Chap: 05 IMPERFECTIONS IN SOLIDS

Chapter 4-

IMPERFECTIONS IN SOLIDS
ISSUES TO ADDRESS...
What are crystal imperfections? 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- 1

Why bother about imperfections?

Defects or disrupted regions may be as small as 0.01%. Can be ignored if we are studying structure insensitive properties. Properties of crystalline materials dealt in engineering practice are structure sensitive. Even ppm level imperfection can radically change the properties.
Chapter 4-

The Big Picture

Mechanical properties are often related to the defect structure, with macroscopic failure commonly resulting from a coalescence of damage around existing flaws in a material compact

We have to better understand material structure in order to predict mechanical performance of a material.
Chapter 4-

The Bigger Picture

Presence of imperfections are not always bad. Point imperfections in the form of controlled impurities can improve the properties of the materials drastically. eg. Alloys where presence of impurities improve the mechanical properties of the material.

Dopants in semiconductors drastically improves the electrical properties.

Chapter 4-

What are imperfections?

We can define imperfections or defects in a crystal as:

Discontinuity or absence of periodicity in certain region of the space lattice.

Chapter 4-

TYPES OF IMPERFECTIONS
Vacancy atoms Interstitial atoms Substitutional atoms Dislocations Grain Boundaries
Foreign particle/ Large Voids/pores/ Non-Cryst regions~10
Chapter 4-

Point defects
(0-D)

Line defects
(1-D)

Area defects
(2-D)

Volume defects
3-D

POINT IMPERFECTIONS

Imperfections of zero dimensions May be created at the time of formation of crystals May be created at a later time due to some thermal disorder They are thermodynamically stable

Chapter 4-

POINT DEFECTS
Vacancies:
-vacant atomic sites in a structure.

Vacancy
distortion of planes

Impurity

Substitutional

Interstitial

Chapter 4- 3

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

distortion of planes

selfinterstitial

Low probability because atoms are substantially larger than the void
Chapter 4-

Defects in Ceramics
Still have interstitials and vacancies

Chapter 4-

Substitutional ions

Chapter 4-

DEFECTS IN CERAMIC STRUCTURES

Frenkel Defect --a cation is out of place. Schottky Defect --a paired set of cation and anion vacancies.
Schottky Shottky
Defect:
Adapted from Fig. 13.20, Callister 5e. (Fig. 13.20 is from W.G. Moffatt, G.W. Pearsall, and J. Wulff, The Structure and Properties of Materials, Vol. 1, Structure, John Wiley and Sons, Inc., p. 78.) See Fig. Frenkel 12.21, Callister 6e.

Defect

Equilibrium concentration of defects

~e

QD /2 kT

Chapter 4- 7

Imperfections in ionic crystals

Impurities must also satisfy charge balance Ex: NaCl

Na+

Clcation vacancy

Substitutional cation impurity

Ca2+ Na+ Na+ initial geometry Ca2+ impurity

Ca2+ resulting geometry

anion vacancy

Substitutional anion impurity

O2-

initial geometry

ClClO2- impurity

resulting geometry
Chapter 4- 8

Nonstoichiometry

Fe 2+ O 2- Fe 2+ O 2O 2Fe 3+ O 2Fe 2+ O 2-

O 2- Fe 2+ Fe 2+ O 2-

Fe 3+ O 2-

O 2- Fe 2+ O 2- Fe 2+

O 2-

Fe 3+ O 2-

Fe 2+ O 2- Fe 2+ O2Chapter 4-

Consequences of presence of point imperfections

Introduces distortion in crystals Elastic strains created in the neighborhood of the defect. large atom creates compressive stress-strain smaller atom introduces tensile stress-strain all these increases the energy of the system to reach a stable state G/F has to be minimum
Chapter 4-

The variation of Gibbs free energy with the number of point imperfections.
Chapter 4-

MEASURING ACTIVATION ENERGY

We can get Q from an experiment. Measure this...

Q ND = D exp kT N
Replot it...
ND ln N 1 slope -QD/k

ND N
exponential dependence!

defect concentration

1/T
Chapter 4- 5

ESTIMATING VACANCY CONC.

Find the equil. # of vacancies in 1m 3 of Cu at 1000C. Given: = 8.4 g/cm3 ACu = 63.5g/mol QV = 0.9eV/atom NA = 6.02 x 1023 atoms/mole 0.9eV/atom Q ND D -4 = exp

For 1m3, N =

Answer:

1273K 8.62 x 10-5 eV/atom-K NA x 1m3 = 8.0 x 1028 sites x ACu

kT

= 2.7 10

ND = 2.7 10-4 8.0 x 1028 sites = 2.2x 1025 vacancies

Chapter 4- 6

Impurities in Solids
Completely pure metal (or other substance) Impossible!! for 99.9999% - purity still 1022 to 1023 impurities per m3

Alloy deliberately add impurity to engineer properties. Copper (7.5%) in silver

Chapter 4-

Terminology - Alloys

Solvent component in highest concentration also called host Solute component present in minor concentration

Chapter 4-

POINT DEFECTS IN ALLOYS

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

OR
Substitutional alloy (e.g., Cu in Ni) Interstitial alloy (e.g., C in Fe)

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.
Chapter 4- 8

Factors that Govern Solid Solution

Hume-Rothary empirical rules

Atomic size - < 15% difference Crystal structure same Electro-negativity - ?? Valences more likely to dissolve another metal of higher valence Ag-Au, Cu-Ni, Ge-Si are ideal examples
Chapter 4-

Copper and Nickel

Element Radii Unit cell Electro negativity Oxidation (Valence) Cu 0.128 nm FCC 1.9 +1 (+2) Ni 0.125 FCC 1.8 +2

Expect to form solid solution? Ni 3d8 4s2 (28) Cu - 3d10 4s1 (29) Substitutional solid solution
Chapter 4-

Copper-Zinc
Unit cell Zn (HCP) Cu (FCC)

35% of Zn dissolves in Cu where as 1% of Cu dissolves in Zn. The extra bonding electron of Zn is more easily accommodated than a deficiency of bonding electron.

In brass 50 Cu-50 Zn the crystal structure is BCC

Chapter 4-

Carbon in Iron
Element Radii Unit cell Electro negativity Valence
Solid solution ? Interstitial or substitional? C - 2s2 2p2 Fe 3d6 4s2

C 0.071 nm Hex 2.5 +4

Fe 0.124nm BCC/FCC 1.6 +2 (+3)

Octahedral void in fcc Fe has radius 0.53 Tetrahedral void in bcc Fe has radius 0.365
Chapter 4-

Specification of Composition of Alloy of 1 and 2 Weight % Atom % C1 = [m1 / m1 + m2] x 100 nm1 = m1/ / A1 C1/ = [nm1 / nm1 + nm2] x 100 C2/ = [nm2 / nm1 + nm2] x 100

Composition conversion:

C1/ = [C1A2 / C1A2 + C2A1] x 100 C2/ = [C2A1 / C1A2 + C2A1] x 100 C1 = [C1/A1 / C1/A1 + C2/A2] x 100 C2 = [C2/A2 / C1/A1 + C2/A2] x 100 C1 + C2 = 100 C1/ + C2/ = 100
Chapter 4-

Wt. % to mass of 1 component / unit volume of material C1// = [C1 / (C1/1) + (C2/2)] x 1000 C2// = [C2 / (C1/1) + (C2/2)] x 1000
ave = [100 / (C1/ 1) + (C2/ 2)] ave = (C1/A1 + C2/A2) / [(C1/A1/ 1) + (C2/A2)/ 2] A ave = [100 / (C1/ A1) + (C2/ A2)] A ave = (C1/A1 + C2/A2) / 100
Chapter 4-

Derivation of composition conversion equation C1/ = [C1A2/(C1A2 + C2A1)] x 100 Total alloy mass : M/ = m1/ + m2/ (in units of grams) C1/ = (nm1/ nm1 + nm2) x 100 = [(m1/ /A1) (m1/ /A1) + (m2/ /A2)] x 100 m1/ = C1M // 100A1 ( since C1 = (m1 / / m1 / + m2 / ) x 100) C1/ = [(C1M // 100A1)(C1M // 100A1+ C2M // 100A2)] x 100 C1/ = (C1A2/C1A2 + C2A1) x 100 Problem: Determine the composition in atom percent of an alloy that consists of 97 wt% Al and 3 wt% Cu

Chapter 4-

AlAl-Cu alloy composition

CAl/ = {(CAlACu) / (CAlACu + CCuAAl} x 100 = {(97 x 63.55 g/mol) / (97x63.55 g/mol + 3x26.98 g/mol)} x 100 = 98.7 at% CCu/ = {(CCuAAl) / (CAlACu + CCuAAl} x 100 = {(3)(26.98 g/mol) / (3)(26.98 g/mol) + (97)(63.55 g/mol)} x 100 = 1.30 at%
Chapter 4-

LINEAR DEFECTS
Dislocations:
are linear defects,

geometrically one dimensional defect may arise due to incomplete crystal plane or due to plastic deformation crystal undergoes shear part of the crystal is displaced in the direction of the shear due to the shear stress cause slip between crystal plane when they move, produce permanent (plastic) deformation. Boundary between slipped and unslipped region is the line of dislocation
Chapter 4- 11

Schematic of a Zinc (HCP):

before deformation

after tensile elongation slip steps

Chapter 4-

Edge dislocations

a
T

Slip vector

a. Elastic strain around the dislocation. b. A possible arrangement of Atoms

Chapter 4-

Edge Dislocation: Movement b

Chapter 4-

Dislocation line Slip plane

Chapter 4-

To determine the Burgers vector of a dislocation in a twodimensional primitive square lattice, proceed as follows: Trace around the end of the dislocation plane to form a closed loop. Record the number of lattice vectors traveled along each side of the loop (shown here by the numbers in the boxes):

Chapter 4-

Screw dislocation: The dislocation line is parallel to the the slip vector.
Chapter 4-

Screw Dislocation

Chapter 4-

Motion of Screw Dislocation

Apply shear

Chapter 4-

Chapter 4-

Mixed Dislocation

Chapter 4-

 Dislocations of the same sign repel and

those of opposite sign cancel each other Dislocations can interact with point imperfections Dislocations usually appear during growth of crystals or as a result of prior mechanical deformation of the crystal. Unlike point imperfections they are not thermodynamically stable They can be removed by proper post treatment
Chapter 4-

BOND BREAKING AND REMAKING

Dislocation motion requires the successive bumping of a half plane of atoms (from left to right here). Bonds across the slipping planes are broken and remade in succession.

Atomic view of edge dislocation motion from left to right as a crystal is sheared.

For metallic materials, b will point in A close-packed crystallograhic direction and will be of magnitude Chapter 4- 13 Equal to interatomic spacing.

Motion of edge dislocation

Chapter 4-

AREA DEFECTS
2 D imperfections Regions of distortions that lie on the surface or grain boundaries having a layer of thickness of a few Surface atoms are bonded to less nearest neighbours as compared to coordination numbers. Hence they are at higher energy state compared to atoms in the interior. The broken bonds of these atoms give rise to surface energy.
Chapter 4-

AREA DEFECTS: GRAIN BOUNDARIES

Grain boundaries:
are boundaries between crystals. are produced by the solidification process, for example. have a change in crystal orientation across them. impede dislocation motion.

grain boundaries
heat flow

Angle of misalignment

Chapter 4-

Area Defects
Tilt Boundary array of edge defects Twin Boundary

Twist Boundary array of screw defects (atleast 2 sets of parallel screw dislocation)
Chapter 4-

Twin Boundaries

A twin boundary is a special type of grain boundary across which there is a specific mirror lattice symmetry. Atoms on one side of the boundary are located in mirror-image positions of the atoms on the other side. The region of material between these boundaries is termed a twin.
Chapter 4-

Twin Boundary

Twinned region

Twin boundaries
Chapter 4-

Other Interfacial defects

Stacking faults

ABCABCABABCABC Stacking fault is a thin region of hcp in fcc lattice. ABCACBCA Twin stacking fault Bulk defects like pores, cracks etc during process occur

Atomic vibrations Not all atoms vibrate with same energy, distribution of energies Chapter 4present.

OPTICAL MICROSCOPY (1)

Useful up to 2000X magnification. Polishing removes surface features (e.g., scratches) Etching changes reflectance, depending on crystal orientation.
microscope

Adapted from Fig. 4.11(b) and (c), Callister 6e. (Fig. 4.11(c) is courtesy of J.E. Burke, General Electric Co.

micrograph of Brass (Cu and Zn)

0.75mm
Chapter 4- 16

OPTICAL MICROSCOPY (2)

Grain boundaries...
are imperfections, are more susceptible to etching, may be revealed as dark lines, change direction in a polycrystal.
ASTM grain size number

microscope polished surface surface groove grain boundary

Adapted from Fig. 4.12(a) and (b), Callister 6e. (Fig. 4.12(b) is courtesy of L.C. Smith and C. Brady, the National Bureau of Standards, Washington, DC [now the National Institute of Standards and Technology, Gaithersburg, MD].)

N = 2n-1
no. grains/in2 at 100x magnification

Fe-Cr alloy

Chapter 4- 17

SUMMARY
Point, Line, and Area defects arise 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- 18

Top view of screw dislocation

Atoms above the slip plane

C
Chapter 4-

Mixed dislocation

Edge dislocation

Screw dislocation
Chapter 4-