulus and associated mechanical properties is vested in the production and use of directionally grown turbine blades from superalloy compositions. This chapter provides examples of this phenomenon from both a historical and contemporary perspective. These examples epitomize the development and control of microstructure to achieve specific properties and performance based on processing schedules and selective routines.

Composite materials in the simplest case are composed of some phase (a second phase) included in a matrix. The properties of the matrix are altered depending upon the volume fraction of this phase, as well as its geometry and orientation relative to an applied stress.

Examples of eutectic fibers formed in a metal matrix by directional solidification are presented.

Natural or biological composites are reviewed with a number of appropriate examples: human bone and teeth, wood, pearls, mother of pearl, and related shell structures.

Some examples of man-made composites are presented in this chapter, sporting goods, wind turbine blades, aircraft structures, automobile structures, and home construction, which can provide an example of a broad range of composite structures in everyday life.

Proteins are the building blocks of biological materials, and fundamental to these building blocks are 20 amino acids. The evolution of RNA and DNA is also fundamental to living materials and to primary life forms such as viruses and bacteria. This chapter begins with a historical perspective involving DNA. The structures and functions of virus and bacteria are then described in relation to both RNA and DNA. The catalytic role of bacteria is illustrated in specific examples involving the leaching of copper from porphyry copper waste.

Keratin, complimentary fibrous proteins to collagen, is represented by two classes or molecular structures, alpha (α) and beta (β), having similar amino acid sequences and biological functions. Prominent examples include wool and silk fibers, avian materials, biological armor (including varieties of scales and shells), and exoskeleton composites.

A comparison of materials properties for natural (biological) materials and engineering materials is accomplished by reproducing Ashby plots or diagrams: Young’s modulus versus density, toughness, fracture toughness, and strength, along with specific modulus (or stiffness) and specific strength.

Nature provides a vast array of biological materials and materials systems which have inspired innovations in novel applications and in new materials developments. These have included natural (animal) armor, flight systems inspired of course by birds, fasteners and attachments, and an array of photonic structures. Microbes producing methane and keratin–rubber composites pose novel systems along with branched biological systems which include trees, lungs, circulatory structures, and the like, which are governed by fractal geometry. The concept of protein factories is revisited in this chapter where virus and bacterial systems can act as protein factories to produce a complex array of drugs and related organic materials and functional systems.

Following a brief description and review of hydroxyapatite-reinforced polymeric and related systems for bone replacement strategies, the use of biodegradable metals and polymers is discussed as temporary bone support systems to allow bone regrowth and healing, including screws. The use of these materials for a variety of nonpermanent stents is described in the context of novel stent structures, including shape memory materials and the fabrication of auxetic structures to achieve stent shapes.

In contrast to biodegradable implant materials and appliances, many implant metals and alloys are permanent: teeth, cranial-facial, orthopedic appliances for knee and hip replacement, rods, screws, etc. The design and fabrication of biomechanically compatible orthopedic (bone) implants will be discussed, especially with regard to reducing or eliminating stress shielding through controlled density and porosity to reduce stiffness (or Young’s modulus).

This chapter describes concepts of tissue engineering and scaffold fabrication and function as these relate to 3D cell and tissue growth and function which may lead to complex organ manufacture. Scaffold materials are described, including natural (biological) scaffold materials such as collagen, chitosan, and silk as well as metals and polymers.

Photolithography as it relates to lithography fundamentals is described and applied to the lithography process utilized in producing integrated circuits (ICs) and layered electronic device structures. These structures have some thickness or layering restrictions but are nonetheless layer-manufactured structures on an electronic landscape, usually a silicon wafer substrate.

Aside from photolithography to produce electronic integrated circuits and device system, 3D printing can allow these circuits to be directly printed using novel ink compositions or nanoparticles and integrated printer heads. Printed electronics in its various forms and innovations can revolutionize electronics manufacturing. This chapter outlines contemporary developments and future innovations in 3D electronics printing.

Using living cells in place of nanoparticles of other materials in an ink matrix, it is conceptually possible to print 3D organs. Using ink jet arrays controlled by CAD software, vascular cells can introduce appropriate vascularization or cylindrical vessels to allow blood flow. The successful integration of these functions into tissue engineering can allow for human organ printing. This chapter describes contemporary innovations in tissue engineering and 3D organ printing.

Rapid prototyping or solid freeform fabrication fundamentals and processes are described in this chapter. These include concepts of layer printing to produce 3D objects by fused deposition modeling and selective laser melting. Stereolithography as it is applied to fabrication by additive manufacturing forms the basis for these technologies for materials processing.

The fabrication of integrated circuits by lithography technologies is a limited dimension 3D printing concept which can be expanded by building larger dimension structures in which mechanical-electromechanical and related device structures can be embedded. These involve hybrid, interconnected, layered, functional electronics along with power sources and other device structures fabricated by either some form of 3D printing or other novel placement.

Novel structure printing is illustrated through the fabrication of negative Poisson’s ratio or auxetic structures and negative index of retraction structures or cloaking structures and stealth configurations.

Laser and electron beam melting technologies are presented in this chapter along with a range of examples of metal and alloy products fabricated by these technologies. Laser beam melting or selective laser melting (SLM) in contrast to electron beam melting (EBM) processes metal or alloy powders in an inert atmosphere as opposed to a vacuum. Complex melting and solidification of the layers invokes new directional solidification metallurgy.

Many aspects of materials science and engineering structures are conveniently and effectively rendered by 3D imaging and related or associated properties. As these structures evolve systematically with time, such systematic renderings are characterized as 4D. Examples of these concepts are presented in this chapter.

Aspects of 3D printing and additive or layer manufacturing can be treated as modular manufacturing or modular components of manufacturing in the contemporary sense. Such modular manufacturing involves specialized product design and fabrication or product customization. These processes incorporate new materials along with new design strategies to achieve new performance features.

Like Mayan blue, involving indigo dye trapped in palygorskite nanofibers (chapter “Examples of Materials Science and Engineering in Antiquity”), Egyptian blue and Chinese (or Han) blue and purple represent nano-pigments with rich roles in Egyptian and Chinese antiquity. Kaolin nanosilicate sheets also contributed to Chinese porcelain in antiquity. While these examples represent nano-particulate materials, the role of carbon and carbide nanoparticles in bulk iron matrices and related accidental nanotechnology in antiquity, manifested in the development of Damascus and related patterned swords and daggers, represents the application of the materials science and engineering paradigm in antiquity: structure–properties–processing–performance interactions and relationships. These issues are presented in this chapter which, along with other developments in the many parts of this handbook, attest to the evolution of nanomaterials and nanotechnologies over many millennia.

Nanomaterials are characterized by free nanoparticles of various nanodimensions: 1D, 2D, or 3D in classifying nanosheets such as graphene, 2D needles or filaments, and 3D particles, including aggregates. These geometries can be included in a contiguous solid as dispersed or precipitated phases or contiguous nanocrystals forming nanograin solids. These nanomaterials structures are generally observed directly using imaging techniques such as SEM, TEM, FIM, STM, or AFM, which are principal characterization tools. The distinctive features of nanomaterials especially nanocrystalline forms are the high surface-to-volume ratio and the dominant role of interfacial (and surface) energy. Nanostructured materials might be thought of as the interfacial state. These issues of characterization and classification of nanomaterials and nanostructures as well as interfacial phenomena in nanomaterials are treated in this chapter.

Nanoparticles and nanoparticle aggregates are produced as colloids and related nanocrystals by sol–gel and wet chemical synthesis as well as a variety of vapor, spray, and plasma processes, including flames. Vapor-phase material can be condensed or deposited on variously heated or cooled substrates, even crystalline substrates where films, islands, and quantum dots can be grown. The role of catalysts in promoting reactions is described. Sputter deposition and other physical vapor deposition (PVD) processes are discussed, including arc evaporation. Chemical vapor deposition (CVD), including reaction product production and collection, is presented. Molecular beam epitaxy (MBE) and atomic layer deposition are described. Collected nanopowders can be statically or dynamically consolidated to form bulk billets. Mechanical alloying and mechanochemical synthesis of nanomaterials are discussed along with electrodeposition, friction-stir processing (FSP), and equal-channel angular processing (ECAP) or extrusion as these apply to severe plastic deformation (SPD) processes to produce nanocrystalline bulk solids.

Properties, especially mechanical properties of nanocrystalline metals and alloys are described along with other behavior related to nanocrystal structures which create quantum confinement at dimensions <6 nm. The transition from the larger length scales in the characterization of engineering polycrystalline materials through the nanoregime to the amorphous state is discussed in relation to polycrystal grain size D in relation to the grain boundary or grain boundary phase width, Δt: D > > Δt (coarse-grain, micron regime), D > Δt (nanograin regime), and D ∼ Δt (amorphous phase regime). Over these length scales, a Hall–Petch relationship is shown to be generally applicable up to a plateau which converges to the amorphous state in common metals such as Cu (fcc) and Fe (bcc). Deformation mechanisms also change from slip (or dislocation generation, glide, and pileup) to grain boundary sliding, to mixtures of these. In nanocrystalline metals, stacking-fault and twin boundary free energies are suppressed and partial dislocation emission and associated twin formation can occur. Deformation in small samples can favor surface sources in contrast to grain boundary dislocation sources depending upon grain boundary structure and the number of grains in the specimen thickness. There is a critical specimen thickness, Δ-to-grain size, D, ratio for nanocrystalline metals similar to engineering test samples having coarse-grain sizes, where Δ/D > 8.

After more than 2,000 years, chrysotile asbestos continues to pose a health risk in spite of its roughly 3,000 or more applications. Contemporary nanomaterials, especially nanoparticulate materials, are produced in millions of metric tons to create products ranging from cosmetics to composites. While many health concerns for contemporary nanomaterials are historically grounded in documented episodes involving chronic respiratory and digestive health issues, including cancers, there is limited associations with many nanoparticulate materials, although cytotoxic assays performed on a variety of nanoparticles and nanoparticle aggregates using human respiratory or lung cell models almost invariably demonstrate some degree of proinflammatory response, and more extensive concerns.

Fundamentals of plane shock wave loading are described in relation to spherical shock loading which is the characteristic of ballistic and hypervelocity impact and penetration of materials, particularly metals and alloys. The evolution of microstructure with shock pressure and especially shock-wave-induced twinning and the role of stacking-fault free energy in fcc metals and alloys are discussed along with critical shock pressure for twinning and the twinning-microband microstructure transition for oblique shock loading and spherical shock associated with impact crater production and subsequent penetration of targets. This includes the role played by dynamic recrystallization (DRX) in solid-state flow which facilitates crater formation. The penetration of rods in contrast to spherical projectiles in thick targets and plug formation and ejection by adiabatic shear band formation is described along with the fundamental, dynamic recrystallization (DRX) microstructure which characterizes such shear bands. Shaped charge and explosively formed penetrator structures and performance as penetrators in thick target materials are described. The role of DRX in these processes is also discussed. Finally, rail erosion characteristic of DRX in railgun operation is illustrated briefly as a related example of extreme plastic deformation along with the concept of explosively driven magnetic flux generation.

The use of explosives to manipulate and process materials epitomizes extreme deformation processing and provides additional evidence for the role played by dynamic recrystallization or related solid-state flow induced by strong shock waves. The explosive bonding or cladding of large areas of planar metal or alloy laminates by variations of interlocking weld waves or shallow DRX microstructures often resembles rim structures characteristic of ballistic impact craters and penetration channels. Novel forming by explosive charges in water creating hydroforming environments is presented. The explosive consolidation of powder materials can provide novel cylindrical precursors for more conventional materials processing or new materials fabrication not tenable by conventional materials processing routes.

Friction-stir welding (FSW) creates solid-state flow in butted metals and alloys which are mixed in the resulting weld zone. A rotating tool stirs one material into the other by the creation of DRX grains which result by extreme deformation, creating adiabatic heating at the tool/material interface. The process bonds or joins same or dissimilar metals and alloys and is not limited by thermodynamic considerations in conventional fusion welds. Unlike fusion welding, the tool is not purposely consumed. Friction-stir processing (FSP) uses a rotating tool as in FSW with some dimensional restrictions to allow controlled surface depths to be altered, microstructural alteration. Continuous tool traverse and overlapping stir regimes produce a modified or remodeled surface region or thickness where second phase as well as other microstructures can be homogeneously distributed. Bubbles or voids can be eliminated in cast materials. Properties and performance such as superplasticity can be affected by creating DRX nanograins.

In this chapter, extreme deformation phenomenon is examined in several key areas of metal working, material working science, and technology: sliding and sliding friction, grinding and machining as classical examples of subtractive manufacturing, and extrusion and wire drawing, which can involve high strains and high-strain rates, producing uniform DRX grain structures. Especially notable in sliding and grinding is the deformation zone which extends from 10 10 μm mu;m to several hundred microns, sometimes in lamellar DRX grain layers. Drawn wires, especially pearlitic steel wires, can have yield strengths in excess of 5 GPa and represent the limits of extreme deformation or severe deformation processing.

Breaking bonds of any type is the fundamental precursor to crack nucleation. Catastrophic brittle or cleavage fracture produces essentially only cleavage steps, while variations in ductile fracture produce different sizes of cup-cone (ductile-dimple) fracture surface structures. Steels in particular are prone to low-temperature ductile – brittle transitions while variations or cycles in stress produce fatigue structures and behavior. Fracture induced by creep, fatigue, creep-fatigue, impact, as well as ductile/brittle fracture modes are illustrated. Crack nucleation, coalescence, and growth are described in detail along with crack initiation sites corresponding to the various fracture modes. Complex interactions of fracture modes in various stress, temperature, and chemical environments are illustrated.

Degradation and failure in chemical and electrochemical environments are described and illustrated in the context of corrosion as it relates to oxidation and reduction chemistry, electrode potentials of metals, galvanic corrosion, stress corrosion, and hydrogen embrittlement. Electropositive metal precipitation and its role in crevice and pitting corrosion in copper-containing aluminum alloys are described. Corrosion in atmospheric acidic environments especially by steels and cathodic protection of buried steel pipelines and other vessels is discussed. Fundamentals of embrittlement and especially related diffusional issues, grain boundary segregation, and crack nucleation by gas (hydrogen embrittlement)-, fluid (liquid metal embrittlement)-, and solid-phase production such as metal hybrids acting as stress-related crack nucleation sites are illustrated.

Extreme environments associated with turbine operation in power generation and turbines and turbine components as well as systems and components of nuclear reactors are discussed in the context of extremes in temperature, stress and stress variations, radiation, extreme chemical environments, and their complex interactions. Other energy production-related environments in oil and gas production and general chemical and high-pressure environments are presented. Special attention is devoted to space environments, especially low Earth orbit (LEO) where micrometeoroid and space debris impacts, atomic oxygen effects, radiation and thermal cycling, and related and interactive degradation features pose concerns and important design strategies.

Although there are many complex, integrated, and interactive systems such as automobiles, aircraft, electrical generation, and distribution systems, integrated circuits and especially very-large-scale integrated (VLSI) and ultra-large-scale integrated (ULSI) device systems demonstrate a length-scale system, in contrast, which is unique because of its continuous evolution. This evolution, driven for roughly four decades by Moore’s law, involves feature sizes driven to the low-nanometer-size regime and transistor densities exceeding billions/cm2. Electromigration is discussed in the context of these phenomena along with related circuit failure phenomena as these relate to product reliability.

Magnetic physical principles and properties are reviewed to establish a basis for their application. Classifications of magnetic materials are presented as these apply to the role of magnetic dipole moments or magnetic polarization as it applies to magnetic memory and recording innovations and applications. The role of magnetic induction in power isolation and conversion is described, and functional and multifunctional magnetic materials innovations are discussed in terms of properties which include magnetoresistance, giant magnetoresistance, magnetostriction and magnetic shape-memory effects, magnetocaloric effect as it applies to magnetic refrigeration, and temperature effects on magnetic materials properties and performance.

This chapter begins with solid-state drives and flash memory materials and device structures. Thin-film transistor (TFT) innovations are described. TFT-LCD are discussed along with photodiode and photovoltaic materials and structures, including LED display concepts. Photovoltaic materials and devices – solar cells and multijunction solar cell arrays – are described along with dye-sensitized solar cells. Thermionic materials and devices are described along with innovations in hybrid photovoltaic/thermoelectric systems and devices. Battery technologies and energy storage materials, including thin-film battery concepts which include Li-ion and Li–air batteries, are described. Supercapacitors and supercapacitor energy storage materials and device innovations are discussed followed by sensor materials and device concepts and fundamentals.

In contrast to conventional or even natural materials which derive their electromagnetic characteristics from the properties of the composing atoms and molecules, photonic crystals and related metamaterials allow for the design of meta-atoms or superatoms as well as artificial structures which allow for new optical and electromagnetic functionalities. These features are briefly presented in this chapter beginning with tunable photonic crystal structures to fabricate an array of inks activated by electric and magnetic fields as well as external stresses. The manipulation of permittivity in dielectric materials and permeability, especially in developing composite structures with negative index of refraction, is discussed in the context of fabrication permitted by 3D printing and related technologies.

Computer simulation is described as a comprehensive method for studying materials and materials systems. Computational methods used on different length and time scales for the simulation of materials structures and behavior are described along with process features involved in the implementation, verification, and validation of computer simulations. Computer simulation in the context of integrated computational materials engineering as this relates to the materials genome initiative concept for materials innovation and advanced materials development and deployment is discussed.

As the culmination of this handbook, this chapter represents more than 12 orders of magnitude in length scales (in meters) and more than 25 orders of magnitude in timescales (in seconds) representing materials structures, properties, processing and performance issues, and phenomena as these are related to computer simulations and especially example applications. These illustrate atomistic simulations and simulations applied to large engineering structures such as the Francis hydraulic turbine runner blade castings for the Three Gorges Dam (China), weighing over 400 t. These examples also illustrate the concepts of verification and validation essential in successfully applying computational materials science and engineering to the widest spectrum of materials and materials systems.