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Introduction To Materials Science, Chapter 1, Introduction
MSE 209: Introduction to the Science and Engineering of Materials Instructor: Leonid Zhigilei Office: Materials Science Building 227 Spring 2001 MSE 209 - Section 6 Instructor: Leonid Zhigilei Tuesday, Thursday, 9:30 AM - 10:45 AM Olsson Hall 005 Class web page: http://www.people.virginia.edu/~lz2n/mse209/ Class e-mail list: MSE209-6@toolkit.virginia.edu Graduate Teaching Assistants: E-mail eemr aisha cts2v hw2e 982-5689 982-5689
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Contact Information:
Grading:
Homework: 20% Three 1 hour tests: 50 % The final exam: 30%
Office Hours: 11:00 am to 12:00 pm Monday, Friday & open Telephone: (804) 243 3582 E-mail: lz2n@virginia.edu
Homework: 11 problem sets will be will be assigned and will be due at the beginning of class one week after assignment. Homework solutions should be neat and stapled. Homework does not require the pledge and cooperation among students is permitted.
Late homework is not accepted
Tests: pledged, closed-book and closed-notes
Phone
Textbook:
Brian Mays Aisha Moore Tom Schamp Jason Wang

University of Virginia, Dept. of Materials Science and Engineering 1
W. D. Callister, Materials Science and Engineering: An Introduction (John Wiley 1999, 5th edition)
I will also post my lecture notes on the web.
University of Virginia, Dept. of Materials Science and Engineering
Syllabus: Types of materials (metals, ceramics, polymers,

semiconductors) Stone Bronze
Historical Perspective Chapter Outline Historical Perspective

Iron
Beginning of the Material Science - People began to make tools from stone Start of the Stone Age about two million years ago. Natural materials: stone, wood, clay, skins, etc. Advanced materials
Properties of materials (mechanical, thermal, electrical, optical) Different levels of structure in materials (atomic, microscopic, macroscopic) Relation among material processing, structure, properties, and performance
What is Materials Science and Engineering ?

Processing Structure Properties
Performance
Classification of Materials
Metals, Ceramics, Polymers, Semiconductors
The Stone Age ended about 5000 years ago with introduction of Bronze in the Far East. Bronze is an alloy (a metal made up of more than one element), copper + < 25% of tin + other elements. Bronze: can be hammered or cast into a variety of shapes, can be made harder by alloying, corrode only slowly after a surface oxide film forms.
Advanced Materials
Electronic materials, superconductors, etc.
The main objective is to understand the basic concepts and language of Materials Science
Modern Material's Needs, Material of Future

Biodegradable materials, Nanomaterials, Smart materials
The Iron Age began about 3000 years ago and continues today. Use of iron and steel, a stronger and cheaper material changed drastically daily life of a common person.
Age of Advanced materials: throughout the Iron Age many new types of materials have been introduced (ceramic, semiconductors, polymers, composites). Understanding of the relationship among structure, properties, processing, and performance of materials. Intelligent design of new materials.
University of Virginia, Dept. of Materials Science and Engineering 4 University of Virginia, Dept. of Materials Science and Engineering 5
A better understanding of structure-compositionproperties relations has lead to a remarkable progress in properties of materials. Example is the dramatic What is Materials Science and Engineering ?
progress in the strength to density ratio of materials, that resulted in a wide variety of new products, from dental materials to tennis racquets.
Structure
Subatomic level (Chapter 2)

Processing Materials Optimization Loop
Electronic structure of individual atoms that defines interaction among atoms (interatomic bonding).
Atomic level (Chapters 2 & 3)
Arrangement of atoms in materials (for the same atoms can have different properties, e.g. two forms of carbon: graphite and diamond)
Structure Observational
Properties
Microscopic structure (Ch. 4)

Material science is the investigation of the relationship among processing, structure, properties, and performance of materials.
Arrangement of small grains of material that can be identified by microscopy.
Macroscopic structure
Structural elements that may be viewed with the naked eye.

Monarch butterfly ~ 0.1 m
THE SCALE OF THINGS

0.1 1027
Length and Time Scales from the point of view of Materials Modeling.
Things Natural
Things Manmade
100 m
1 meter (m)
Length-scales Angstrom = 1 = 1/10,000,000,000 meter = 10-10 m Nanometer = 10 nm = 1/1,000,000,000 meter = 10-9 m Micrometer = 1m = 1/1,000,000 meter = 10-6 m Millimeter = 1mm = 1/1,000 meter = 10-3 m
10-1 m
0.1 m 100 mm
LengthMesosc Scale, opic number Length Scale,of atoms meters

Dislocation Dynamics Nature, 12 February, 1998
Progress in miniaturiza tion

Monarch butterfly ~ 0.1 m Cat ~ 0.3 m
Objects fashioned from metals, ceramics, glasses, polymers ...
10-2 m
0.01 m 1 cm 10 mm
Head of a pin 1-2 mm
ia Scale, nd a seconds , S ture llm Ho r frac modehbet anula otts a liz rgr lo P E ter Micros In t e C a copic on M
Time
Bee ~ 15 mm Dust mite 300
10-3 m
1 millimeter (mm)
Microelectronics
MEMS (MicroElectroMechanical Systems) Devices 10 -100 wide
10-4 m
Human hair ~ 50 wide Fly ash ~ 10-20
0.1 mm 100 m
The 21st century challenge -- Fashion materials at the nanoscale with desired properties and functionali ty
The Microworld
10-5 m
0.01 mm 10 m
Red blood cells Pollen grain
Interatomic distance ~ a few A human hair is ~ 50 m Elongated bumps that make up the data track on CD are ~ 0.5 m wide, minimum 0.83 m long, and 125 nm high
10-8 106 10-7 109
Mo Li, JHU, Atomistic model of a nanocrystalline
Magnetic domains garnet film 11 wide stripes
Red blood cells with white cell ~ 2-5
10-6 m
1 micrometer (m)
Visible spectrum
10-7
Indium arsenide quantum dot Schematic, central core ATP synthase
Quantum dot array -germanium dots on silicon
Farid Abraham, IBM MD of crack propagation
Progress 10-7 m in atomic-lev The el Nanoworld understan ding

10 nm
0.1 m 100 nm
10-8 m
0.01 m 10 nm
Biomotor using ATP
Nanosc opic
10-9
Leonid Zhigilei, UVA Phase transformation on diamond surfaces
Self-assembled mushroom Cell membrane
10-9 m
1 nanometer (nm)
DNA ~2 nm wide Atoms of silicon spacing ~tenths of nm
10-10 m
0.1 nm
10-9 103
University of Virginia, Dept. of Materials Science and Engineering University of Virginia, Dept. of Materials Science and Engineering 10
10-12
meter centimeter millimeter micrometer nanometer m cm mm nm 100 10-2 10-3 10-6 10-9
Quantum corral of 48 iron atoms on copper surface positioned one at a time with an STM tip Corral diameter 14 nm 1m 0.01 m 0.001 m 0.000001 m
Chart from http://www.sc.doe.gov/production/bes/scale_of_things.html
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0.000000001 m University of Virginia, Dept. of Materials Science and Engineering
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Properties
Properties are the way the material responds to the environment and external forces. Mechanical properties response to mechanical forces, strength, etc. Electrical and magnetic properties - response electrical and magnetic fields, conductivity, etc. Thermal properties are related to transmission of heat and heat capacity. Optical properties include to absorption, transmission and scattering of light. Chemical stability in contact with the environment corrosion resistance. Semiconductors: the bonding is covalent (electrons are shared between atoms). Their electrical properties depend strongly on minute proportions of contaminants. Examples: Si, Ge, GaAs. Ceramics: atoms behave like either positive or negative ions, and are bound by Coulomb forces. They are usually combinations of metals or semiconductors with oxygen, nitrogen or carbon (oxides, nitrides, and carbides). Hard, brittle, insulators. Examples: glass, porcelain. Polymers: are bound by covalent forces and also by weak van der Waals forces, and usually based on C and H. They decompose at moderate temperatures (100 400 C), and are lightweight. Examples: plastics rubber. Metals: valence electrons are detached from atoms, and spread in an 'electron sea' that "glues" the ions together. Strong, ductile, conduct electricity and heat well, are shiny if polished. Let us classify materials according to the way the atoms are bound together (Chapter 2).
Types of Materials
Metals
Several uses of steel and pressed aluminum.
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Ceramics
Composites Polymers
Examples of ceramic materials ranging from household to high performance combustion engines which utilize both metals and ceramics.
Polymer composite materials: reinforcing glass fibers in a polymer matrix. Polymers include Plastics and rubber materials
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Semiconductors Material Selection

Different materials exhibit different crystal structures (Chapter 3) and resultant Properties
Material Selection
Different materials exhibit different microstructures (Chapter 4) and resultant Properties
Micro-ElectricalMechanical Systems (MEMS)
Si wafer for computer chip devices. (a) force (b)
Superplastic deformation involves low-stress sliding along grain boundaries, a complex process of which material scientists have limited knowledge and that is a subject of current investigations.
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Material Selection
Composition, Bonding, Crystal Structure and Microstructure DEFINE Materials Properties
Future of materials science
Design of materials having specific desired characteristics directly from our knowledge of atomic structure.
Composition
Miniaturization:Nanostructured" materials, with microstructure that has length scales between 1 and 100 nanometerswithunusualproperties.Electronic components, materials for quantum computing.
Bonding
Crystal Structure
Smart materials: airplane wings that deice themselves, buildings that stabilize themselves in earthquakes
Environment-friendly materials: biodegradable or photodegradable plastics, advances in nuclear waste processing, etc.
Thermomechanical Processing
Learning from Nature: shells and biological hard tissue can be as strong as the most advanced laboratory-produced ceramics, mollusces produce biocompatible adhesives that we do not know how to reproduce
How do you decide on a specific material for your application ?
Microstructure
Materials for lightweight batteries with high storage densities, for turbine blades that can operate at 2500C, room-temperature superconductors? chemical sensors (artificial nose) of extremely high sensitivity, cotton shirts that never require ironing
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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding
Chapter Outline Review of Atomic Structure Electrons, Protons, Neutrons, Quantum mechanics of atoms, Electron states, The Periodic Table
Charges: Electrons and protons have negative and positive charges of the same magnitude, 1.6 10-19 Coulombs. Neutrons are electrically neutral. Atoms = nucleus (protons and neutrons) + electrons
Review of Atomic Structure
Atomic mass units. Atomic weight.
The atomic mass unit (amu) is often used to express atomic weight. 1 amu is defined as 1/12 of the atomic mass of the most common isotope of carbon atom that has 6 protons (Z=6) and six neutrons (N=6).
Atomic Bonding in Solids Bonding Energies and Forces Periodic Table

Masses:
Mproton Mneutron = 1.66 x 10-24 g = 1 amu.
The atomic mass of the 12C atom is 12 amu.
Primary Interatomic Bonds Ionic Covalent Metallic

Protons and Neutrons have the same mass, 1.67 10-27 kg. Mass of an electron is much smaller, 9.11 10-31 kg and can be neglected in calculation of atomic mass.
The atomic weight of an element = weighted average of the atomic masses of the atoms naturally occurring isotopes. Atomic weight of carbon is 12.011 amu.
The atomic weight is often specified in mass per mole.
Secondary Bonding (Van der Waals)

Three types of Dipole Bonds
The atomic mass (A) = mass of protons + mass of neutrons # protons gives chemical identification of the element # protons = atomic number (Z) # neutrons defines isotope number
A mole is the amount of matter that has a mass in grams equal to the atomic mass in amu of the atoms (A mole of carbon has a mass of 12 grams).
Molecules and Molecular Solids Understanding of interatomic bonding is the first step towards understanding/explaining materials properties
The number of atoms in a mole is called the Avogadro number, Nav = 6.023 1023. Nav = 1 gram/1 amu.
Example: Atomic weight of iron = 55.85 amu/atom = 55.85 g/mol

Some simple calculations

The number of atoms per cm3, n, for material of density d (g/cm3) and atomic mass M (g/mol):
n = Nav d / M Graphite (carbon): d = 2.3 g/cm3, M = 12 g/mol n = 61023 atoms/mol 2.3 g/cm3 / 12 g/mol = 11.5 1022 atoms/cm3 Diamond (carbon): d = 3.5 g/cm3, M = 12 g/mol n = 61023 atoms/mol 3.5 g/cm3 / 12 g/mol = 17.5 1022 atoms/cm3 Water (H2O) d = 1 g/cm3, M = 18 g/mol n = 61023 molecules/mol 1 g/cm3 / 18 g/mol = 3.3 1022 molecules/cm3 For material with n = 6 1022 atoms/cm3 we can calculate mean distance between atoms L = (1/n)1/3 = 0.25 nm. the scale of atomic structures in solids a fraction of 1 nm or a few A.
Electrons in Atoms (I)

The electrons form a cloud around the nucleus, of radius of 0.05 2 nm.
Electrons in Atoms (II)
The quantum numbers arise from solution of Schrodingers equation
Pauli Exclusion Principle: only one electron can have a given set of the four quantum numbers.
This picture looks like a mini planetary system.But quantum mechanics tells us that this analogy is not correct:
The Number of Available Electron States in Some of the Electron Shells and Subshells
Principal Q. N., n 1 (l=0) 2 (l=0) 2 (l=1) 3 (l=0) 3 (l=1) 3 (l=2) 4 (l=0) 4 (l=1) 4 (l=2) 4 (l=3) Subshells s s p s p d s p d f
Electrons move not in circular orbits, but in 'fuzzy orbits. Actually, we cannot tell how it moves, but only can say what is the probability of finding it at some distance from the nucleus. Only certain orbits or shells of electron probability densities are allowed. The shells are identified by a principal quantum number n, which can be related to the size of the shell, n = 1 is the smallest; n = 2, 3 .. are larger. The second quantum number l, defines subshells within each shell. Two more quantum numbers characterize states within the subshells.
Number of States 1 1 3 1 3 5 1 3 5 7
Number of Electrons Per Subshell Per Shell 22 28 6 218 6 10 232 6 10 14
Electrons in Atoms (III)
Periodic Table
Periodic Table - Electronegativity
Figure 2.7 from the textbook. The electronegativity values.
Electronegativity - a measure of how willing atoms are to accept electrons

Subshells by energy: 1s,2s,2p,3s,3p,4s,3d,4s,4p,5s,4d,5p,6s,4f,
Electrons that occupy the outermost filled shell the valence electrons they are responsible for bonding. Electrons fill quantum levels in order of increasing energy (only n, l make a significant difference). Example: Iron, Z = 26: 1s22s22p63s23p63d64s2
Elements in the same column (Elemental Group) share similar properties. Group number indicates the number of electrons available for bonding.
0: Inert gases (He, Ne, Ar...) have filled subshells: chem. inactive IA: Alkali metals (Li, Na, K) have one electron in outermost occupied s subshell - eager to give up electron chem. active VIIA: Halogens (F, Br, Cl...) missing one electron in outermost occupied p shell - want to gain electron - chem. active
Subshells with one electron - low electronegativity Subshells with one missing electron -high electronegativity
Electronegativity increases from left to right
Metals are electropositive they can give up their few valence electrons to become positively charged ions
Bonding Energies and Forces

repulsion Potenti al Energ y, E 0 attraction Potenti al Energ y
Bonding Energies and Forces

a0
The electron volt (eV) energy unit convenient for description of atomic bonding
Ut=Ur+Ua
Electron volt - the energy lost / gained by an electron when it is taken through a potential difference of one volt.
E=qV
E0
E0 bond energy F= dE/da a0 equilibrium distance at a0, dE/da = 0, Fa = Fr
a0
equilibrium This is typical potential well for two interacting atoms The repulsion between atoms, when they are brought close to each other, is related to the Pauli principle: when the electronic clouds surrounding the atoms starts to overlap, the energy of the system increases abruptly. The origin of the attractive part, dominating at large distances, depends on the particular type of bonding.
Tensile (+)
For q = 1.6 x 10-19 Coulombs V = 1 volt
1 eV = 1.6 x 10-19 J
Force
Compressive (-)
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Types of Bonding
Primary bonding: e- are transferred or shared Strong (100-1000 KJ/mol or 1-10 eV/atom) Formation of ionic bond: 1. Mutual ionization occurs by electron transfer (remember electronegativity table) Ion = charged atom Anion = negatively charged atom Cation = positively charged atom
Ionic Bonding (I) eNa
Ionic Bonding (II) Cl
Na+
Cl-
Ionic: Strong Coulomb interaction among negative atoms (have an extra electron each) and positive atoms (lost an electron). Example - Na+ClCovalent: electrons are shared between the molecules, to saturate the valency. Example - H2 Metallic: the atoms are ionized, loosing some electrons from the valence band. Those electrons form a electron sea, which binds the charged nuclei in place Secondary Bonding: no e- transferred or shared Interaction of atomic/molecular dipoles Weak (< 100 KJ/mol or < 1 eV/atom) 11 Protons Na 1S2 2S2 2P6 3S1 11 Protons Na+ 1S2 2S2 2P6 Fluctuating Induced Dipole (inert gases, H2, Cl2) Permanent dipole bonds (polar molecules - H2O, HCl...) Polar molecule-induced dipole bonds (a polar molecule
like induce a dipole in a nearby nonpolar atom/molecule)
Electron transfer reduces the energy of the system of atoms, that is, electron transfer is energetically favorable
2. Ions are attracted by strong coulombic interaction Oppositely charged atoms attract An ionic bond is non-directional (ions may be attracted to one another in any direction Example: NaCl Na has 11 electrons, 1 more than needed for a full outer shell (Neon) donates e10 e- left
Note relative sizes of ions: Na shrinks and Cl expands
Cl has 17 electron, 1 less than needed for a full outer shell (Argon) 17 Protons Cl 1S2 2S2 2P6 3S2 3P5 17 Protons Cl- 1S2 2S2 2P6 3S2 3P6 receives e18 e14
Ionic bonds: very strong, nondirectional bonds
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Covalent Bonding (I)

In covalent bonding, electrons are shared between the molecules, to saturate the valency. The simplest example is the H2 molecule, where the electrons spend more time in between the nuclei than outside, thus producing bonding.
Covalent Bonding (II)

Example: Carbon materials. Zc = 6 (1S2 2S2 2P2) N = 4, 8 - N = 4 can form up to four covalent bonds
Covalent Bonding (III)
2-D schematic of the spaghetti-like structure of solid polyethylene
ethylene molecule: Formation of covalent bonds: Cooperative sharing of valence electrons Can be described by orbital overlap Covalent bonds are HIGHLY directional Bonds - in the direction of the greatest orbital overlap ethylene mer Covalent bond model: an atom can covalently bond with at most 8-N, N = number of valence electrons Example: Cl2 molecule. ZCl =17 (1S2 2S2 2P6 3S2 3P5) N = 7, 8 - N = 1 can form only one covalent bond polyethylene molecule:
diamond: (each C atom has four covalent bonds with four other carbon atoms)
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Covalent Bonding (IV)

The potential energy of a system of covalently interacting atoms depend not only on the distances between atoms, but also on angles between bonds
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Introduction To Materials Science, Chapter 3, The structure of crystalline solids
Chapter Outline How do atoms arrange themselves to form solids? Fundamental concepts and language Unit cells Crystal structures Face-centered cubic Body-centered cubic Hexagonal close-packed Close packed crystal structures Density computations Types of solids Single crystal Polycrystalline Amorphous
Single crystal: atoms are in a repeating or periodic array over the entire extent of the material Polycrystalline material: crystals or grains comprised of many small Amorphous: lacks a systematic atomic arrangement Crystalline material: atoms self-organize in a periodic array
Types of Solids
Crystal structure
To discuss crystalline structures it is useful to consider atoms as being hard spheres with well-defined radii. In this hard-sphere model, the shortest distance between two like atoms is one diameter.
We can also consider crystalline structure as a lattice of points at atom/sphere centers.
Crystalline
Amorphous
3.73.10 Crystallography Not Covered / Not Tested 3.15 Diffraction Not Covered / Not Tested Learning objectives #5, #6 - Not Covered / Not Tested SiO2
Unit Cell
The unit cell is the smallest structural unit or building block that can describe the the crystal structure. Repetition of the unit cell generates the entire crystal.
Face-Centered Cubic (FCC) Crystal Structure (I) Metallic Crystal Structures

Metals are usually (poly)crystalline; although formation of amorphous metals is possible by rapid cooling As we learned in Chapter 2, the atomic bonding in metals is non-directional no restriction on numbers or positions of nearest-neighbor atoms large number of nearest neighbors and dense atomic packing Atom (hard sphere) radius, R, defined by ion core radius - typically 0.1 - 0.2 nm The most common types of unit cells are the facedcentered cubic (FCC), the body-centered cubic (FCC) and the hexagonal close-packed (HCP).
Atoms are located at each of the corners and on the centers of all the faces of cubic unit cell Cu, Al, Ag, Au have this crystal structure
Example: 2D honeycomb net can be represented by translation of two adjacent atoms that form a unit cell for this 2D crystalline structure
Example of 3D crystalline structure:
Two representations of the FCC unit cell Different choices of unit cells possible, generally choose parallelepiped unit cell with highest level of symmetry
Face-Centered Cubic Crystal Structure (II)

Corner and face atoms in the unit cell are equivalent FCC crystal has APF of 0.74, the maximum packing for a system equal-sized spheres FCC is a close-packed structure
Face-Centered Cubic Crystal Structure (III)
Body-Centered Cubic (BCC) Crystal Structure (I)
Atom at each corner and at center of cubic unit cell Cr, , Mo have this crystal structure
R
FCC can be represented by a stack of close-packed planes (planes with highest density of atoms)
a
The hard spheres or ion cores touch one another across a face diagonal the cube edge length, a= 2R2 The coordination number, CN = the number of closest neighbors to which an atom is bonded = number of touching atoms, CN = 12 Number of atoms per unit cell, n = 4. (For an atom that is shared with m adjacent unit cells, we only count a fraction of the atom, 1/m). In FCC unit cell we have:
6 face atoms shared by two cells: 6 x 1/2 = 3 8 corner atoms shared by eight cells: 8 x 1/8 = 1
Atomic packing factor, APF = fraction of volume occupied by hard spheres = (Sum of atomic volumes)/(Volume of cell) = 0.74 (maximum possible)
Body-Centered Cubic Crystal Structure (II)
Hexagonal Close-Packed Crystal Structure (I)

HCP is one more common structure of metallic crystals Six atoms form regular hexagon, surrounding one atom in center. Another plane is situated halfway up unit cell (c-axis), with 3 additional atoms situated at interstices of hexagonal (close-packed) planes Cd, Mg, Zn, Ti have this crystal structure
Hexagonal Close-Packed Crystal Structure (II)
Unit cell has two lattice parameters a and c. Ideal ratio c/a = 1.633
The coordination number, CN = 12 (same as in FCC)
Number of atoms per unit cell, n = 6. 3 mid-plane atoms shared by no other cells: 3 x 1 = 3
12 hexagonal corner atoms shared by 6 cells: 12 x 1/6 = 2
a
The hard spheres touch one another along cube diagonal the cube edge length, a= 4R/3 The coordination number, CN = 8 Number of atoms per unit cell, n = 2 Center atom (1) shared by no other cells: 1 x 1 = 1 8 corner atoms shared by eight cells: 8 x 1/8 = 1 Atomic packing factor, APF = 0.68 Corner and center atoms are equivalent
2 top/bottom plane center atoms shared by 2 cells: 2 x 1/2 = 1
Atomic packing factor, APF = 0.74 (same as in FCC)
All atoms are equivalent
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Close-packed Structures (FCC and HCP)

Both FCC and HCP crystal structures have atomic packing factors of 0.74 (maximum possible value) Both FCC and HCP crystal structures may be generated by the stacking of close-packed planes The difference between the two structures is in the stacking sequence
FCC: Stacking Sequence ABCABCABC...
HCP: Stacking Sequence ABABAB...
Third plane is placed above the holes of the first plane not covered by the second plane
Third plane is placed directly above the first plane of atoms HCP: ABABAB...
FCC: ABCABCABC
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Density Computations
Since the entire crystal can be generated by the repetition of the unit cell, the density of a crystalline material, = the density of the unit cell = (atoms in the unit cell, n ) (mass of an atom, M) / (the volume of the cell, Vc) Atoms in the unit cell, n = 2 (BCC); 4 (FCC); 6 (HCP) Mass of an atom, M = Atomic weight, A, in amu (or g/mol) is given in the periodic table. To translate mass from amu to grams we have to divide the atomic weight in amu by the Avogadro number NA = 6.023 1023 atoms/mol The volume of the cell, Vc = a3 (FCC and BCC) a = 2R2 (FCC); a = 4R/3 (BCC) where R is the atomic radius Thus, the formula for the density is:
Polymorphism and Allotropy

Some materials may exist in more than one crystal structure, this is called polymorphism. If the material is an elemental solid, it is called allotropy. An example of allotropy is carbon, which can exist as diamond, graphite, and amorphous carbon.
Single Crystals and Polycrystalline Materials
Single crystal: atoms are in a repeating or periodic array over the entire extent of the material
Polycrystalline material: comprised of many small crystals or grains.The grains have different crystallographic orientation. There exist atomic mismatch within the regions where grains meet. These regions are called grain boundaries.
nA = Vc N A
Atomic weight and atomic radius of many elements you can find in the table at the back of the textbook front cover.
Pure, solid carbon occurs in three crystalline forms diamond, graphite; and large, hollow fullerenes. Two kinds of fullerenes are shown here: buckminsterfullerene (buckyball) and carbon nanotube.
Grain Boundary
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Polycrystalline Materials
Polycrystalline Materials
Anisotropy
Different directions in a crystal have a different packing. For instance, atoms along the edge of FCC unit cell are more separated than along the face diagonal. This causes anisotropy in the properties of crystals, for instance, the deformation depends on the direction in which a stress is applied.
In some polycrystalline materials, grain orientations are random, so bulk material properties are isotropic
Some polycrystalline materials have grains with preferred orientations (texture), so properties are dominated by those relevant to the texture orientation and the material exhibits anisotropic properties
Atomistic model of a nanocrystalline solid by Mo Li, JHU Simulation of annealing of a polycrystalline grain structure
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Non-Crystalline (Amorphous) Solids

In amorphous solids, there is no long-range order. But amorphous does not mean random, in many cases there is some form of short-range order.
Summary
Make sure you understand language and concepts: Allotropy Amorphous Anisotropy Atomic packing factor (APF) Body-centered cubic (BCC) Coordination number Crystal structure Crystalline Face-centered cubic (FCC) Grain Grain boundary Hexagonal close-packed (HCP) Isotropic Lattice parameter Non-crystalline Polycrystalline Polymorphism Single crystal Unit cell
Reading for next class:
Chapter 4: Imperfections in Solids Point defects (vacancies, interstitials) Dislocations (edge, screw) Grain boundaries (tilt, twist) Weight and atomic composition
Schematic picture of amorphous SiO2 structure
Optional reading (Parts that are not covered / not tested):
4.9 Microscopy
4.10 Grain size determination

Amorphous structure from simulations by E. H. Brandt
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Introduction To Materials Science, Chapter 4, Imperfections in solids
Chapter Outline Crystals are like people, it is the defects in them which tend to make them interesting! - Colin Humphreys. Defects Introduction (I)
Real crystals are never perfect, there are always defects
Defects Introduction (II)
Defects have a profound impact on the macroscopic properties of materials
Defects in Solids
0D, Point defects vacancies interstitials impurities, weight and atomic composition
Bonding + Structure + Defects

Schematic drawing of a poly-crystal with many defects by Helmut Fll, University of Kiel, Germany.
1D, Dislocations edge screw 2D, Grain boundaries tilt twist 3D, Bulk or Volume defects Atomic vibrations 4.9 - 4.10 Microscopy & Grain size determination Not Covered / Not Tested
Properties
Defects Introduction (III)

The processing determines the defects
Types of Defects
Defects may be classified into four categories depending on their dimension: 0D, Point defects: atoms missing or in irregular places in the lattice (vacancies, interstitials, impurities)
Point defects: vacancies & self-interstitials
Composition
Bonding
Crystal Structure
1D, Linear defects: groups of atoms in irregular positions (e.g. screw and edge dislocations) 2D, Planar defects: the interfaces between homogeneous regions of the material (grain boundaries, external surfaces)
Self-interstitials
Vacancy
Thermomechanical Processing
3D, Volume defects: extended defects (pores, cracks)
defects introduction
and manipulation
Vacancy - a lattice position that is vacant because the atom is missing.
Microstructure
Interstitial - an atom that occupies a place outside the normal lattice position. It may be the same type of atom as the others (self interstitial) or an impurity interstitial atom.
How many vacancies are there?

Lets estimate the number of vacancies in Cu at room T QvN v = N s exp k BT The Boltzmanns constant kB = 1.38 10-23 J/atom-K = 8.62 10-5 eV/atom-K The temperature in Kelvin T = 27o C + 273 = 300 K. kBT = 300 K 8.62 10-5 eV/K = 0.026 eV The energy for vacancy formation Qv = 0.9 eV/atom The number of regular lattice sites Ns = NA/cu NA = 6.023 1023 atoms/mol = 8.4 g/cm3 Acu = 63.5 g/mol The equilibrium number of vacancies formed as a result of thermalvibrationsmaybecalculatedfrom thermodynamics:
Other point defects: self-interstitials, impurities
Qv N v = N s exp k BT
where Ns is the number of regular lattice sites, kB is the Boltzmann constant, Qv is the energy needed to form a vacant lattice site in a perfect crystal, and T the temperature in Kelvin (note, not in oC or oF).
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Schematic representation of different point defects: (1) vacancy; (2) self-interstitial; (3) interstitial impurity; (4,5) substitutional impurities
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Using this equation we can estimate that at room temperature in copper there is one vacancy per 1015 lattice atoms, whereas at high temperature, just below the melting point there is one vacancy for every 10,000 atoms.
The arrows show the local stresses introduced by the point defects.
(6.023 10
23
atoms 63.5 g mol
)
8.4 g cm 3 mol
Ns = Note, that the above equation gives the lower end estimation of the number of vacancies, a large numbers of additional (nonequilibrium) vacancies can be introduced in a growth process or as a result of further treatment (plastic deformation, quenching from high temperature to the ambient one, etc.)
22
22 = 8 10 atoms
cm 3
Self-interstitials
atoms 0.9 eV atom=N v = 8 10exp
3 7 = 7.4 10 vacancies cm 0.0263 eV atom cm
Self-interstitials in metals introduce large distortions in the surrounding lattice the energy of self-interstitial formation is ~ 3 times larger as compared to vacancies (Qi ~ 3Qv) equilibrium concentration of self-interstitials is very low (less than one self-interstitial per cm3 at room T).
Impurities Impurities - atoms which are different from the host

All real solids are impure. Very pure metals 99.9999% - one impurity per 106 atoms May be intentional or unintentional Examples: carbon added in small amounts to iron makes steel, which is stronger than pure iron. Boron added to silicon change its electrical properties.
Solid Solutions Solid solutions are made of a host (the solvent or matrix) which dissolves the minor component (solute). The ability to dissolve is called solubility. Solvent: in an alloy, the element or compound present in greater amount Solute: in an alloy, the element or compound present in lesser amount Solid Solution: homogeneous maintain crystal structure containrandomlydispersedimpurities (substitutional or interstitial)
Substitutional Solid Solutions
Ni
Cu
Alloys - deliberate mixtures of metals Example: sterling silver is 92.5% silver 7.5% copper alloy. Stronger than pure silver.
Second Phase: as solute atoms are added, new compounds / structures are formed, or solute forms local precipitates (discussed in Chapter 9)
Whether the addition of impurities results in formation of solid solution or second phase depends the nature of the impurities, their concentration and temperature, pressure
Factors for high solubility: Atomic size factor - atoms need to fit solute and solvent atomic radii should be within ~ 15% Crystal structures of solute and solvent should be the same Electronegativities of solute and solvent should be comparable (otherwise new inter-metallic phases are encouraged) Generally more solute goes into solution when it has higher valency than solvent
10
11
12
Interstitial Solid Solutions

Composition can be expressed in Carbon interstitial atom in BCC iron weight percent, useful when making the solution atom percent, useful when trying to understand the material at the atomic level Weight percent (wt %): weight of a particular element relative to the total alloy weight. For two-component system, concentration of element 1 in wt. % is
Composition / Concentration
Composition Conversions
Weight % to Atomic %:
C1A 2 ' C 1= 100 C1A 2 + C 2 A1
C 2 A1 ' C 2= 100 C1A 2 + C 2 A1
Interstitial solid solution of C in . The C atom is small enough to fit, after introducing some strain into the BCC lattice.
m1 C1 = 100 m1 + m 2
Atom percent (at %): number of moles (atoms) of a particular element relative to the total number of moles (atoms) in alloy.For two-component system, concentration of element 1 in at. % is
Atomic % to Weight %:
C A1 1 C1 = ' 100
'
'
Factors for high solubility: For fcc, bcc, hcp structures the voids (or interstices) between the host atoms are relatively small atomic radius of solute should be significantly less than solvent Normally, max. solute concentration 10%, (2% for C-Fe)
C1A1 + C 2 A 2
n m1 ' C1 = 100 n m1 + n m 2
where nm1 = m1/A1 m1 is weight in grams of element 1, A1 is atomic weight of element 1)
C A2 2 C2 = ' 100
'
'
C1A1 + C 2 A 2
Textbook, pp. 71-74
15
DislocationsLinear Defects
Dislocations are linear defects: the interatomic bonds are significantly distorted only in the immediate vicinity of the dislocation line. This area is called the dislocation core. Dislocations also create small elastic deformations of the lattice at large distances.
Description of DislocationsBurgers Vector

To describe the size and the direction of the main lattice distortion caused by a dislocation we should introduce socalled Burgers vector b. To find the Burgers vector, we should make a circuit from from atom to atom counting the same number of atomic distances in all directions. If the circuit encloses a dislocation it will not close. The vector that closes the loop is the Burgers vector b.
Edge and screw dislocations
Dislocations shown in previous slide are edge dislocations, have Burgers vector directed perpendicular to the dislocation line.
There is a second basic type of dislocation, called screw dislocation. The screw dislocation is parallel to the direction in which the crystal is being displaced (Burgers vector is parallel to the dislocation line).
Dislocations are very important in mechanical properties of material (Chapters 6, 7, 8). Introduction/discovery of dislocations in 1934 by Taylor, Orowan and Polyani marked the beginning of our understanding of mechanical properties of materials.
Dislocations shown above have Burgers vector directed perpendicular to the dislocation line. These dislocations are called edge dislocations.
Find the Burgers vector of a screw dislocation. How a screw dislocation got its name?
16
17
18
Mixed/partial dislocations (not tested)

The exact structure of dislocations in real crystals is usually more complicated than the ones shown in this pages. Edge and screw dislocations are just extreme forms of the possible dislocation structures. Most dislocations have mixed edge/screw character. External Surfaces Surface atoms have have unsatisfied atomic bonds, and higher energies than the bulk atoms Surface energy, (J/m2)
Interfacial Defects
High and Low Angle Grain Boundaries
Depending on misalignments of atomic planes between adjacent grains we can distinguish between the low and high angle grain boundaries
Surface areas tend to minimize (e.g. liquid drop) Solid surfaces can reconstruct to satisfy atomic bonds at surfaces.
Grain Boundaries Polycrystalline material comprised of many small crystals or grains.The grains have different crystallographic orientation. There exist atomic mismatch within the regions where grains meet. These regions are called grain boundaries.
To add to the complexity of real defect structures, dislocation are often split in "partial dislocations that have their cores spread out over a larger area.
Surfaces and interfaces are reactive and impurities tend to segregate there. Since energy is associated with interfaces, grains tend to grow in size at the expense of smaller grains to minimize energy. This occurs by diffusion (Chapter 5), which is accelerated at high temperatures.
20
21
Tilt and Twist Grain Boundaries

Low angle grain boundary is an array of aligned edge dislocations. This type of grain boundary is called tilt boundary (consider joint of two wedges)
Twin Boundaries (not tested)

Low-energy twin boundaries with mirrored atomic positions across boundary may be produced by deformation of materials. This gives rise to shape memory metals, which can recover their original shape if heated to a high temperature. Shape-memory alloys are twinned and when deformed they untwin. At high temperature the alloy returns back to the original twin configuration and restore the original shape.
Electron Microscopy (not tested)
Transmission electron microscope image of a small angle tilt boundary in Si. The red lines mark the edge dislocations, the blue lines indicate the tilt angle
Dislocations in Nickel (the dark lines and loops), transmission electron microscopy image, Manchester Materials Science Center.
Twist boundary - the boundary region consisting of arrays of screw dislocations (consider joint of two halves of a cube and twist an angle around the cross section normal)
High-resolution Transmission Electron Microscope image of a tilt grain boundary in aluminum, Sandia National Lab.
24
Summary Bulk or Volume Defects Pores - can greatly affect optical, thermal, mechanical properties
Heat causes atoms to vibrate Vibration amplitude increases with temperature Melting occurs when vibrations are sufficient to rupture bonds
Atomic Vibrations
Make sure you understand language and concepts:
Cracks - can greatly affect mechanical properties Foreign inclusions - can greatly affect electrical, mechanical, optical properties
Vibrational frequency ~ 1013 Hz Average atomic energy due to thermal excitation is of order kT A cluster of microcracks in a melanin granule irradiated by a short laser pulse. Computer simulation by L. V. Zhigilei and B. J. Garrison.
Alloy Atom percent Atomic vibration Boltzmanns constant Burgers vector Composition Dislocation line Edge dislocation Grain size Imperfection Interstitial solid solution Microstructure Point defect Screw dislocation Self-Interstitial Solid solution Solute Solvent Substitutional solid solution Vacancy Weight percent
26
27
Reading for next class:
Chapter 5: Diffusion Diffusion Mechanisms (vacancy, interstitial) Steady-State Diffusion (Ficks first law) Factors That Influence Diffusion Other Diffusion Paths
Optional reading (Part that is not covered / not tested):
5.4 Nonsteady-state diffusion
28

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Introduction To Materials Science, Chapter 1, Introduction

Introduction To Materials Science, Chapter 1, Introduction

Introduction To Materials Science, Chapter 1, Introduction

Homework: 20% Three 1 hour tests: 50 % The final exam: 30%

Late homework is not accepted

Tests: pledged, closed-book and closed-notes

Brian Mays Aisha Moore Tom Schamp Jason Wang

I will also post my lecture notes on the web.

University of Virginia, Dept. of Materials Science and Engineering

University of Virginia, Dept. of Materials Science and Engineering

Introduction To Materials Science, Chapter 1, Introduction

Introduction To Materials Science, Chapter 1, Introduction

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Syllabus: Types of materials (metals, ceramics, polymers,

Historical Perspective Chapter Outline Historical Perspective

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Modern Material's Needs, Material of Future

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Introduction To Materials Science, Chapter 1, Introduction

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Subatomic level (Chapter 2)

Atomic level (Chapters 2 & 3)

Microscopic structure (Ch. 4)

Arrangement of small grains of material that can be identified by microscopy.

Structural elements that may be viewed with the naked eye.

Monarch butterfly ~ 0.1 m

University of Virginia, Dept. of Materials Science and Engineering

Introduction To Materials Science, Chapter 1, Introduction

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THE SCALE OF THINGS

LengthMesosc Scale, opic number Length Scale,of atoms meters

Progress in miniaturiza tion

Objects fashioned from metals, ceramics, glasses, polymers ...

Head of a pin 1-2 mm

Bee ~ 15 mm Dust mite 300

MEMS (MicroElectroMechanical Systems) Devices 10 -100 wide

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Magnetic domains garnet film 11 wide stripes

Red blood cells with white cell ~ 2-5

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Farid Abraham, IBM MD of crack propagation

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DNA ~2 nm wide Atoms of silicon spacing ~tenths of nm

Chart from http://www.sc.doe.gov/production/bes/scale_of_things.html

0.000000001 m University of Virginia, Dept. of Materials Science and Engineering

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Introduction To Materials Science, Chapter 1, Introduction

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University of Virginia, Dept. of Materials Science and Engineering 13

University of Virginia, Dept. of Materials Science and Engineering

University of Virginia, Dept. of Materials Science and Engineering

Introduction To Materials Science, Chapter 1, Introduction

Introduction To Materials Science, Chapter 1, Introduction

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University of Virginia, Dept. of Materials Science and Engineering

University of Virginia, Dept. of Materials Science and Engineering

University of Virginia, Dept. of Materials Science and Engineering