CHAPTER 4

IMPERFECTION IN SOLIDS

Vacancy Equation:
−𝑄 𝑣
𝑁 𝑣 = 𝑛 exp ( 𝑘𝑇
)
− 𝑄𝑣
𝑁 𝑣 = 𝑛 exp ( )
𝑅𝑇

In the equation, N is the total number of atomic sites, 𝑄 𝑣 is the energy required of the
formation of a vacancy (J / mol or eV / atom), T is the absolute temperature in Kelvin, k is
the Boltzmann’s constant, where k is 1.38 ∗ 10 −23 atom∗K or 8.62 ∗ 10 −5 atom∗K.
J eV

If 𝑁 𝑣 is given, the equation would be:

𝑁𝑣 − 𝑄𝑣
ln = exp ( )
𝑁 𝑘𝑇

Sample Problem 1.

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

Solution:

atoms g 106 cm 3
(6.022 ∗ 10 23 )(8.4 3 )( )
NA ρ mol cm m3 atoms
NCu = = g = 8.19 ∗ 10 28
A Cu 63.5 m3
mol
−Q v atoms 0.9 eV vacancies
Nv = n exp = 8.19 ∗ 10 28 exp [− = 2.25 ∗ 10 25
kT m3 eV
(8.62∗10 −5 )(1273 K) m3
K

Substitutional Solid Solution it is when the solute or impurity atoms replace or

substitute for the host atoms. The Hume – Rothery Rule is expressed when several
features of the solute and solvent atoms determine the degree to which the former
dissolves in the latter:

1. Atomic Size Factor – Appreciable quantities of a solute may be accommodated

in this type of solid solution only when the difference in atomic radii between the
 two atom types is less than about 15%. Otherwise, the solute atoms create
substantial lattice distortion and a new phase forms.
2. Crystal Structure – For appreciable solid solubility, the crystal structures for
metals of both atom types must be the same.
3. Electronegativity Factor – The more electropositive the one element is and the
more electronegative the other, the greater the likelihood that they will form an
intermetallic compound instead of a substitutional solid solution.
4. Valences – Other factors being equal, a metal has more of a tendency to dissolve
metal of a higher valency than to dissolve one of a lower valency.

Weight Percent it is the weight of a particular element relative to the total alloy weight.
𝑚1
𝐶1 = ∗ 100
𝑚1 + 𝑚1

Atom Percent it is the number of moles of an element in relation to the total mass of a
hypothetical element in relation to the total moles of the elements in an alloy.
𝑚1
𝑛 𝑚1 =
𝐴1

Composition Conversion, Weight Percent to Atom Percent

𝐶1 𝐴2
𝐶1 = ∗ 100
𝐶1 𝐴2 + 𝐶2 𝐴1
𝐶2 𝐴1
𝐶2 = ∗ 100
𝐶1 𝐴2 + 𝐶2 𝐴1

Composition Conversion, Atom Percent to Weight Percent

𝐶1 𝐴1
𝐶1 = ∗ 100
𝐶1 𝐴1 + 𝐶2 𝐴2
𝐶2 𝐴2
𝐶2 = ∗ 100
𝐶1 𝐴1 + 𝐶2 𝐴2

Composition Conversion, Weight Percent to Mass per unit volume

𝐶1
𝐶1 = ∗ 103
𝐶1 𝐶2
𝜌1 + 𝜌2

𝐶2
𝐶2 = ∗ 103
𝐶1 𝐶2
𝜌1 + 𝜌2
Average Atomic Weight Of A Two Component Alloy
100
𝐴 𝐴𝑣𝑒 =
𝐶1 𝐶2
+
𝐴1 𝐴2
𝐶 𝐴 + 𝐶2 𝐴2
𝐴 𝐴𝑣𝑒 = 1 1
100

Computation of Density
100
𝜌 𝐴𝑣𝑒 =
𝐶1 𝐶2
𝜌1 + 𝜌2
𝐶 𝐴 + 𝐶2 𝐴2
𝜌 𝐴𝑣𝑒 = 1 1
𝐶1 𝐴1 𝐶2 𝐴2
𝜌1 + 𝜌2

Sample Problem 2.

What is the composition, in atom percent, of an alloy that consists of 30% wt. Zn and 70%
wt. Cu?
A 1 = Zinc, 30%, 65.39

A 2 = Copper, 70%, 63.55

Solution:
𝐶1 𝐴2 30 ∗ 63.55
𝐶1 = ∗ 100 → ∗ 100 = 29.40%
𝐶1 𝐴2 + 𝐶2 𝐴1 30 ∗ 63.55 + 70 ∗ 65.39

𝐶2 𝐴1 70 ∗ 65.39
𝐶2 = ∗ 100 ∗ 100 = 70.60%
𝐶1 𝐴2 + 𝐶2 𝐴1 30 ∗ 63.55 + 70 ∗ 65.39

Sample Problem 3.

Determine the composition, in atom percent, of an alloy that consists of 97 wt.% aluminum
and 3 wt.% copper.

Solution:

and 𝐶 2 = 𝐶
𝐶 1𝐴 2 𝐶 2𝐴 1
𝐶1 = 𝐶 ∗ 100 ∗ 100
1𝐴 2+𝐶 2𝐴 1 1𝐴 2+𝐶 2𝐴 1

Let 𝐶 1 𝑎𝑛𝑑 𝐴 1 = 𝑎𝑙𝑢𝑚𝑖𝑛𝑢𝑚, 26.98 𝑚𝑜𝑙

𝑔
Let 𝐶 2 𝑎𝑛𝑑 𝐴 2 = 𝑐𝑜𝑝𝑝𝑒𝑟, 63.55 𝑚𝑜𝑙
𝑔

97 ∗ 63.55
𝐶1 = ∗ 100 = 98.7 𝑎𝑡. %
97 ∗ 63.55 + 3 ∗ 26.98
3 ∗ 26.98
𝐶2 = ∗ 100 = 1.3 𝑎𝑡. %
3 ∗ 26.98 + 97 ∗ 63.55

Sample Problem 4.

Calculate the activation energy for vacancy formation in aluminum, given that the
equilibrium number of vacancies at 500°C (773 K) is 7.57 × 1023 m−3 . The atomic weight
and density (at 500°C) for aluminum are, respectively, 26.98 g/mol and 2.62 g/cm3.

Solution:

Nv = 7.57 × 1023 m−3

Atomic weight = 26.98 g/mol

Density = 2.62 g/cm3

atoms g 106 cm 3
(6.022 ∗ 10 23 )(2.62 3 )( )
NA ρ mol cm m3 atoms
NAl = = g = 5.85 ∗ 10 28
A Al 26.98 m3
mol
Nv − Qv 7.57 ∗ 10 23 Q
ln = exp = ln = exp [− ] = 0.75 eV / atom
N kT 5.85 ∗ 10 28 eV
8.62 ∗ 10 −5 773K
K

Sample Problem 5.

What is the composition, in weight percent, of an alloy that consists of 6 at% Pb and 94
at% Sn?

Solution:
A 1 = Lead, 6% atomic weight, 207.2

A 2 = Tin, 94% atomic weight, 118.71

𝐶1 𝐴1 6 ∗ 207.2
𝐶1 = ∗ 100 → = 10.02%
𝐶1 𝐴1 + 𝐶2 𝐴2 6 ∗ 207.2 + 94 ∗ 118.71
 𝐶2 𝐴2 94 ∗ 118.71
𝐶2 = ∗ 100 → = 89.98%
𝐶1 𝐴1 + 𝐶2 𝐴2 6 ∗ 207.2 + 94 ∗ 118.71

Sample Problem 6.

Calculate the composition, in weight percent, of an alloy that contains 218.0 kg titanium,
14.6 kg of aluminum, and 9.7 kg of vanadium.

Solution:
A 1 = Titanium, 218 kg

A 2 = Aluminum, 14.6 kg

A 3 = Vanadium, 9.7 kg

218
C1 = ∗ 100 = 89.97%
218 + 14.6 + 9.7
14.6
C2 = ∗ 100 = 6.03%
218 + 14.6 + 9.7
9.7
C3 = ∗ 100 = 4.00 %
218 + 14.6 + 9.7

CHAPTER 5

DIFFUSION IN SOLIDS
Fick’s First Law

Diffusion is a time – dependent process. The quantity of an element that is transported

within another is a function of time. The rate is expressed as diffusion flux, J, defined as
the mass, M diffusing through and perpendicular to a unit cross – sectional area of solid
per unit of time. A denotes the area across which the diffusion is occurring and t is the
elapsed diffusion time.
𝑀
𝐽=
𝐴𝑡

At steady – state diffusion in a single (x) direction, the flux is proportional to the
concentration gradient, 𝑑𝑥 . Where D is the diffusion coefficient, where the negative sign
𝑑𝐶

indicates that diffusion is down the concentration gradient, from high to a low
concentration.
𝑑𝐶
𝐽 =− 𝐷
𝑑𝑥

Steady State Diffusion it happens when it reaches a state wherein the diffusion flux does
not change with time, the mass of diffusing species entering the plate on the high –
pressure side is equal to the mass exiting from the low – pressure surface, such that there
is no accumulation of diffusing species in the plate.

Concentration Gradient it is the slope at a particular point when C is plotted within the
solid x.

𝑑𝐶 ∆𝐶 𝐶 𝐴 − 𝐶 𝑏
𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝐺𝑟𝑎𝑑𝑖𝑒𝑛𝑡 = = =
𝑑𝑥 ∆𝑥 𝑥𝑎 − 𝑥𝑏

Sample Problem 7.

A plate of iron is exposed to a carburizing (carbon – rich) atmosphere on one side and a
decarburizing (carbon – deficient) atmosphere on the other side at 700 ˚C (1300 ˚F). If a
condition of a steady – state is achieved, calculate the diffusion flux of carbon through the
plate if the concentrations of carbon at positions of 5 and 10 mm 5 ∗ 10−3 𝑎𝑛𝑑 10 −2 𝑚)
beneath the carburizing surface are 1.2 and 0.8 , respectively. Assume a diffusion
𝑘𝑔
𝑚3

coefficient of 3 ∗ 10−11 at this temperature.

𝑚2
𝑠

Solution:
 𝑘𝑔
2 1.2 − 0.8
𝐽 =− 𝐷
𝑑𝐶 𝑚
= − 3 ∗ 10−11 [ 𝑚 3 = 2.4 ∗ 10 −9 𝑘𝑔
𝑑𝑥 𝑠 5 ∗ 10−3 − 10−2 𝑚 𝑚2 ∗ 𝑠

Fick’s Second Law – Non – Steady State Diffusion

Diffusion flux and the concentration gradient at some particular point in a solid vary with
time, with a net accumulation or depletion of the diffusing species resulting. If the diffusion
coefficient is independent of composition, the equation would be:

𝜕𝐶 𝜕2 𝐶
=𝐷
𝜕𝑡 𝜕𝑥2

Following certain conditions, the ideal equation will yield the solution:

𝐶𝑥 − 𝐶𝑜 𝑥 𝐶𝑥 − 𝐶𝑜 𝑥2
= 1 − erf 𝑜𝑟 = 1 − erf
𝐶𝑠 − 𝐶𝑜 𝐶𝑠 − 𝐶𝑜 𝐷𝑡
2 𝐷𝑡

Sample Problem 8.

Consider such alloy that initially has a uniform carbon concentration of 0.25 wt.% and is
to be treated at 950 ˚C (1750 ˚F). If the concentration of carbon at the surface is suddenly
brought to and maintained at 1.20 wt.%, how long will it take to achieve a carbon content
of 0.80 wt.% at a position 0.5 mm below the surface? The diffusion coefficient for carbon
in iron at this temperature is 1.6 ∗ 10 −11 , assume that the steel piece is semi – infinite.
𝑚2
𝑠

Solution:
𝐶 0 = 0.25 𝑤𝑡. % 𝐶

𝐶 𝑠 = 1.20 𝑤𝑡.% 𝐶

𝐶 𝑥 = 0.80 𝑤𝑡. % 𝐶

𝑥 = 0.50 𝑚𝑚 = 5 ∗ 10 −4 𝑚

𝑚2
𝐷 = 1.6 ∗ 10 −11
𝑠

𝐶𝑥 − 𝐶𝑜 𝑥 0.80 − 0.25 5 ∗ 10−4 𝑚

= 1 − erf = = 1 − erf
𝐶𝑠 − 𝐶𝑜 1.20 − 0.25
2 𝐷𝑡 𝑚2
2 1.6 ∗ 10 −11 𝑠 𝑡
 62.5 𝑠 0.5
0.4210 = erf ( )
𝑡

Z erf (z)
0.35 0.3794
z 0.4210
0.40 0.4284

𝑧 − 0.35 0.4210 − 0.3794

= = 𝑧 = 0.392
0.40 − 0.35 0.4284 − 0.3794
2
62.5 𝑠 0.5
𝑡= = 25420.72 𝑠 = 7.06 ℎ𝑜𝑢𝑟𝑠
0.392

Sample Problem 9.

The diffusion coefficients for coper in aluminum at 500 ˚C and 600 ˚C are 4.8 ∗ 10 −14 and
, respectively. Determine the approximate time at 500 ˚C that will produce
𝑚2
5.3 ∗ 10 −13 𝑠
the same diffusion result (in terms of concentration of Cu at some specific point in Al) as
a 10 – h heat treatment at 600 ˚C.

Solution:

𝑥 2𝑜 𝑥 2𝑜
= → 𝐷 500 𝑡500 = 𝐷 600 𝑡600
𝐷 500 𝑡500 𝐷 600 𝑡600
2
−13 𝑚
𝐷 𝑡 (5.3 ∗ 10 𝑠 )(10ℎ) = 110.42 ℎ
𝑡500 = 600 600 =
𝐷 500 𝑚2
4.8 ∗ 10 −14 𝑠

Sample Problem 10.

Nitrogen from a gaseous phase is to be diffused into pure iron at 700°C. If the surface
concentration is maintained at 0.1 wt% N, what will be the concentration 1 mm from the
surface after 10 h? The diffusion coefficient for nitrogen in iron at 700°C is 2.5 × 10−11
m2 /s.

Solution:

Factors That Influence Diffusion

1. Diffusing Species
 2. Temperature – it has profound influence on the coefficients and diffusion rates.
The temperature dependence of the diffusion coefficient is:
𝑄
𝐷 = 𝐷 𝑜 exp − 𝑑
𝑅𝑇
Where:
𝐷 𝑜 = 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 − 𝑖𝑛𝑑𝑒𝑝𝑒𝑛𝑑𝑒𝑛𝑡 𝑝𝑟𝑒𝑒𝑥𝑝𝑜𝑛𝑒𝑛𝑡𝑖𝑎𝑙
𝑄 𝑑 = 𝑎𝑐𝑡𝑖𝑣𝑎𝑡𝑖𝑜𝑛 𝑒𝑛𝑒𝑟𝑔𝑦 𝑓𝑜𝑟 𝑑𝑖𝑓𝑓𝑢𝑠𝑖𝑜𝑛
𝐽 𝑒𝑉
𝑅 = 𝑔𝑎𝑠 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡, 8.31 𝑖𝑓 𝑚𝑜𝑙 , 8.62 ∗ 10 −5 𝑖𝑓 𝑎𝑡𝑜𝑚
𝑇 = 𝑎𝑏𝑠𝑜𝑙𝑢𝑡𝑒 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 (𝐾)

Taking natural logarithms, the equation would yield:

𝑄 1
ln 𝐷 = ln 𝐷 𝑜 − 𝑑 ( )
𝑅 𝑇

CHAPTER 6

MECHANICAL PROPERTIES OF METALS

Engineering Stress it is the applied load divided by the original cross – sectional area
of a material. It is also called nominal stress. Where F is the instantaneous load applied
perpendicular to the specimen cross sectional area and 𝐴 𝑜 is the original cross – sectional
area.
𝐹
𝜎=
𝐴𝑜

1 + cos 2𝜃
𝑓𝑜𝑟 𝑔𝑒𝑜𝑚𝑒𝑡𝑟𝑖𝑐 𝑐𝑜𝑛𝑠𝑖𝑑𝑒𝑟𝑎𝑡𝑖𝑜𝑛𝑠: 𝜎 = 𝜎 cos 2 𝜃 𝑜𝑟 𝜎( )
2

Engineering Strain it is the amount that a material deforms per unit length in a tensile
test. It is also called as nominal strain. Where 𝑙 𝑜 is the original length before any load is
applied, 𝑙 𝑖 is the instantaneous length. Strain can be unitless but meters per meter of
inches per inch is often used.
𝑙 𝑖 − 𝑙 𝑜 ∆𝑙
𝜀= =
𝑙𝑜 𝑙𝑜

Torsion it is a variation of pure shear in which a structural member is twisted in the

manner. Torsional forces produce a rotational motion about the longitudinal axis of one
end of the member relative to the other end.
 𝐹
𝜏=
𝐴𝑜

sin 2𝜃
𝑓𝑜𝑟 𝑔𝑒𝑜𝑚𝑒𝑡𝑟𝑖𝑐 𝑐𝑜𝑛𝑠𝑖𝑑𝑒𝑟𝑎𝑡𝑖𝑜𝑛𝑠: 𝜏 = 𝜎 𝑠𝑖𝑛 𝜃 cos 𝜃 𝑜𝑟 𝜎( )
2

Hooke’s Law states that stress and strain are proportional to each other.
𝜎 = 𝐸𝜀

Sample Problem 10.

A piece of copper originally 305 mm (12 in.) long is pulled in tension with a stress of 276
MPa (40,000 psi). If the deformation is entirely plastic, what will be the resultant
elongation? Given that elongation of copper is 110 gigapascals.

Solution:

∆𝐿 𝜎𝑙
𝜎 = 𝜀𝐸 = 𝐸 → ∆𝑙 = 𝑜
𝑙𝑜 𝐸

276 𝑀𝑃𝑎 ∗ 305 𝑚𝑚

∆𝑙 = = 0.77 𝑚𝑚 𝑜𝑟 3 𝑖𝑛𝑐ℎ𝑒𝑠
110 ∗ 10 3 𝑀𝑃𝐴

Poisson’s Ratio it is defined as the ratio of the lateral and axial strains.
𝜀𝑥 𝜀𝑦
𝑣 =− =−
𝜀𝑧 𝜀𝑧

Necking it happens when maximum stress is attained and there is a small constriction
begins to form at some point, and all subsequent deformation is confined at the
constriction point.

Ductility it is a measure of the degree of plastic deformation that has been sustained by
a fracture.
𝑙𝑓 − 𝑙𝑜
% 𝐸𝐿 = ∗ 100
𝑙𝑜

𝐴𝑜 − 𝐴𝑓
% 𝑅𝐴 = ∗ 100
𝐴𝑜

Brittle it happens when a metal that experiences little or no plastic deformation upon
fracture.

True Stress it is defined as the load F divided by instantaneous cross – sectional area
A, over which deformation is occurring.
 𝐹
𝜎𝑇 =
𝐴𝑖

𝜎 𝑇 = 𝜎(1 + 𝜖)

𝜎 𝑇 = 𝐾𝜖 𝑛 𝑇

True Strain it is defined as the change in length with respect to instant length.
𝑙𝑖
𝜀 𝑇 = ln
𝑙𝑜

𝜀 𝑇 = ln (1 + 𝜖)

𝑖𝑓 𝑛𝑜 𝑣𝑜𝑙𝑢𝑚𝑒 𝑐ℎ𝑎𝑛𝑔𝑒𝑠 𝑑𝑢𝑟𝑖𝑛𝑔 𝑑𝑒𝑓𝑜𝑟𝑚𝑎𝑡𝑖𝑜𝑛: 𝐴 𝑖 𝑙 𝑖 = 𝐴 𝑜 𝑙 𝑜

Sample Problem 12.

A cylindrical specimen of steel having an original diameter of 12.8 mm (0.505 in.) is tensile
tested to fracture and found to have an engineering fracture strength 𝜎 𝑓 of 460 MPa
(67,000 psi). If its cross – sectional diameter at fracture is 10.7 mm (0.422 in.). Determine:

a. The ductility in terms of percentage reduction area

b. The true stress at fracture

Solution:

12.8 𝑚𝑚 2 10.7 𝑚𝑚 2
𝜋− 𝜋
%𝑅𝐴 = 2 2 ∗ 100 = 30%
2
12.8 𝑚𝑚
𝜋
2

𝑁 1 𝑚2
𝐹 = 𝜎 𝑓 𝐴 𝑓 = (460 ∗ 10 6 ∗ 128.77 𝑚𝑚 2 = 59,200 𝑁
𝑚2 106 𝑚𝑚 2
𝐹 59,200 𝑁
𝜎𝑇 = = = 6.6 ∗ 10 8 𝑜𝑟 660 𝑀𝑃𝑎
𝐴𝑖 2 1𝑚 2
𝑚2
89.9 𝑚𝑚 ∗ 6
10 𝑚𝑚 2

Sample Problem 13.

For some metal alloy, a true stress of 415 MPa (60,175 psi) produces a plastic true strain
of 0.475. How much does a specimen of this material elongate when a true stress of 325
MPa (46,125 psi) is applied if the original length is 300 mm (11.8 in.)? Assume a value of
0.25 for the strain-hardening exponent n.
Solution:

True Stress = 415 MPa or 60,175 psi

True Strain = 0.475

n = 0.25

Original length = 300 mm (11.8 in)

Second True Stress = 325 MPa or 46,125 psi

𝜎 𝑇 = 𝐾𝜖 𝑛 𝑇

415 415
𝐾= = = 500 𝑀𝑃𝑎
0.475 0.25 0.8302

325
500𝜖 0.25 𝜖 0.25 = = 0.65 4
= 0.1785
500

𝜀 𝑇 = ln 1 + 𝜖 → 𝑒 0.1785 − 1 = 0.1954

∆𝐿 = 𝜖𝐿 𝑜 = 0.1954 ∗ 300 = 58.62 𝑚𝑚