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LECTURE #08

PPooiinntt DDeeffececttss iinn CCrysrysttaallss

ChapterChapter 55

Learning objectives:

1. What are the different types of defects in materials?

2. What do these defects do to the structure and properties of materials?

Relevant Reading for this Lecture

Pages 135-142.

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TypesTypes ofof Imperfections:Imperfections:

There is no such thing as a perfect crystal

• Vacancy atoms

• Interstitial atoms

• Substitutional atoms

• Dislocations

• Grain Boundaries

• Cracks, voids

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Point defects

Line defects

Planar defects

Volume defects

[0-D]

[1-D]

[2-D]

[3-D]

Cracks, voids 2 Point defects Line defects Planar defects Volume defects [ 0 - D ]

ZeroZero –– DimensionalDimensional DefectsDefects

• A substitutional defect:

another type of atom ‘substitutes’ on a particular lattice site.

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of atom ‘substitutes’ on a particular lattice site. 3 In chemistry, you are likely are familiar
of atom ‘substitutes’ on a particular lattice site. 3 In chemistry, you are likely are familiar
of atom ‘substitutes’ on a particular lattice site. 3 In chemistry, you are likely are familiar

In chemistry, you are likely are familiar with mixing two liquids to make a ‘liquidsolution….you can do the same with solids! But in this case the different atoms in the solid occupy the equivalent crystal (lattice) sites making a ‘solid’ solution

SolidSolid SolutionSolution

Solid solution of nickel in copper shown along a (100) plane. This is a substitutional solid solution with nickel atoms substituting for copper atoms on FCC atom lattice sites.

substituting for copper atoms on FCC atom lattice sites. r = 0 128 nm . Cu
substituting for copper atoms on FCC atom lattice sites. r = 0 128 nm . Cu

r

= 0 128 nm

.

Cu

r Ni = 0.125 nm

Ni = solute, Cu = solvent

• Ni and Cu are so close in size, they can form a solid solution

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in all proportions

MECHANICALMECHANICAL PROPERTIES:PROPERTIES: CuCu--NiNi SystemSystem

• Effect of solid solution strengthening on:

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--Tensile strength (TS)

--Ductility (%EL,%AR)

400 TS for pure Ni 300 TS for pure Cu 200 0 20 40 60
400
TS for
pure Ni
300
TS for pure Cu
200
0
20
40
60
80
100
Cu
Ni
Tensile
Strength
(MPa)
Elon gation (
%EL)

Composition, wt%Ni

60 %EL for pure Cu 50 %EL for pure Ni 40 30 20 0 20
60
%EL for pure Cu
50
%EL for
pure Ni
40
30
20
0
20
40
60
80 100
Cu
Ni

Composition, wt%Ni

Adapted from Fig. 9.5(a), Callister 6e.

--Peak as a function of C o

Adapted from Fig. 9.5(b), Callister 6e.

--Min. as a function of C o

r Cu = 0.128nm r Ni = 0.125nm Small atomic size difference causes the bonds
r Cu = 0.128nm
r Ni = 0.125nm
Small atomic size difference causes the bonds to stretch
which makes the alloy stronger!

HumeHume--RotheryRothery RulesRules forfor FormingForming aa SolidSolid SolutionSolution

1. < 15% difference in atomic radii

2. The same crystal structure

3. Similar electronegativity (i.e., ability of an atom to attract an electron)

4. Same valence

If one or more of these rules are violated, only partial solubility is possible.

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OrderingOrdering ofof thethe solidsolid solutionsolution-- IntermetallicsIntermetallics

inin thethe AuCuAuCu 33 alloyalloy system.system.

inin thethe AuCuAuCu 3 3 alloyalloy system.system. (a) > ~390 ° C, random distribution of Au

(a) > ~390°C, random distribution of Au and Cu atoms among FCC sites.

(b) < ~390°C, Au atoms preferentially occupy corners, while Cu atoms occupy faces (the Au forms a simple cubic Bravais lattice).

ZeroZero –– DimensionalDimensional DefectsDefects

An interstitial defect: the placement of an atom in a interstitial (in between regular lattice sites).

atom in a interstitial (in between regular lattice sites). 9 InterstitialInterstitial SolidSolid SolutionsSolutions

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InterstitialInterstitial SolidSolid SolutionsSolutions

Some atoms are too small to substitute for primary atoms. They may occupy interstitial sites.

HUME-ROTHERY RULES DO NOT APPLY TO INTERSTITIALS.

sites. HUME-ROTHERY RULES DO NOT APPLY TO INTERSTITIALS. Figure 4.4 enough to fit with some strain

Figure 4.4

enough to fit with some strain in the interstice (or opening) among adjacent Fe atoms in

this

compared with that shown in Figure 3.4b.]

Interstitial solid solution of carbon in α-iron. The carbon atom is small

[This unit-cell structure can be

structure of importance to the steel industry.

ZeroZero –– DimensionalDimensional DefectsDefects

• A vacancy :a vacant lattice site

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DefectsDefects • A vacancy :a vacant lattice site 11 12 AreAre vacanciesvacancies anan equilibriumequilibrium

AreAre vacanciesvacancies anan equilibriumequilibrium defect?defect?

• Yes, vacancies contribute to entropy to the system and can help to reduce the crystal’s energy, up to a point.

can help to reduce the crystal’s energy, up to a point. Energy to breaking bonds +
Energy to breaking bonds + –n w V G Total energy V number of vacancies,
Energy to breaking bonds
+
–n
w
V
G
Total energy
V
number of vacancies, n V
n
1
n
e
–TS
Ene rgy

Energy gained by entropy (disorder)

Do you think vacancy concentration goes up with temperature?

• In ionic crystals (such as NaCl), single vacancies can not occur. Why?

Because of the constraints of charge neutrality, either a Frenkel defect OR a Schottky defect forms . Frenkel defect OR a Schottky defect forms.

Frenkel defect: vacancy-interstitial combination. : vacancy-interstitial combination.

Schottky defect: pair of oppositely charged ion vacancies. : pair of oppositely charged ion vacancies.

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defect : pair of oppositely charged ion vacancies. 13 Shottky Defect: Frenkel Defect Adapted from Fig.12.21,

Shottky

Defect:

Frenkel

Defect

Adapted from Fig.12.21, Callister & Rethwisch 8e. (Fig. 12.21 is from W.G. Moffatt, G.W. Pearsall, ff

and J. Wul , The Structure and Properties of Materials, Vol. 1, Structure, John Wiley and Sons, Inc., p. 78.)

, Vol. 1, Structure , John Wiley and Sons, Inc., p. 78.) Random, Random, substitutional substitutional

Random,Random, substitutionalsubstitutional solidsolid solutionsolution ofof NiONiO inin MgOMgO

The O 2 arrangement is unaffected. The substitution occurs only among Ni 2+ and Mg 2+ ions.

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. The substitution occurs only among Ni 2 + and Mg 2 + ions. 14 R

R i = 0.069 nm

R i = 0.072 nm

. The substitution occurs only among Ni 2 + and Mg 2 + ions. 14 R

What happens if the charges do not balance?

Substitutional solid solution of Al 2 O 3 in MgO is not as simple as

NiO in MgO. The overall compound must be charge neutral, this permits only two Al 3+ ions to fill every three Mg 2+ vacant sites, leaving one Mg 2+ vacancy.

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R i = 0.053 nm R i = 0.072 nm
R i = 0.053 nm
R i = 0.072 nm
one Mg 2 + vacancy . 15 R i = 0.053 nm R i = 0.072
one Mg 2 + vacancy . 15 R i = 0.053 nm R i = 0.072

In class example:

Calculate the number of Mg 2+ vacancies produced by the solubility of 1 mol of Al O in 99 mol of MgO

2

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Approach:

• Calculate amount of O

• Calculate amount of cations

• Difference btw. O & cations = amt. vacancies

ti ons • Difference btw. O & cations = amt. vacancies 99 mol O sites (from

99 mol O sites (from MgO)

+ 3 mol O sites (from Al 2 O 3 )

102 mol O sites in solid solution

99 mol cation sites (from MgO)

+ 2 mol cation sites (from Al 2 O 3 )

101 mol cation sites in solid solution

102 mol – 101 mol = I mol Mg 2+ vacancies or 6.02 x10 23 vacancies

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101 mol cation sites in solid solution 102 mol – 101 mol = I mol Mg

StoichiometricStoichiometric vs.vs. Non-Non-StoichiometricStoichiometric CompoundsCompounds

Stoichiometric

The amounts (moles) of each element are given by the formula, Fe 2 O 3 , NiO 2 , Fe 3 0 4 , CuSO 4 , etc.

The ratio does not vary!

Non-Stoichiometric

• The amounts (moles) of each element does vary, this can be reflected by using variables in the formula, Fe x O y or Fe 1-x O (x 0.05)

• The ratio does vary!

17 Fig. 4.7 Iron oxide, Fe 1−x O (x ≈ 0.05), is an example of
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Fig. 4.7
Iron oxide, Fe 1−x O (x ≈ 0.05), is an example of a nonstoichiometric
compound. Similar to Fig 4.6, both Fe 2+ and Fe 3+ ions occupy the cation sites.
One Fe 2+ vacancy occurs for every two Fe 3+ ions.
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Example: Ferrous oxide, FeO (Fe 2+ + O 2- )

– If an Fe 3+ (the ferric state) is substituted for an Fe 2+ , cation vacancies are needed to offset charge

– Extra oxygen associated with the ferric iron is accommodated in the normal oxygen sublattice (leaves some cation ion sites unoccupied)

– Thus the composition is Fe 1-x O, where x is small and <1 (~ 0.05)

is Fe 1 - x O, where x is small and <1 (~ 0.05) 19 •

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• If different valence ions exist in the lattice as impurities, the concentration of vacancies adjusts.

• Example: Adding a Ca 2+ to NaCl. Extra Na + vacancies are needed to maintain charge neutrality.

• Nonstoichiometric composition can cause color differences

• Consequence is the number of anion sites vacant (electrons associated with the anion sites to keep charge neutrality)

Electrons near the vacancy, vibrate differently yielding a color change (NaCl becomes yellowish-brown)

yielding a color change (NaCl becomes yellowish-brown) Structure controls properties (optical properties in this
yielding a color change (NaCl becomes yellowish-brown) Structure controls properties (optical properties in this

Structure controls properties (optical properties in this case!)

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NaClNaCl

NaClNaCl (Na(Na ( 1 ( 1 - - x ) x ) CaCa x x ))Cl

(Na(Na (1(1--x)x) CaCa xx ))ClCl

( 1 ( 1 - - x ) x ) CaCa x x ))Cl Cl

http://1.bp.blogspot.com/_EBqHz1Oipb4/TCtpx7Sk6jI/AAAAAAAAABQ/_2Os- http://www.fromnaturewithlove.com/images/SaltBolivianCoarse.jpg

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inoQ5Q/s1600/sodium-chloride.jpg

SummarySummary

Three types of 0-D defects (Point Defects):

•Vacancies

•Interstitial atoms

Substitutional atoms

• Vacancies help control charge neutrality in ionic crystals; variations in charge state change vac. Concentration and properties (like color)

What is a solid solution?

A solid solution forms when, as the solute atoms are added to the host material, the crystal structure is maintained and no new crystal structures are formed.

Hume-Rothery Rules:

1. < 15% difference in atomic radii

2. The same crystal structure

3. Similar electronegativity (i.e. ability of an atom to attract an electron)

4. Same valence

WHY ARE HR RULES IMPORTANT:

If one or more rules are violated, only partial solubility is possible.

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