MME 297: Lecture 05,06

Structure-Property Correlation
The structure of solids 2
 Topics to discuss today ...

 Polymer structures
 Occurrence and importance of crystalline imperfections
 Classification of crystalline imperfections
 Point defects

References:
1. W D Callister, Jr. and D G Rethwisch. Materials Science and Engineering – An Introduction
9th Ed, Wiley, 2014
 POLYMER MOLECULES
 Polymer molecules are very large: they are macromolecules.

 Most polymers consist of long

and flexible chains with a string
of C atoms as a backbone.
 C atoms are side-bonded to H
atoms or radicals
 Double bonds are possible in
both chain and side bonds

Three ways to represent the structure of

polyethylene:
(a) a solid three-dimensional model,
(b) a three-dimensional “space” model, and
(c) a simple two-dimensional model.
 Polymer molecular shape

 The angle between the singly bonded

carbon atoms is 109°
 carbon atoms form a zigzag pattern in
a polymer molecule.

r = ln

 While maintaining the 109° angle r = head-toe distance

n = no. of steps
between bonds, polymer chains can l = length of step
rotate around single C-C bonds random kinks and coils lead to
entanglement, like in the spaghetti structure
(although double, triple bonds are very rigid).
 Polymer molecular structure

Branched polymers
• Inefficient chain packing
causes reduced density
• Examples: LDPE
Linear polymers
• Van der Waals bonding between chains.
• Examples: polyethylene, nylon, HDPE. Network polymers
 3D networks made from trifunctional mers.
 Examples: epoxies, phenol formaldehyde

Cross-linked polymers
• Chains are connected by
covalent bonds.
• Example: rubbers.
 HDPE

LDPE
(a) Linear, unbranched polymer (b) Linear, branched polymer

Branching increases the

volume and thus reduces
(c) Cross-linked, unbranched polymer (d) Cross-linked, branched polymer the density of the polymer.
Schematic showing linear and branched polymers. Note that branching can occur in any type of polymer (e.g.,
thermoplastics, thermosets, and elastomers), but not cross-linking. (a) Linear unbranched polymer: notice chains are
not straight lines and not connected. Different polymer chains are shown using different shades and design to show
clearly that each chain is not connected to another. (b) Linear branched polymer: chains are not connected, however
they have branches. (c) Thermoset polymer without branching: chains are connected to one another by covalent
bonds but they do not have branches. Joining points are highlighted with solid circles, (d) Thermoset polymer that has
branches and chains that are interconnected via covalent bonds. Different chains and branches are shown in different
shades for better contrast. Places where chains are actually chemically bonded are shown with filled circles.
 Polymer crystallinity

 Atomic arrangement in polymer crystals is complex.

 Polymer molecules are often semi-crystallined, with partially crystalline region
crystalline regions dispersed within amorphous material.

rc (rs–ra)
% Crystallinity = x100
rs (rc–ra)
rc = density of perfect crystalline polymer
ra = density of completely amorphous polymer
rs = density of partially crystalline polymer sample

amorphous region
 The degree of crystallinity depends on
1. Rate of cooling (faster cooling, less crystallinity)  annealing causes crystalline
regions to grow %  crystallinity ↑
2. Type of polymer (simple structure, more crystallinity)
3. Linear polymer more easily form crystals.  Density, TS, E ↑ with crystallinity
 EXAMPLE PROBLEM 14.2
Computations of the Density and Percent Crystallinity of Polyethylene

(a) Compute the density of totally crystalline polyethylene. The orthorhombic unit cell
for polyethylene, which is equivalent of two ethylene repeat units, is contained within
each unit cell, has the edge lengths of a=0.741 nm, b=0.494 nm, and c=0.255 nm.

(b) Using the answer to part (a), calculate the percent crystallinity of a branched
polyethylene that has a density of 0.925 g/cm3. The density for the totally amorphous
material is 0.870 g/cm3.
 n = number of repeat units within the unit cell (for polyethylene n = 2)

A = repeat unit molecular weight, which for polyethylene is

2(AC) + 4(AH) = (2)(12.01 g/mol) + (4)(1.008 g/mol) = 28.05 g/mol

VC = unit cell volume (which is the product of the three unit cell edge lengths)
VC = (0.741 nm)(0.494 nm)(0.255 nm) = 9.33*10-23 cm3/unit cell

Then, density of polyethylene

(b) To calculate the percent crystallinity of the branched polyethylene,
we have rc = 0.998 g/cm3, ra = 0.870 g/cm3, and rs = 0.925 g/cm3.

𝜌𝑐 𝜌𝑠 − 𝜌𝑎
% crystallinity = x 100
𝜌𝑠 𝜌𝑐 − 𝜌𝑎

0.998 g/cm3 (0.925 g/cm3 – 0.870 g/cm3)

= x 100
0.925 g/cm3 (0.998 g/cm3 – 0.870 g/cm3)

= 46.4%
 CRYSTALLINE IMPERFECTIONS

“Crystals are like people, it is the defects in them

which tend to make them interesting!”
Colin Humphreys, Professor and Director Research
Department of Materials Science and metallurgy, University of Cambridge, UK

 Real crystals are never perfect, there are always defects

 Most atoms are in ideal locations, only small numbers are out of place
 Most defects cause the periodicity of the crystal to be disturbed
over distances of several atomic diameters from the defect
 Defects have a profound impact
on the macroscopic properties of materials

 Based on the bond strength, most materials should be

much stronger than they are. Why?
Strength of an ionic bond ≈ 106 psi,
but more typical strength is 40x103 psi.

 Materials do not usually fail by breaking bonds!!

Bonding
+
Structure Properties
+
Defects
 The processing of materials
determines the nature and amount of defects in it.

Composition

Bonding Crystal structure

Thermo-mechanical processing

defect introduction and manipulation

Microstructure
 why are defects important ?

 Defects, even in very small concentrations, can have

a dramatic impact on properties of material.

 Without defects:
• solid-state electronic devices could not exist
• metals would be much stronger
• ceramics would be much tougher
• crystals would have no color
CLASSIFICATION OF CRYSTAL DEFECTS
based on dimensions of defects

0D, Point defects 1D, Line defects

 vacancies
 interstitials  dislocations
 substitutional

2D, Surface defects 3D, Bulk / Volume defects

 external surfaces  porosity
 grain boundaries  crack
 twin boundaries  foreign inclusion
 POINT DEFECTS

 Localized disruptions in the lattice involving one or more atoms.

 All real materials have point defects.

More can be added by
• heating of material
• processing of material
• introducing impurities during materials processing
• intentionally adding during alloying

 Affect material properties by influencing

• atomic movement (diffusion process)
• dislocation movement (strengthening methods)
Classification of Point defects:
(a) Vacancy (c) Small substitutional atom (e) Frenkel defect (vacancy-interstitial pair)
(b) Interstitial atom (d) Large substitutional atom (f) Schottky defect (anion-cation vacancy pair)
 vacancy
• a lattice position that is vacant because the atom is missing
• occurs as a result of the periodic oscillation or thermal vibration of atoms
• controls atomic motion in solids
Concentrations of vacancies increase with:
• increasing temperature, T
• decreasing activation energy, QV
How many vacancies are there?
Defect
concentration, exponential
−𝑄𝑣 Nv / N
𝑁𝑣 = 𝑁 exp dependence
𝑘𝑇
NV = number of vacancies
N = total number of atomic sites T
QV = activation energy for the formation of a vacancy Slope = - (Qv / k)
ln (Nv / N)
K = Boltzmann’s constant = R/NA
= 1.38x10-23 J/atom-K = 8.62x10-5 eV/atom-K
T = temperature in Kelvin

T
 Example 1:
The effect of temperature on vacancy concentrations

Calculate the equilibrium number of vacancies per cubic meter for copper at 27 °C
and 1000°C. The energy for vacancy formation is 0.9 eV/atom; the atomic weight
and density for copper are 63.5 g/mol and 8.4 g/cm3, respectively.

Number of regular atomic sites per m3 for copper

NA r
N =
ACu
(6.023*1023 # atom/mol) x (8.4 g/cm3) x (106 cm3/m3)
= (63.5 g/mol)

= 7.96*1028 # atom/m 3
The number of vacancies at 27°C (= 300 K):
NV = N exp (-QV / kT)
- 0.9 eV/atom
= ( 7.96*1028 # atoms/m3 ) x exp
(8.62*10-5 eV/K) x (300 K)
= 6.11*1013 vacancies/m 3

About one vacancy in every 1000 trillion (1015) lattice atoms

The number of vacancies at 1000°C (= 1273 K):

NV = N exp (-QV / kT)
- 0.9 eV/atom
= (7.96*1028 # atoms/m ) x exp
3

(8.62*10-5 eV/K) x (1273 K)

= 2.18*1025 vacancies/m 3

About one vacancy in every 3000 lattice atoms

 Impurities and alloys

 Impurity atoms are different from the host atoms.

 All real solids are impure. Very pure metals are only about
99.9999% pure (i.e., ~ one impurity per 106 host atoms)

 May be intentional or unintentional

Examples:
 Carbon added in small amounts to iron makes steel,
which is stronger than pure iron (alloying)
 Sulphur remained in steel due to difficulties in synthesis (impurity)
 Sulphur lowers transverse ductility and notched impact toughness
 Two outcomes, when an alloying element B is added to a host A:

 Form a solid solution of B in A (i.e., random distribution of point defects)

OR

Substitutional alloy Interstitial alloy

(e.g., Cu in Ni) (e.g., C in Fe)

 Form a solid solution of B in A plus formation of new phase

second phase particle

--different composition
--often different structure
 Interstitial solid solution

 Metallic materials have relatively high APF, making interstitial

positions relatively small.

 An atom must be fairly tiny to fit into the interstitial holes.

 The maximum allowable concentrations of interstitial impurities

is ~10% (Example: only 2% max. C in Fe-C system)

 Even very small impurity atoms are larger than interstitial sites,
so all interstitial impurities introduce lattice strains on the
adjacent host atoms.
  Carbon distorts the BCC crystal structure more
than the FCC crystal –why?

 Fewer carbon atoms enter the interstitial positions

in BCC iron than in FCC iron –why?

Application: Enhancement of properties of steel by heat treatment

• FCC steel structure can absorb up to 2% C at a temperature above 723°C

• During slow cooling, FCC steel changes into BCC steel, which can absorb only about
0.008% C at room temperature
• So the extra C comes out from the FCC steel and BCC steel is formed, which, having
a very low C, is very soft and ductile
• But, if the FCC steel is cooled very fast, the extra C cannot come out of it and the
FCC steel cannot form BCC steel during cooling
• Instead, a distorted BCT structure with high C is formed, which is very hard and brittle
 Linear Defects

 Line defects, a.k.a. dislocations, are one-dimensional imperfections

in crystal structure where a row of atoms have a local structure that
differs from the surrounding crystal.

 These type of defects are almost always present in a real crystals.

 In a typical material, about 5 out of every 100 million atoms
(0.000005%) belongs to a line defect.
 In a 10-cm3 chunk of material (about the size of a six-sided die),
there will be about 1017 atoms belonging to line defects!

 Line defects have a dramatic impact on yielding (i.e., mechanical

deformation) of materials.
 characteristics of dislocations

 Intrinsic defect

 Not equilibrium defects

 Concentrations not given by Boltzmann factors
 Given enough time and thermal energy, atoms will rearrange
to eliminate dislocations

 Caused by processing conditions (how the material is made),

and by mechanical forces that act on the material

 Line defects are identified by

 Dislocation line — indicates position and orientation of dislocation
 Burger’s vector — describes unit slip distance (magnitude and direction )
 classification of dislocations

 Edge dislocation - A dislocation introduced into the crystal

by adding an “extra half plane” of atoms

 Screw dislocation - A dislocation produced by skewing a

crystal so that one atomic plane produces a spiral ramp
about the dislocation.

 Mixed dislocation - A dislocation that contains partly edge

components and partly screw components.
 edge dislocations

 Can be viewed as an extra part of a plane of atoms inserted

into the structure, which terminates somewhere inside the crystal.
 The termination of this extra part-plane of atoms creates a
defect line (dislocation line) in the lattice (line DC in figure ).

edge
• The edge dislocation is dislocation
designated by a
perpendicular sign, either
⊥ if the half plane is above
the dislocation line, or T
if the plane is below the
dislocation line.

slip plane
 screw dislocations

 A dislocation produced by skewing a crystal so that one atomic

plane produces a spiral ramp about the dislocation
 Formed due to the application of a shear stress

• The perfect crystal is

horizontally cut and sheared one
atom spacing.
• The top region of the crystal is
then shifted/twisted one atomic
distance rightward relative to the
bottom side of the crystal.
• The line along which shearing
occurs is a screw dislocation.

dislocation
line
Burgers vector, b
 mixed dislocations

 When a line defect has both an edge

and screw dislocation component, a
mixed dislocation results.

• In this case, the Burger’s vector is

neither parallel nor perpendicular to the
dislocation line, but can be resolved into
edge and screw components.

 The exact structure of dislocations in real crystals is usually more complicated.

Edge and screw dislocations are just extreme forms of the possible dislocation
structures. Most dislocations have mixed edge/screw character.
 Surface defects

 Surface defects – Imperfections that form a two-dimensional

plane within the crystal.

 Classes of surface defects

1. External surface
2. Grain boundary
3. Twin boundary
 External surfaces

 Surface atoms have unsatisfied atomic bonds, and higher surface

energies, g (J/m2 or, erg/cm2) than the bulk atoms.

 To reduce surface free energy, material tends to minimize its surface

areas against the surface tension.
• For example, liquids assume a shape having a minimum area
—the droplets become spherical.
• Of course, this is not possible with solids, which are mechanically rigid,
and have very high surface tension.
 Grain boundaries
 Polycrystalline material comprised of many small crystals or grains having
different crystallographic orientations.
 Atomic mismatch occurs within the regions where grains meet.
These regions are called grain boundaries.
 Segregation of impurities occurs at grain boundary.
 Dislocations can usually not cross the grain boundary.

(a) The atoms near the

boundaries of the three
grains do not have an
equilibrium spacing or
arrangement.
(b) Grains and grain
boundaries in a stainless
steel sample.
 Twin boundaries

 Special grain boundaries with mirrored atomic positions across the boundary.
 Produced by shear deformation of BCC/HCP materials (mechanical twin), or
during annealing following deformation (annealing twin) of FCC materials.

Application of a stress to the perfect crystal (a) may cause a displacement of the atoms,
(b) causing the formation of a twin. Note that the crystal has deformed as a result of twinning.
 Bulk or Volume Defects

Pores
affect optical, thermal, and mechanical properties

Cracks
act as stress concentrator and affect mechanical properties

Foreign inclusions
affect electrical, mechanical, optical properties