The Structure of Solids

Quantum Theory
Wave – Particle Duality Model
 Most accepted structural model of the electron
 In this model, the electron sometime behaves like a wave and sometimes behave like a particle but do not
behave both particle and wave at the same time
 For example, electron behaves like a particle if you touch an object. You can feel material since it’s a particle.
The electron becomes wavelike if used on the operation of cathode ray tubes in TVs
Implication of Wave Particle Duality
 Since electrons sometimes behave in a wavelike property, we can only determine the most probable position an
electron can be at a given time
 Comparison of the (a) Bohr atom and (b) wave mechanical atom models in
terms of electron distribution.

Atomic Bonding in Solids

Bonding forces and energies:
 When 2 isolated atoms are at a distant proximity with each other, attractive
forces will pull each other together
 However, at very close proximity, repulsive force will be the dominant force that
will keep each other apart
The dependence of repulsive, attractive, and
net forces on interatomic separation for two
isolated atoms.

 From classical physics, the total resultant force is the sum of all the forces
acting on the particle. In this case, the resultant force is the sum of the
repulsive and attractive forces or
 F resultant = F repulsive + F attractive
 Therefore at the state of equilibrium, the resultant force is zero
Bonding Energy
 Energy Eo required to separate 2 atoms to an infinite or very long distance
 The bonding energy is dependent on the type of atomic bonding the atoms have
 This implies that high bonding energies have high melting point/temperature
 Solid substances are formed if there is high bonding energy
 Gaseous State is favored for low bonding energy
PRIMARY INTERATOMIC BONDS
 Ionic Bonds
 Covalent Bonds
 Metallic Bonds
Ionic Bonding
 Type of chemical bond formed through an electrostatic attraction
between two oppositely charged ions.
 Ionic bonds are formed between a cation, which is usually a metal, and
an anion, which is usually a nonmetal. Atoms of a metallic element
easily give up their valence electrons to the nonmetallic atoms. In the
process all the atoms acquire stable or inert gas configurations and
they become ions

PRIMARY INTERATOMIC BONDS

Covalent Bonding

 Sharing of electrons between 2 atoms

 Two atoms that are covalently bonded will each contribute at least one electron to the bond, and the shared
electrons may be considered to belong to both atoms.
 Schematic representation of covalent bonding in a molecule of methane

Metallic Bond

 Bond existing in metals wherein the electrons are freely roaming on the metal
 Since the electrons are freely roaming, the electrons can be stated as “electron
clouds” inside the materials
 Metallic bonding showing electron clouds

Secondary Bond or Van Der Waals

 Exists in every atoms and molecules

 Due to interaction between poles (positive and negative) of molecules
 Hydrogen Bonds exists for molecules with hydrogen atoms

 Secondary Bonding or Van der Waals Bonding. The Figure shows the schematic
representation of polar hydrogen chloride molecule. The hydrogen parts maybe
considered the positive part while the chlorine side denotes the negative part

 The hydrogen from the right molecule is attracted to the

Fluorine from the left molecule creating the hydrogen bonding between the 2
molecules

Effect of Bonds to properties

 Diamond have covalent bonds which are very stable. This is the reason why diamonds are very hard to
fracture
 Metals are good conductors of electricity and heat because the electrons can freely move from one atom to
another
 In contrast, ionic and covalent bonded materials are insulators due to lack of freely moving electrons
Knowledge Application - Volume Expansion of Water upon Freezing

The arrangement of water molecules in (a) solid ice, and (b) liquid water. In solid ice, the oxygen
molecule can combine with 2 other hydrogen atoms from nearby water molecule. This forms a
structure that is less dense than that of liquid water wherein there is less structure and thus,
molecules can pack more together

STRUCTURE OF CRYSTALLINE SOLIDS

Crystalline Materials

 A crystalline material is one in which the atoms are situated in a repeating or periodic array
over large atomic distances
 All metals, many ceramic materials, and certain polymers form crystalline structures under normal solidification
conditions
 Non-crystalline or amorphous materials have small or no repeating structures

Types of Crystal Structures

Unit Cell

 Basic structural unit or building block of the crystal structure and defines the crystal structure by virtue of its
geometry and the atom positions within

The Face-Centered Cubic Crystal Structure

 The atoms are located at the corners and center of the cubes faces
 Structure of most metals Cu, Ag, Au, Al
 Unit cell edge length a with radius R for face-centered cubic

 a  2R 2
 For the FCC crystal structure, each corner atom is shared among eight
unit cells, whereas a face-centered atom belongs to only two. Therefore, one-eighth of each of the eight corner
atoms and one-half of each of the six face atoms, or a total of four whole atoms, may be assigned to a given unit
cell

The Body-Centered Cubic Crystal System

 A cubic unit cell with atoms located at all eight corners and a single atom at the cube center.
 Center and corner atoms touch one another along cube diagonals, and unit cell length a and atomic radius R are
related through
4R
a
 3
a) Hard Sphere representation of BCC
b) Reduced sphere representation of BCC
c) Aggregate of many atoms with unit cell
The Hexagonal Close-Packed Crystal Structure

 The top and bottom faces of the unit cell consist of six atoms that form
regular hexagons and surround a single atom in the center
 Another plane that provides three additional atoms to the unit cell is
situated between the top and bottom planes
 The equivalent of six atoms is contained in each unit cell; one-sixth of
each of the 12 top and bottom face corner atoms, one-half of each of
the 2 center face atoms, and all 3 mid-plane interior atoms
a) Reduced sphere unit-cell
b) Aggregate of many atoms

Lattice Parameter Relationships and Figures Showing Unit Cell Geometries for the Seven Crystal Systems

Single Crystals

When the periodic and repeated arrangement of atoms is perfect

or extends throughout the entirety of the specimen without
interruption, the result is a single crystal.

Polycrystalline Materials

Crystalline solids are

composed of a collection of
many small crystals or
grains

 Small crystallite nuclei

 Growth of crystallite
 Grains are formed
 Grains seen on
microscope

Anisotropy

 Associated with the change in the properties of the material

due to the variance of atomic or ionic spacing with
crystallographic direction
 Substances in which measured properties are independent of
the direction of measurement are isotropic.
 For many polycrystalline materials, the crystallographic
orientations of the individual grains are totally random. Under
these circumstances, even though each grain may be anisotropic, a specimen composed of the grain aggregate
behaves isotropically.

Mechanical Properties of Materials

 Stress - Force or load per unit area of cross-section over which the force or load is acting.
 Strain - Elongation change in dimension per unit length.
 Young’s modulus - The slope of the linear part of the stress-strain curve in the elastic region, same as modulus of
elasticity.
 Shear modulus (G) - The slope of the linear part of the shear stress-shear strain curve.
 (c)2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson

a) Schematic illustration of how a tensile load produces an elongation and

positive linear strain. Dashed lines represent the shape before deformation;
solid lines, after deformation.
b) Schematic illustration of how a compressive load produces contraction and a
negative linear strain
c) Schematic representation of shear strain γ
d) Schematic representation of torsional deformation (i.e., angle of twist )
produced by an applied torque T

Engineering Stress

 F is defined as instantaneous load applied perpendicular to the specimen cross section, in units of newtons (N)
 Ao is the original cross-sectional area before any load is applied (m2 or in2)
 The units of engineering stress σ (referred to subsequently as just stress) are megapascals, MPa (SI) (where 1
MPa N/m2), and pounds force per square inch, psi
F


Ao
Engineering Strain

 Δl is the change in length at some instant, as referenced to the original length lo

 lo is the original length before any load is applied
 Engineering strain ε (subsequently called just strain) is unitless
l


lo
Tensile stress-strain curves for different materials. Note that
these are qualitative
Shear Stress

 Shear Stress is computed as the ratio of the pure shear force applied parallel to the upper and lower faces, each
of which has an area of Ao
F


A0
Shear Strain - Defined as the tangent to the angle θ shown in the figure

l
  tan  

lo

Hooke’s Law

 For most metals, stress and strain are proportional to each other as described by Hooke’s law. E is the constant
of proportionality (in Gpa or psi). E is called modulus of elasticity or Young’s modulus

   E
Young’s modulus (Modulus of Elasticity)

 This modulus may be thought of as stiffness, or a material’s resistance to elastic deformation. The greater the
modulus, the stiffer the material

Elastic Deformation

 Deformation in which the stress and strain are directly proportional is called elastic
deformation

Tangent or secant modulus

 If the elastic deformation is nonlinear as in the case for polymers and

concrete, the tangent to the line will be used
 Tangent modulus is taken as the slope of the stress–strain curve at some
specified level of stress, while secant modulus represents the slope of a
secant drawn from the origin to some given point of the stress-strain curve

Shear Modulus

 Defined as the slope of the shear stress and shear strain

   G
ELASTIC PROPERTIES OF MATERIALS

Poisson’s Ratio

 Defined as the ratio of lateral and axial strains

 The figure shows the change in the cylindrical tube and how the strains and poisson’s
equation can be applied. When the force F is applied, the specimen will elongate in
the z direction and at the same time experience a reduction in diameter Δd
 y
x
  
z z
Plastic Deformation

 For most metallic materials, elastic deformation persists only to strains of about 0.005. As
the material is deformed beyond this point, the stress is no longer proportional to strain
and permanent, non-recoverable, or plastic deformation occurs
 The transition from elastic to plastic is a gradual one for most metals; some curvature
results at the onset of plastic deformation, which increases more rapidly with rising stress
 Typical stress– strain behavior for a metal showing elastic and plastic deformations, the
proportional limit P, and the yield strength as determined using the 0.002 strain offset
method.

Tensile Properties

Yielding - the stress level at which plastic deformation begins

Proportional limit - For metals that experience this gradual elastic–plastic transition, the point of yielding may be
determined as the initial departure from linearity of the stress–strain curve

Yield Strength - The stress corresponding to the intersection of this line and the stress–strain curve as it bends over in
the plastic region

Tensile Strength - The stress at the maximum on the engineering stress–strain curve

Typical engineering stress– strain behavior to fracture, point F. The tensile strength TS
is indicated at point M. The circular insets represent the geometry of the deformed
specimen at various points along the curve.

Ductility

 It is a measure of the degree of plastic deformation that has been sustained at

fracture. A material that experiences very little or no plastic deformation upon
fracture is termed brittle
 Schematic representations of tensile stress–strain behavior for brittle and ductile
materials loaded to fracture

Toughness

 it is a measure of the ability of a material to absorb energy up to fracture

 It is the area under the σ – ε curve up to the point of fracture
 For a material to be tough, it must display both strength and ductility
F
True Stress - Defined as the load F divided by the instantaneous cross-sectional area Ai over which  
Ai
deformation is occurring.
l 
True Strain - Defined as the natural logarithm of the final length li divided by the original length lo   ln  i 
 lo 
Relationship of Engineering and True Stress and Strain

 t   e 1    These equations will hold only on the onset of necking

 t  ln 1   
True Stress-Strain curve

 For some metals and alloys the region of the true stress–strain curve from the onset of plastic deformation to
the point at which necking begins may be approximated by
 t  K tn
log  t  log K  n log  tn

 In this expression, K and n are constants and will depend on the condition of the material (i.e., whether it has
been plastically deformed, heat treated, etc.). The parameter n is often termed the strain hardening exponent
and has a value less than unity
 By plotting the log of stress-strain curve, you will get the values for K and n

Hardness

 Measure of a material’s resistance to localized plastic deformation (e.g., a small dent or a scratch)
 Quantitative hardness techniques have been developed in which a small indenter is forced into the surface of a
material to be tested
 The depth or size of the resulting indentation is measured, which in turn is related to a hardness number
 The softer the material, the larger and deeper is the indentation, and the lower the hardness index number