Chapter 4 -

Defects - Introduction
Crystals are like people, it is the defects in them which tend to make them interesting! (Colin Humphreys) Real crystals are never perfect, there are always defects

Chapter 4 -

Chapter 4: Imperfections in Solids

ISSUES TO ADDRESS...
What are the solidification mechanisms? What types of defects arise in solids?

Can the number and type of defects be varied and controlled?

How do defects affect material properties? Are defects undesirable?

Chapter 4 - 3

Defects - Introduction
Defects have a profound impact on the macroscopic properties of materials The processing determines the defect Control defects control

properties

Imperfections in Solids
Solidification- result of casting of molten material
2 steps
Nuclei form Nuclei grow to form crystals grain structure

Start with a molten material all liquid

nuclei liquid

crystals growing

grain structure

Adapted from Fig. 4.14(b), Callister & Rethwisch 8e.

Crystals grow until they meet each other

Chapter 4 - 5

Imperfections in Solids
There is no such thing as a perfect crystal. What are these imperfections? Why are they important?
Many of the important properties of materials are due to the presence of imperfections.

Chapter 4 - 6

Types of Imperfections
Vacancy atoms Interstitial atoms Substitutional atoms

Point defects

Dislocations Grain Boundaries

Pores

Line defects
Area defects Volume defects
Chapter 4 - 7

Types of Defects
Defects may be classified into four categories depending on their dimensions
0D, point defects: atoms missing or in irregular places in the lattice (vacancies, interstitials, impurities) 1D, linear defects: groups of atoms in irregular positions (e.g. screw and edge dislocations) 2D, planar effects: the interfaces between homogeneous regions of the material (grain boundaries, external surfaces) 3D volume defects: extended effects (pores, cracks)

Chapter 4 -

Point Defects in Metals

Vacancies: vacant atomic sites in a structure.

Vacancy
distortion of planes Inwards

Self-Interstitials: "extra" atoms positioned between atomic sites.

selfinterstitial
distortion of planes Outwards
Chapter 4 - 9

Equilibrium Concentration: Point Defects

Equilibrium concentration varies with temperature!

Activation energy
No. of defects

Qv N v = N exp - kT
Boltzmann constant

No. of potential defect sites

-23

Temperature

(1.38 x 10 J/atom-K) -5 (8.62 x 10 eV/atom-K) Each lattice site is a potential vacancy site

Chapter 4 - 10

Estimating Vacancy Concentration

Find the equil. # of vacancies in 1 m3 of Cu at 1000C. Given: A Cu = 63.5 g/mol = 8.4 g/cm3 Qv = 0.9 eV/atom NA = 6.02 x 1023 atoms/mol 0.9 eV/atom

Nv Qv = exp - = 2.7 x 10-4 kT N 1273 K

8.62 x 10-5 eV/atom-K NA 3 x 1 m3 = 8.0 x 1028 sites For 1 m , N = A Cu

Nv = (2.7 x 10-4)(8.0 x 1028) sites = 2.2 x 1025 vacancies

Chapter 4 - 11

For 1

m3 ,

NA N= A Cu

x 1 m3 = 8.0 x 1028 sites

mass 3 volume = mass in 1 m volume

NA = # atoms / g Acu

Chapter 4 - 12

Measuring Activation Energy

We can get Qv from an experiment. Measure this... Nv N
exponential dependence!

-Q v Nv = exp kT N
Replot it... Nv N slope -Q v / k

ln

1/ T
Chapter 4 - 13

defect concentration

Observing Equilibrium Vacancy Conc.

Low energy electron microscope view of a (110) surface of NiAl. Increasing temperature causes surface island of atoms to grow. Why? The equil. vacancy conc. increases via atom motion from the crystal to the surface, where they join the island.
I sland grows/shrinks to maintain equil. vancancy conc. in the bulk.
Click once on image to start animation

Reprinted with permission from Nature (K.F. McCarty, J.A. Nobel, and N.C. Bartelt, "Vacancies in Solids and the Stability of Surface Morphology", Nature, Vol. 412, pp. 622-625 (2001). Image is 5.75 mm by 5.75 mm.) Copyright (2001) Macmillan Publishers, Ltd.

Chapter 4 - 14

Defects in Surface Science & Catalysis

fig_04_10

Chapter 4 -

Transmission Electron Microscopy (TEM)

Dots? Raws? Guess where is the d-spacing??

fig_04_11

Chapter 4 -

here is the dspacing??

Chapter 4 - 17

Impurities in Solids
A pure metal with only one type of atom does not exist In alloys impurity is added intentionally to impart specific properties (e.g. mechanical properties and corrosion) E.g. sterling Ag (92.5% Ag-7.5%Cu) Solid Solutions: When impurity is added into host material and crystal structure is maintained with no new crystals formed The impurity is randomly dispersed Substitution: when substitution on host atoms take pace with impurity Solute and Solvent or Host and Guest
Chapter 4 - 18

Imperfections in Metals (i)

Two outcomes if impurity (B) added to host (A):
Solid solution of B in A (i.e., random dist. of point defects)

HOST GUEST OR

Substitutional solid soln. (e.g., Cu in Ni) RCu = 0.128 nm RNi = 0.125 nm FCC structure

Interstitial solid soln. (e.g., C in Fe) RFe = 0.124 nm RC = 0.071 nm

Small voids in metals due to ????. Interstitial atom should be very small. Less than 10%
Chapter 4 - 19

 Solid solution of B in A plus particles of a new phase (usually for a larger amount of B)
Second phase particle -- different composition -- often different structure.

CeO2-ZrO2 solid solution: By adding ZrO2 into c-CeO2 there is a certain composition range where the c-CeO2 lattice is preserved. But due to Zr r the XRD pattern is shifted to higher 2theta

Ce3+ (102.5pm) vs. Zr4+ (72pm)

Chapter 4 - 20

Role of Metal Atoms Size

Why?

Ce-Sm-O
20/80 60/40

Ce-Zr-O

20/80

40/60

40/60

80/20
100/0
20 30 40 50 60 70 80
20 30 40 50 60 70

60/40

80/20

100/0

2 (degrees)

80

2 (degrees)

Ce3+ (102.5pm) vs. Zr4+ (72pm), (radius difference 30%)

Ce3+ = 102.5 pm; Sm3+ = 127 pm (radius difference 6.5%)
K. Polychronopoulou, unpublished results
Chapter 4 - 21

For substitutional defects, theyll do so if

Atoms should have similar properties: Hume-Rothery rules (for solid solution formation): Similar radii (less than 15% difference) (otherwise: high distortions and new phase will be formed) Similar electronegativity (x increases intermetallic and not solid solution) Same crystalline structures (FCC, BCC, HCP,) Valency compatibility Valency rule: All else being identical, a metal will have higher tendency to dissolve metals of higher valency Example: Cu-Ni, FCC both, x: 1.9 & 1.8, rCu=0.128 nm And rNi=0.125 nm Chapter 4 - 22

Impurities in Solids
Specification of composition
weight percent

m1 C1 = x 100 m1 + m2

m1 = mass of component 1

atom percent

nm1 C = x 100 nm1 + nm 2

' 1

nm1 = number of moles of component 1

Chapter 4 - 23

Composition Conversion Weight percent Atom percent (self study)

Chapter 4 - 24

Imperfections in Solids
Linear Defects (Dislocations)
Are one-dimensional defects around which atoms are misaligned

Edge dislocation:
extra half-plane of atoms inserted in a crystal structure

b perpendicular to dislocation line

Screw dislocation:
spiral planar ramp resulting from shear deformation

b parallel to dislocation line

Burgers vector, b: measure of lattice distortion (magnitude+ direction!)
Chapter 4 - 25

Imperfections in Solids
Edge Dislocation (symbiol: )
Slight curvature due to the stress introduced to the lattice far from the defect Bottom of the crystal () Localized lattice distortion

Pull apart squeezed

Fig. 4.3, Callister & Rethwisch 8e.

Chapter 4 -26

Burger s Vector

For edge dislocation their direction is perpendicular and for Screw dislocation the are parallel Neither parallel nor perpendicular for mixed dislocation

Chapter 4 -

Imperfections in Solids
Screw Dislocation (also linear): formed by a shear stress
Screw Dislocation
View From above

Dislocation line Burgers vector b (a)

b (b) Adapted from Fig. 4.4, Callister & Rethwisch 8e.

When shear stress is applied One atomic distance shift of the upper part of the crystal to the right AB line: dislocation line Spiral path around the dislocation Burger vector // dislocation line

Chapter 4 - 28

Burger s Vector

Chapter 4 -

Edge, Screw, and Mixed Dislocations

Mixed for regions in between A-B

Edge
Adapted from Fig. 4.5, Callister & Rethwisch 8e.

Screw
Chapter 4 - 31

Along the mixed dislocation line the burger vector remains the same

Imperfections in Solids
Dislocations are visible in electron micrographs (TEM)

Ti-alloy (dark lines are dislocations)

Dislocations play significant role in the plastic deformation of metals and ceramics!

Fig. 4.6, Callister & Rethwisch 8e.

Chapter 4 - 32

Interface of CdTe (cubic)/CdS (hexagonal)

Thin Solid Films, 519, Issue 21 (2011) Pages 71687172

Chapter 4 - 33

 External surface (crystal Structure terminates, Unsaturated atoms, surface energy in J/m2)
Grain boundaries Phase boundaries Twin boundaries

Types of 2D (Interfacial defects) boundaries

http://www.mete.metu.edu.tr/pages/tem/projects/samples/samples.htm P34

doi: 10.1590/S1516-14392008000100020

Chapter 4 -

Polycrystalline Materials
Grain Boundaries
regions between crystals transition from lattice of one region to that of the other Different crystallographic orientation (atomic mismatch) slightly disordered low density in grain boundaries
high mobility high diffusivity high chemical reactivity
Adapted from Fig. 4.7, Callister & Rethwisch 8e.

Chapter 4 - 35

Planar Defects in Solids

One case is a twin boundary (plane)
Essentially a reflection of atom positions across the twin plane. Mechanical forces or annealing (mechanical-BCC, HCP & annealing twins-FCC)

Adapted from Fig. 4.9, Callister & Rethwisch 8e.

Stacking faults
For FCC metals an error in ABCABC packing sequence Ex: ABCABABC

Chapter 4 - 36

Bulk OR Volume Defects

Pores, cracks, foreign inclusions are examples

Atomic Vibrations
Atomic vibrations are thought of being defects The temperature of a solid is just the measure of vibration activity of its atoms and molecules
Chapter 4 - 37

Grain Size Determination

~670 um /7=95.7 um

~670 um /8=83.8 um

Chapter 4 - 38

Sizes of Several Structures in Materials

fig_04_15a

Chapter 4 -

Resolution Sizes of Microscopies

fig_04_15b

Chapter 4 -

Chapter 4 -

fig_04_13a

Microscopies
Incoming beam of e-

Backscattered eX-rays secondary ephotons

sample

Diffracted e-

outgoing e-

SEM: Scanning electron microscopy X100,000 TEM: Transmission electron microscopy Chapter 4 - 42 X1,000,000

Summary
Point, Line, and Area defects exist in solids. The number and type of defects can be varied and controlled (e.g., T controls vacancy conc.) Defects affect material properties (e.g., grain boundaries control crystal slip).

Defects may be desirable or undesirable

(e.g., dislocations may be good or bad, depending on whether plastic deformation is desirable or not.)

Chapter 4 - 43