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A Quantum Approach to Alloy Design: An Exploration of Material Design and Development Based Upon Alloy Design Theory and Atomization Energy Method
A Quantum Approach to Alloy Design: An Exploration of Material Design and Development Based Upon Alloy Design Theory and Atomization Energy Method
A Quantum Approach to Alloy Design: An Exploration of Material Design and Development Based Upon Alloy Design Theory and Atomization Energy Method
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A Quantum Approach to Alloy Design: An Exploration of Material Design and Development Based Upon Alloy Design Theory and Atomization Energy Method

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A Quantum Approach to Alloy Design: An Exploration of Material Design and Development Based Upon Alloy Design Theory and Atomization Energy Method presents a molecular orbital approach to alloy design that is based on electronic structure calculations using the DV-X alpha cluster method and new alloying parameters obtained from these calculations. Topics discussed include alloy properties, such as corrosion resistance, shape memory effect and super-elasticity that are treated by using alloying parameters in biomedical titanium alloys. This book covers various topics of not only metals and alloys, but also metal oxides, hydrides and even hydrocarbons.

In addition, important alloy properties, such as strength, corrosion resistance, hydrogen storage and catalysis are treated in view of electron theory.

  • Presents alloy design theory and the atomization-energy method and its use for the fundamental understanding of materials and materials design and development
  • Discusses, for the first time, the atomization-energy analysis of the local lattice strains introduced around alloying elements in metals
  • Illustrates a simplified approach to predict the structure and phases stability of new alloys/materials
LanguageEnglish
Release dateNov 16, 2018
ISBN9780128147078
A Quantum Approach to Alloy Design: An Exploration of Material Design and Development Based Upon Alloy Design Theory and Atomization Energy Method
Author

Masahiko Morinaga

Masahiko Morinaga is a fellow with the Toyota Physical and Chemical Research Institute, as well as an Emeritus Professor with Nagoya University where prior to his retirement he served as the department head of the material science and engineering department of Nagoya University. Before coming to Nagoya University, Professor Morinaga was a professor with the Toyohashi (Japan) University of Technology. From 2004-2010 Dr. Morinaga was chairman of the 176th Committee on Process Created Materials Function for the Japan Society for the Promotion of Science, Tokyo. He is a member of the Japan Institute Metals, an organization where he has held a number of roles including a journal editorial member since 1995; vice president 2005-2006, and president from 2008-2009. Dr. Morinaga was also president from 2004 - 2010 of the Discrete Variational-Xalpha Society Japan. Dr. Morinaga is the co-author of the publications Quantum Chemistry of Metallic Materials and Quantum Alloy Design and Hydrogen Storage Alloys, as well as numerous journal articles.

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    A Quantum Approach to Alloy Design - Masahiko Morinaga

    India

    Preface

    Masahiko Morinaga, Nagoya, Japan

    More than 35 years have passed since I started the research of alloy design at the beginning of the 1980s. During this period much progress has been made in the quantum approach to alloy design. For a long time I have been planning to write a book on this subject, because I have felt that it is my primary duty to present this quantum approach in as straightforward a way as possible.

    Complex alloy problems are treatable with the aid of the molecular orbital calculations of electronic structures of alloys. In view of the electron bonding, it is no longer needed to distinguish between iron and steels and nonferrous alloys, and even the current classification into metals, semiconductors, ceramics, and polymers is not necessarily needed. Therefore, this book covers various topics of not only metals and alloys, but also metal oxides, hydrides, and even hydrocarbons. Besides the phase stability of alloys, the physical and chemical properties such as strength, corrosion resistance, hydrogen storage, and catalysis are treated with the aid of molecular orbital theory. Recently, an atomization energy method has been developed to express a role of each constituent atom in the chemical bond formation of the material in an energy scale. Thus, the theory for alloy design is still in progress. New challenges and trials are important for the further advancement of the theory.

    The opportunity and incentive to prepare this book have been provided by Professor Ma Qian of Royal Melbourne Institute of Technology in Australia and Professor Hirohiko Adachi of Kyoto University in Japan. Professor H. Adachi also helped me in various aspects, so that the present work could not be completed without his collaboration. I express my gratitude to the late Professor N. Yukawa of Toyohashi University of Technology, as he introduced me to the field of alloy design. Professor H. Nakai of Waseda University guided me in the energy density analysis that he developed. I am grateful to Professor Y. Murata, Professor H. Yukawa, Professor M. Yoshino, all of Nagoya University; Professor S. Kamado of Nagaoka University of Technology; Professor H. Ezaki of National Institute of Technology, Suzuka College; and Professor M. Morishita of University of Hyogo for their collaboration with me on the study for alloy design. Finally my wife joins me in expressing our appreciation to the graduate students and young men who worked with me at both Toyohashi University of Technology and Nagoya University.

    September 2018

    1

    Introduction

    Abstract

    This book treats a quantum approach to alloy design developed on the basis of a molecular orbital method. In view of the electron bonding, it is no longer needed to distinguish between iron and steels and nonferrous alloys, and even the current classification into metals, semiconductors, ceramics and polymers is not necessarily required. The present quantum approach is useful not only for the fundamental understanding of alloys, but also for alloy design without relying on trial-and-error experiments.

    In this introduction, first, characteristics of alloy properties are explained, while touching on several current topics of structural alloys. Second, previous electronic approaches to metals and alloys are reviewed concisely to understand the present status of electron theory. Information on the electronic state appears to be very limited in solute-rich alloys as compared with pure metals or impurity-containing metals. Third, a series of investigations of wide scope is outlined briefly to survey a new approach to alloy design.

    Keywords

    Alloy design; structural alloy; electronic structure; molecular orbital calculation; atomization energy; working processing

    1.1 Alloy Properties

    Superior alloy has a beautiful microstructure. For example, the micrograph shown in Fig. 1-1 is taken from a heat resistant single-crystal Ni-based superalloy for use of the blades in jet engines and gas turbines. The cuboidal γ′ (Ni3Al) precipitates with the submicrometer size are arranged three-dimensionally and periodically in the γ (fcc Ni) matrix. The volume fraction of the γ′ phase is as high as 60%–65%. This beautiful microstructure is, however, no longer sustained, if any harmful phase (i.e., the σ phase) precipitates in the γ matrix, which deteriorates mechanical properties of alloys. Therefore, it is strongly needed to control the alloy composition to be free from the σ-phase precipitation. For this purpose, the phase computation (PHACOMP) method was developed in 1964. Since then, we have used the term alloy design.

    Figure 1-1 The γ′ phase precipitated in a single crystal Ni-based superalloy. The γ phase exists in the interface region between adjacent cubes of the γ′ phase. By courtesy of Dr. T. Ohno (Hitachi Metals Ltd.). The micrograph used in the cover of this book is the same as this picture, that is taken from Hitachi Metals Technical Review, vol. 13, 1997.

    Needless to say, mechanical strength is one of the most important properties of the structural alloys. Plastic deformation takes place readily in most alloys, and both the size and the shape change easily by either cold or hot working. This is a great advantage of metals and alloys over other materials. Even new functions could emerge in some alloy by cold working. For example, gum metals (Ti alloys, e.g., Ti-9%Nb-3%V-6%Zr-1.5%O and Ti-23%Nb-0.7%Ta-2%Zr-1.2%O (mol%)) have been developed recently [1]. A typical stress–strain curve is shown in Fig. 1-2A. By applying the 90% cold working to this alloy, nonlinear elastic deformation takes place as in gum material. Also, as shown in Fig. 1-2B, in case gum metal is 90% cold worked, elastic constant and linear thermal expansion coefficient keep constant in the temperature range of −200°C (73 K) to 400°C (673 K). Such unique properties are called the elinvar and the invar properties, respectively.

    Figure 1-2 (A) Stress vs. strain curves for gum metals (Ti alloys) and (B) elinvar and invar properties emerge in them by cold working. By courtesy of Dr. T. Saito (Toyota Physical and Chemical Reserch Institute).

    Recently, there have been several trials to get superior mechanical properties by introducing severe plastic deformation to metals and alloys by using special processes such as equal channel angular processing (ECAP), high pressure torsion (HPT), and accumulative roll bonding (ARB) [2–4]. No size or shape changes are produced by these processes, but instead ultrafine grained (UFG) materials with 200–20 nm in grain sizes are produced. For example, very high strength Al and Fe metals are developed by the ARB process [5,6].

    Besides the mechanical properties, for example, oxidation resistance is required for high-temperature alloys such as Ni-based, Co-based, and Fe-based alloys. If these alloys are exposed to air at high temperatures, metal oxide of Cr2O3, Al2O3, or SiO2 is formed depending on the temperature. Such oxides formed on the surface protect the alloy from further oxidation.

    To understand the oxidation process, it is important to know the defect structure in the oxide. For example, as shown in Fig. 1-3A, the formation energies of lattice defects are calculated in SiO2 and Al2O3 [7]. The lattice defect in the oxide is assumed here to be either the Schottky defect, or the cation or anion Frenkel defect. The Schottky defect is a pair of anion and cation vacancies, and the cation (or anion) Frenkel defect consists of a vacancy and an interstitial of cation (or anion) [8]. Judging from the formation energies listed in Fig. 1-3A, the anion (O) Frenkel defect is dominant in SiO2, and the cation (Al) Frenkel defect is dominant in Al2O3 as illustrated in Fig. 1-3B. Each lattice defect assists ionic diffusion in the oxide at high temperature. As a result, as shown in Fig. 1-3C, the SiO2 layer is formed on the Si surface by inner diffusion of anion (O), whereas the Al2O3 layer is formed on the Al surface by outer diffusion of cation (Al), in agreement with experiments [7]. Thus, to reduce the oxidation rate at high temperature, we may need to control the defect structure in the oxides in some way, for example, by alloying. Thus, we need to learn metal oxides as well as alloys to understand a whole feature of the oxidation behavior in a fundamental manner. In other words, wide knowledge and information are necessary to understand the alloy property.

    Figure 1-3 Formation of oxide layer formed on metal surface. (A) Calculated formation energies of lattice defects, (B) lattice defects in SiO2 and Al2O3, and (C) ionic diffusion mechanism during oxidation at high temperature.

    In particular, in the case of structural alloys it is strongly requested to have an excellent combination of various properties such as mechanical properties (e.g., tensile strength, creep strength), corrosion resistance, and oxidation resistance. However, it is rather difficult to predict these alloy properties in a reasonable way. In this book, several trials are presented to resolve a part of such difficulties using electron theory, since most of physical and chemical properties of alloys are related closely to the electronic states.

    In the next section, previous electronic approaches will be reviewed briefly to deepen our understanding of electron theory for metals and alloys.

    1.2 Electronic Approaches to Metals and Alloys

    Pure metals have been investigated extensively from both experiments and theories, and valuable information has been accumulated on the electronic states in pure metals. For example, the Fermi surfaces are determined for a variety of metals [9]. The Fermi surface is spherical in alkali metals such as Na and K, in which a free electron model is satisfied. A nearly free electron model is satisfied for the lightweight metals such as Al and Mg, in which the s and p electrons spread over the crystal space. On the other hand, for transition metals the d electrons are localized around the atom site and the localized d electrons cause the ferromagnetism in Fe group metals. For example, the atomic moment is about 2.2 μB for Fe, 1.7 μB for Co, and 0.6 μB for Ni, where μB is a Bohr magneton.

    Also, the impurity state in metals has been investigated. For example, the magnetic impurity (e.g., Fe, Cr, Mn) in metals (e.g., Au, Ag, Cu) causes a residual resistance minimum at low temperature that is known as the Kondo effect [10]. Also, the Friedel oscillation appears in either the charge distribution or the spin polarization around an impurity atom embedded in metal [10].

    By contrast, electronic information is very limited in the solute-rich alloys. In many cases alloy properties have been analyzed using the electrons-per-atom ratio, e/a. This approach seems natural, since e/a is the number of outer electrons to form the chemical bonds in alloys and compounds. For example, there are the so-called electron compounds proposed by Hume-Rothery. The crystal structures of the intermetallic compounds change depending on the specific e/a values [10]. A rigid band model has been used together with the e/a value to represent the electronic structures of transition metal–based alloys. For example, the atomic moments for binary alloys consisting of the iron group elements are plotted against the group number (i.e., e/a value) of the periodic table of elements; this is well known as the Slater–Pauling curve [11,12].

    Even in the field of alloy design, the electron vacancy number in the d band, Nv, which is expressed approximately as Nv=10.66-(e/a), is used in the PHACOMP method as explained earlier [13]. PHACOMP is a method to predict the formation of harmful and brittle phases (e.g., the σ phase) in nickel-based superalloys. Besides the e/a, the electronegativity and the atomic radius have been employed for treating the solid solubility problem of alloys [14,15]. These parameters are assigned to pure metals and any alloying effects are not involved in them.

    To the author’s limited knowledge, we do not have any alloying parameters despite a long history of metallurgy and metal science. Therefore, for alloy design it is first necessary to determine alloying parameters of elements under the same chemical circumstance as in real alloy. The molecular orbital method is very convenient to calculate local electronic structures around alloying elements in alloy. Thus, a theory for alloy design is constructed on the basis of the molecular orbital calculations.

    The scope and outline of each chapter in this book will be given briefly in the next section.

    1.3 Scope and Outline of Each Chapter

    This book consists of 12 chapters.

    Chapter 1, Introduction

    The necessity of developing a theory for alloy design is explained concisely.

    Chapter 2, Theory for Alloy Design

    In case of transition metal alloys, two alloying parameters are determined for various alloying transition metals by using the DV-Xα molecular orbital method. One parameter is the d orbital energy level, Md, of alloying element, M, in a base metal, X, and another parameter is the bond order, Bo, between M and X atoms. A theory for alloy design is developed with these alloying parameters. The physical and chemical meanings of alloying parameters are explained together with the DV-Xα molecular orbital method, which is a first-principle calculation method.

    Chapter 3, Nickel Alloys

    Alloying parameters, Md and Bo, relevant to nickel alloys are determined and applied to the phase stability problem of the alloys. For example, new PHACOMP is developed to solve various contradictions inherent in the PHACOMP. Also, a single crystal Ni-based superalloy is developed following the theory.

    Chapter 4, Iron Alloys

    Two alloying parameters, Md and Boare the compositional averages of the Bo and the Md parameters in the alloy, respectively. Heat-resistant high-Cr ferritic steel for use of rotors in power plants is developed following the theory.

    Chapter 5, Titanium Alloys

    Alloying parameters, Bo and Md, relevant to titanium alloy are determined and used for predicting phase stability and alloy properties. For example, it is shown that any titanium alloys can be classified into either the α, or α+β, or β type from the alloy composition by using the alloying parameters. Here, α is the hcp-Ti phase and β is the bcc-Ti phase. A concrete way of alloy design is explained using an example of high strength β-type Ti alloys. The corrosion resistance is also treated along this approach. Recent progress in this approach is presented to design titanium alloys for biomedical applications.

    Chapter 6, Aluminum alloys and Magnesium Alloys

    Not only the transition metal–based alloys, but also simple metal–based alloys such as aluminum alloys and magnesium alloys are treated theoretically. Big data of the mechanical properties are put in order using a new alloying parameter (s orbital energy level, Mk). Also, the mechanical properties are treated in an energy scale for the first time.

    Chapter 7, Hydrogen Overpotential of Alloys and Intermetallic Compounds

    A new concept is presented for understanding the catalytic activity for the hydrogen evolution reaction on transition metal–based binary alloys and also on intermetallic compounds of TiAl, FeAl, and NiAl containing alloying 3d transition elements.

    Chapter 8, Crystal Structural Maps for Intermetallic Compounds

    New crystal structure maps are presented for aluminide, silicide, and some transition metal compounds. They are constructed using Bo and Md parameters. There is a clear separation of the crystal structures on the BoMd structure maps. In addition, the brittleness of TiAl compound is discussed in view of the chemical bond between atoms in compounds.

    Chapter 9, A Universal Relation in Electron Density Distribution in Materials

    There is a universal relation between electron density minima and atomic or ionic radii. This is discovered from a series of calculations of electronic structures in matter over 130 species, including gases, water, and solids.

    Chapter 10, Atomization Energy Approach to Alloys and Metal Compounds

    Another electronic approach is newly developed to express the chemical bond between atoms in materials in an energy scale. The atomization energy is calculated for every constituent atom in the material. For example, metal hydrides, complex hydrides, and hydrocarbons can be located on the atomization energy diagram, despite the significant differences in the nature of the chemical bond among them. One of the applications of this approach is the catalyst design. For example, the catalytic activities of metal oxides (e.g., Nb2O5) are evaluated quantitatively on the dehydrogenation reaction of magnesium hydride (MgH2), MgH2→Mg + H2.

    Chapter 11, Local Lattice Strains Around Alloying Elements in Metals

    Local strains are introduced to the lattice around the solute atom due to the size mismatch between solute and solvent atoms in alloy. Local lattice strains around various alloying elements, M, are calculated in a systematic way in Mg, Ti, and Fe metals using the pseudopotential method. Such local lattice strains are found to influence the martensitic transformation start temperature (Ms) in both titanium alloys and iron alloys.

    Chapter 12, Conclusions

    A theory for alloy design is summarized, and a perspective on the alloy design is presented.

    Thus, this book covers various topics of not only alloys and intermetallic compounds, but also metal oxides, hydrides, and even hydrocarbons. The important properties such as phase stability, mechanical strength, corrosion resistance, hydrogen storage, and catalysis are treated in a consistent way in view of electron theory.

    References

    1. Saito T, Furuta T, Hwang JH, et al. Multifunctional alloys obtained via a dislocation-free plastic deformation mechanism. Science. 2003;300:464–467.

    2. Valiev RZ, Estrin Y, Horita Z, Langdon TG, Zehetbauer MJ, Zhu YT. Producing bulk ultrafine-grained materials by severe plastic deformation. JOM. 2006;58:33–39.

    3. Iwahashi Y, Wang J, Horita Z, Nemoto M, Langdon TG. Principle of equal-channel angular pressing for the processing of ultra-fine grained materials. Scripta Materialia. 1996;35:143–146.

    4. Saito Y, Utsunomiya H, Tsuji N, Sakai T. Novel ultra-high straining process for bulk materials-development of the accumulative roll bonding (ARB) process. Acta Mater. 1999;47:579–583.

    5. Tsuji N, Ito Y, Saito Y, Minamino Y. Strength and ductility of ultrafine grained aluminum and iron produced by ARB and annealing. Scripta Materialia. 2002;47:893–899.

    6. Huang H, Hansen N, Tsuji N. Hardening by annealing and softening by deformation in nanostructured metals. Science. 2006;312:249–251.

    7. M. Yoshino, Y.Shinzato, M. Morinaga, Energetics of Native Defects in Al2O3 and SiO2, The 3rd International Symposium on Designing, Processing and Properties of Advanced Engineering Materials, Eds. S. G. Kang, T. Kobayashi, Jeju, South Korea, Nov. 5-8, 2003; Materials Science Forum 449–452, 2004, 713–716.

    8. Kingery WD, Bowen HK, Uhlmann DR. Introduction to Ceramics 2nd Edition New York: John Wiley & Sons; 1976.

    9. Cracknell AP, Wong KC. The Fermi Surfaces of Metals: Its Concept, Determination, and Use in the Physics of Metals Oxford: Clarendon Press; 1973.

    10. Ziman JM. Principles of the Theory of Solids Second Edition Cambridge: Cambridge University Press; 1972.

    11. Kittel C. Introduction to Solid State Physics Fifth Edition New York: John Wiley & Sons, Inc; 1976.

    12. Goldman JE. Atomic moments in alloys. Rev Mod Phys. 1953;25:108–113.

    13. Boesch WJ, Slaney JS. Preventing sigma phase embrittlement in nickel base superalloys. Metal Progress. 1964;86:109–111.

    14. Hume-Rothery W, Raynor GV. Structure of Metals and Alloys London: Institute of Metals; 1954.

    15. Darken L, Gurry RW. Physical Chemistry of Metals London: Institute of Metals; 1954.

    2

    Theory for Alloy Design

    Abstract

    A variety of alloys and steels have been widely used from ancient times to modern times. Most of these materials have been developed relying on many trial-and-error experiments as well as the experience of each researcher. In the present supercomputer age, computer-aided alloy design is, however, needed to save time and cost necessary for alloy development. To meet the needs of the times, a theory for alloy design has been developed recently. In this chapter the theory is explained, in particular, focusing on the philosophy of alloy design. The necessity of new alloying parameters is first explained for the design of commercially available alloys with multiple components, since we do not have any alloying parameters despite a long history of metallurgy and metal science. Two alloying parameters are derived using the DV-Xα molecular orbital method. In this chapter, a new approach to alloy design is presented focusing mainly on the alloying parameters and the DV-Xα molecular orbital method.

    Keywords

    Alloy design; DV-Xα molecular orbital method; electronic structure; commercially available alloy; alloying parameter; transition metal; simple metal

    2.1 Electronic Approach to Alloy Design

    It is well known that physical and chemical properties of metals and alloys are related closely to the electronic state in them. Most commercially available alloys consist of multiple components. For example, nickel-based superalloys consist of about 10 alloying elements. For these complex alloy systems, it is very difficult to calculate the electronic state accurately, and even if the calculation could be performed in some way, it might be meaningless for alloy design, because the number of combinations of alloying species and compositions are infinitely large in the multiple-component alloys.

    For alloy design, it is more practical to use alloying parameters that exhibit explicitly the character of each element in a mother metal. However, despite a long history of metallurgy and metal science, we do not have any alloying parameters. For this reason, most alloy properties have been evaluated by using the parameters assigned to pure metals (e.g., the electrons-per-atom-ratio (e/a), atomic radius, electronegativity) [1,2]. The same value of the parameter is always used for the same element even if the alloy system is varied, resulting in very poor prediction of alloy properties along this approach. To solve this problem, it is first necessary to determine alloying parameters theoretically using molecular orbital methods [3–7]. To make the problem clear, the present approach is compared with the previous approach as shown in Fig. 2-1.

    Figure 2-1 Comparison between the previous approach and the present approach.

    To this end, the DV-Xα cluster method [8–17] is utilized. This is the first-principle calculation method, which is more appropriate to the simulation of the local electronic structure around the alloying element, as compared with the conventional band calculation method. For convenience, the DV-Xα cluster method will be explained

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