Microstructures and mechanical properties of

metals

Bonding
+
Crystal Structure
+ Properties
Defects
Atomic Structure and Interatomic Bonding
Review of Atomic Structure Masses:
• The bonding mechanisms between • Protons and Neutrons have the same
atoms are closely related to the mass, 1.67 × 10-27 kg.
structure of the atoms themselves. • Mass of an electron is much smaller,
9.11 × 10-31 kg and can be neglected in
Atoms = nucleus (protons and neutrons) + electrons calculation of atomic mass
Charges: The atomic mass (A) = mass of protons
+ mass of neutrons
• Electrons and protons have negative • # protons gives chemical
and positive charges of the same identification of the element
magnitude, 1.6 × 10-19 Coulombs.
• Neutrons are electrically neutral. • # protons = atomic number (Z)
• # neutrons defines isotope number
Types of Bonding

Primary bonding Secondary Bonding

e- are transferred or shared Strong (100- no e- transferred or shared Interaction
1000 KJ/mol or 1-10 eV/atom) of atomic/molecular dipoles Weak (<
• Ionic: Strong Coulomb interaction among 100 KJ/mol or < 1 eV/atom)
negative atoms (have an extra electron • Fluctuating Induced Dipole (inert
each) and positive atoms (lost an gases, H2, Cl2…)
electron). Example - Na+Cl-
• Covalent: electrons are shared between • Permanent dipole bonds (polar
the molecules, to saturate the valency. molecules - H2O, HCl...)
Example - H2 • Polar molecule-induced dipole bonds
• Metallic: the atoms are ionized, loosing (a polar molecule
some electrons from the valence band. • induces a dipole in a nearby nonpolar
Those electrons form a electron sea, atom/molecule)
which binds the charged nuclei in place
Types of Solids

Crystalline material: atoms self-

organize in a periodic array

Amorphous: disordered lack of

Polycrystalline material:
a systematic atomic arrangement
Comprised of many small crystals
or grains
Crystal structures

• Why do atoms assemble into ordered structures (crystals)?

Energy of interatomic bond

• Minimize potential energy

• Energy of the crystal < Energy of the amorphous solid

Repulsive energy +Attractive energy

Interatomic distance
The Structure of Crystalline Solids
• The properties of some materials are • When describing crystalline structures,
directly related to their crystal structures. atoms (or ions) are thought of as being
• Solid materials may be classified solid spheres having well-defined
according to the regularity with which diameters.
atoms or ions are arranged with respect UNIT CELLS
to one another • The atomic order in crystalline solids
• A crystalline material is one in which the indicates that small groups of atoms form
atoms are situated in a repeating or a repetitive pattern. Thus, in describing
periodic array over large atomic crystal structures, it is often convenient to
distances; that is, long-range order exists, subdivide the structure into small repeat
such that upon solidification, the atoms entities called unit cells.
will position themselves in a repetitive
three-dimensional pattern, in which each
atom is bonded to its nearest-neighbor
atoms.
METALLIC CRYSTAL STRUCTURES
The Face-Centered Cubic Crystal Structure • These spheres or ion cores touch one another
across a face diagonal; the cube edge length a and
• The crystal structure found for many metals has a the atomic radius R are related through
unit cell of cubic geometry, with atoms located at
each of the corners and the centers of all the cube
faces, face-centered cubic (FCC) crystal structure.
• Some of the familiar metals having this crystal 𝑎 = 2𝑅 2
structure are copper, aluminum, silver, and gold
• 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,
• kk or a total of four whole atoms, may be assigned to
a given unit cell.
• Corner and face positions are really equivalent;
that is, translation of the cube
• corner from an original corner atom to the center
of a face atom will not alter the cell structure.
• Two other important characteristics of • 𝐴𝑃𝐹 =
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑎𝑡𝑜𝑚𝑠 𝑖𝑛 𝑎 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙
a crystal structure are the 𝑡𝑜𝑡𝑎𝑙 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 𝑣𝑜𝑙𝑢𝑚𝑒
coordination number and the atomic
packing factor (APF).
• For the FCC structure, the atomic
• For metals, each atom has the same packing factor is 0.74, which is the
number of nearest-neighbor or maximum packing possible for
touching atoms, which is the spheres all having the same diameter.
coordination number. For face-
centered cubics, the coordination
number is 12.
• The APF is the sum of the sphere
volumes of all atoms within a unit cell
(assuming the atomic hard-sphere
model) divided by the unit cell
volume.
The Body-Centered Cubic Crystal Structure
• Another common metallic crystal structure also
has a cubic unit cell with atoms located at all eight
corners and a single atom at the cube center, body-
centered cubic (BCC).
• 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 • The coordination number for the BCC crystal
• Chromium, iron and tungsten have a BCC structure. structure is 8; each center atom has as nearest
neighbors its eight corner atoms. Because the
• Two atoms are associated with each BCC unit cell: coordination number is less for BCC than FCC, so
the equivalent of one atom from the eight corners, also is the atomic packing factor for BCC lower—
each of which is shared among eight unit cells, and 0.68 versus 0.74.
the single center atom, which is wholly contained
within its cell. In addition, corner and center atom
positions are equivalent.
The Hexagonal Close-Packed Crystal Structure
• HCP unit cells is presented in Figure. The top and • The atoms in this midplane have as nearest
bottom faces of the unit cell consist of six atoms neighbors atoms in both of the adjacent two
that form regular hexagons and surround a single planes.The equivalent of six atoms is contained in
atom in the center. 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 midplane interior
atoms.
• The coordination number and the atomic packing
factor for the HCP crystal structure are the same as
for FCC: 12 and 0.74, respectively

• Another plane that provides three additional

atoms to the unit cell is situated between the top
and bottom planes.
DENSITY COMPUTATIONS
• A knowledge of the crystal • Where; n is number of atoms
structure of a metallic solid associated with each unit cell, A
permits computation of its is atomic weight, VC is volume of
theoretical density through the the unit cell and NA is Avogadro’s
relationship number 16.022 1023
𝑛𝐴 atoms/mol2
𝜌=
𝑉𝑐 𝑁𝐴
POLYMORPHISM AND ALLOTROPY
• Some metals, as well as non- Allotropy: An example of allotropy
metals, may have more than one is carbon, which can exist as
crystal structure, a phenomenon diamond, graphite, and
known as polymorphism. amorphous carbon.
• When found in elemental solids, •
the condition is often termed
allotropy.
• The prevailing crystal structure
depends on both the
temperature and the external
pressure
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.
 Anisotropy

• Different directions in a crystal have 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
•
Defects in Solids
Why are defects important?
• Production of advanced
semiconductor devices require not
only a rather perfect Si crystal as
starting material, but also involve
introduction of specific defects in
small areas of the sample.
• Defects are responsible for color (&
price) of a diamond crystal.
• Forging a metal tool introduces
defects … and increases strength of
the tool.
 Defects in Crystals
• Processing allows one to achieve the
required properties without changes in Real crystals are never perfect,
composition of the material, but just
by manipulating the crystal defects. there are always defects
• Control (and intentional introduction)
of defects is in the core of many types
of material processing.
Imperfections in Solids
Types of Defects

Several different imperfections are Point Defects:Vacancies

discussed in this chapter, including • The simplest of the point defects
point defects:(those associated is a vacancy, or vacant lattice
with one or two atomic positions) site, one normally occupied from
linear (or one-dimensional): which an atom is missing.
defects, and interfacial defects, or
boundaries, which are two-
dimensional. Impurities in solids
are also discussed, because
impurity atoms may exist as point
defects.
• All crystalline solids contain • In this expression, N is the total
vacancies and, in fact, it is not number of atomic sites, is the
possible to create such a material energy required for the formation
that is free of these defects. The of a vacancy, T is the absolute
necessity of the existence of temperature1 in kelvins, and k is
vacancies is explained using the gas or Boltzmann’s constant.
principles of thermodynamics; in The value of k is 1.38 1023 J/atom
essence, the presence of vacancies K, or 8.62 105 eV/atom K,
increases the entropy (i.e., the depending on the units of Qv.2
randomness) of the crystal. 𝑄𝑣
−𝑘𝑇
𝑁𝑣 = 𝑁𝑒𝑥𝑝
• The equilibrium number of
vacancies for a given quantity of
material depends on and increases
with temperature according to
Other point defects: self-interstitials, impurities

Schematic representation of different

1
3 point defects
• (1) vacancy;(2) self-interstitial;
4
(3)interstitial impurity;
(4,5) substitutional impurities
2

5
Dislocations—Linear 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.
Edge and screw dislocations

• Dislocations shown in previous slide are edge dislocations. They 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).
• The number of dislocations in a material is expressed as the
dislocation density - the total dislocation length per unit volume or
the number of dislocations intersecting a unit area. Dislocation
densities can vary from 105 cm-2 in carefully solidified metal crystals
to 1012 cm-2 in heavily deformed metals.
• Most crystalline materials, especially metals, have dislocations in their
as-formed state, mainly as a result of stresses (mechanical, thermal...)
associated with the forming process.
References
• Askeland, Donald R., Wright, Wendelin J Essentials of Materials
Science & Engineering, SI Edition (9781111576868)
• William D. Callister Jr., David G. Rethwisch Materials Science and
Engineering: An Introduction, 10th Edition. . ISBN: 978-1-119-40549-8
January 2018