UNIVERSIDAD NACIONAL DE TRUJILLO

FACULTAD DE INGENIERIA
ESCUELA ACADEMICO PROFESIONAL DE INGENIERIA DE MATERIALES

IMPERFECCIONES CRISTALINAS

MSc. Hebert Vizconde Pomape

E-mail: hvizconde@gmail.com
 En la realidad en los materiales encontramos:
Defectos cristalinos o irregularidades de la red
cristalina

La mayoria de los cristales tienen uno o mas Defectos

Con las dimensiones sobre el orden de un diametro atomico a
varios sitios sobre muchos sitios de la red
Los defectos pueden ser clasificados en:
1. Deacuerdo a la geometria (puntuales, lineales
o planos)
2. Dimensiones de los defectos
La mezcla de agua y alcohol da lugar a una solucion.
La mezcla ocurre a escala atomica.

We can define this

mixture/solution on a
weight or atomic basis

A similar discussion can

apply to mixtures of
metals called alloys
Defectos puntualesEn el estado solido existe mayor predictividad
Vacancies:
-vacant atomic sites in a structure.

Vacancy
distortion
of planes

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

self-
interstitial
distortion
of planes
 Defectos puntuales
El ms simple de los defectos puntuales es la vacancia.
Todo solido cristalino contiene vacancias.
Principios de termodidamica son para esplicar la necesidad de la
existendia de vacancia en solidos cristalinosciples.
La presencia de vacancias incrementa la entropia del crista.
El equlibrio del numero de vacancia, viene dado por la cantidad de
material dependiente del increment de la temperature como sigue:

Total no. of atomic sites Energy required to form vacancy

Equilibrium no. of vacancies
T = absolute temperature in Kelvin
Nv= N exp(-Qv/kT) k = gas or Boltzmanns constant
Defectos puntuales en Aleaciones
Two outcomes if impurity (B) added to host (A):
Solid solution of B in A (i.e., random dist. of point defects)

OR

Substitutional solid soln. Interstitial solid soln.

(e.g., Cu in Ni) (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.
La solucion solidad de niquel en cobre se muestran a lo largo del
plano (100) Esto es una solucin solidad con atomos de Niquel,
sustituyendo atomos de cobre en los sitios atomicos del FCC
Imperfecciones en slidos
Condiciones para que se de una solucion solida
sustitucional (S.S.)
Hume Rothery rules
1. r (atomic radius) < 15%
2. Proximity in periodic table
i.e., similar electronegativities
3. Same crystal structure for pure metals
4. Valency equality
All else being equal, a metal will have a greater tendency to
dissolve a metal of higher valency than one of lower valency
(it provides more electrons to the cloud)
Aplicaciones de la regla de HumeRothery para
solucin solida
Element Atomic Crystal Electro- Valence
Radius Structure nega-
(nm) tivity
1. Would you predict
more Al or Ag Cu 0.1278 FCC 1.9 +2
C 0.071
to dissolve in Zn? H 0.046
More Al because size is closer and val. Is O 0.060
higher but not too much because of Ag 0.1445 FCC 1.9 +1
structural differences FCC in HCP Al 0.1431 FCC 1.5 +3
Co 0.1253 HCP 1.8 +2
2. More Zn or Al Cr 0.1249 BCC 1.6 +3
Fe 0.1241 BCC 1.8 +2
in Cu? Ni 0.1246 FCC 1.8 +2
Pd 0.1376 FCC 2.2 +2
Zn 0.1332 HCP 1.6 +2
Surely Zn since size is closer thus causing
lower distortion (4% vs 12%)
Table on p. 106, Callister 7e.
Imperfecciones en Slidos
Especificacion de composicin
m1
weight percent C1 x 100
m1 m2
m1 = mass of component 1

nm1
atom percent C '
x 100
nm1 nm 2
1

nm1 = number of moles of component 1

Wt. % and At. % -- ejemplo

Typically we work with a basis weight (100g or 1 kg) or moles

given: alloy by weight -- 60% Cu, 40% Ni
600 g
nCu 9.44m
63.55 g / m
400 g
nNi 6.82m
58.69 g / m
9.44
'
CCu .581 or 58.1%
9.44 6.82
6.82
CNi
'
.419 or 41.9%
9.44 6.82
Converting Between: (Wt% and At%)
C1 A2
C
'
100
C1 A2 C2 A1
1
Converts from wt%
to At% (Ai is atomic
C2 A1 weight)
C
'
100
C1 A2 C2 A1
2

C A1
'
C1 ' 1
100
C1 A1 C2 A2
' Converts from at%
to wt% (Ai is atomic
C2' A2 weight)
C2 ' 100
C1 A1 C2 A2
'
Interstitial solid solution applies to carbon in -iron. The
carbon atom is small enough to fit with some strain in the
interstice (or opening) among adjacent Fe atoms in this
important steel structure.

But the interstitial solubility is quite low since the size mismatch of the site to the radius of a
carbon atom is only about 1/4
Random, substitution solid solution can
occur in Ionic Crystalline materials as well.
Here of NiO in MgO. The O2 arrangement is
unaffected. The substitution occurs among
Ni2+ and Mg2+ ions.
A substitution solid solution of Al2O3 in MgO is not as simple as
the case of NiO in MgO. The requirement of charge neutrality in
the overall compound permits only two Al3+ ions to fill every
threeMg2+ vacant sites, leaving oneMg2+ vacancy.
Iron oxide, Fe1xO with x 0.05, is an example of a nonstoichiometric
compound. Both Fe2+ and Fe3+ ions occupy the cation sites, with one
Fe2+ vacancy occurring for every two Fe3+ ions present.
THE OPERATION DEFINING A DEFECT CANNOT
BE A SYMMETRY OPERATION OF THE CRYSTAL

A DEFECT ASSOCIATED WITH A SYMMETRY

OPERATION OF THE CRYSTAL
TOPOLOGICAL DEFECT
 Vacancy
Non-ionic Interstitial
Impurity
crystals
Substitutional
0D
(Point defects) Frenkel defect
Ionic
Other ~
crystals
Schottky defect

Imperfect point-like regions in the crystal about the size of 1-2 atomic
diameters
Vacancy

Missing atom from an atomic site

Atoms around the vacancy displaced
Tensile stress field produced in the vicinity

Tensile Stress
Fields ?
 Relative
size
Interstitial
Compressive
Impurity Stress
Fields
Substitutional

Compressive stress
fields

SUBSTITUTIONAL IMPURITY Tensile Stress

Foreign atom replacing the parent atom in the crystal Fields
E.g. Cu sitting in the lattice site of FCC-Ni
INTERSTITIAL IMPURITY
Foreign atom sitting in the void of a crystal
E.g. C sitting in the octahedral void in FCC-Fe
 Interstitial C sitting in the octahedral void in FCC-Fe

rOctahedral void / rFCC atom = 0.414

rFe-FCC = 1.29 rOctahedral void = 0.414 x 1.29 = 0.53
rC = 0.71
Compressive strains around the C atom
Solubility limited to 2 wt% (9.3 at%)

Interstitial C sitting in the octahedral void in BCC-Fe

rTetrahedral void / rBCC atom = 0.29 rC = 0.71

rFe-BCC = 1.258 rTetrahedral void = 0.29 x 1.258 = 0.364
But C sits in smaller octahedral void- displaces fewer atoms
Severe compressive strains around the C atom
Solubility limited to 0.008 wt% (0.037 at%)
 ENTHALPY OF FORMATION OF VACANCIES

Formation of a vacancy leads to missing bonds and distortion of the

lattice
The potential energy (Enthalpy) of the system increases
Work required for the formaion of a point defect
Enthalpy of formation (Hf) [kJ/mol or eV / defect]
Though it costs energy to form a vacancy its formation leads to
increase in configurational entropy
above zero Kelvin there is an equilibrium number of vacancies

Crystal Kr Cd Pb Zn Mg Al Ag Cu Ni
kJ / mol 7.7 38 48 49 56 68 106 120 168
eV / vacancy 0.08 0.39 0.5 0.51 0.58 0.70 1.1 1.24 1.74
 Let n be the number of vacancies, N the number of sites in the lattice
Assume that concentration of vacancies is small i.e. n/N << 1
the interaction between vacancies can be ignored
Hformation (n vacancies) = n . Hformation (1 vacancy)
Let Hf be the enthalpy of formation of 1 mole of vacancies

G = H T S S = Sthermal + Sconfigurational

G (putting n vacancies) = nHf T Sconfig Larger contribution

zero
G H f S config S config N n
H f n T k ln
n n n n n
G
For minimum 0
n
 H f N n
ln Assuming n << N
kT n
n H f
Considering only configurational entropy exp
N kT
User R instead of k if Hf is in J/mole

Using ?
S = Sthermal + Sconfigurational

n 1 Sthermal H f
exp exp
N k n kT

Independent of temperature, value of ~3

 G (perfect crystal) T (C) n/N
500 1 x 1010
G (Gibbs free energy)
At a given T
1000 1 x 105
Gm in 1500 5 x 104
2000 3 x 103
Equilibrium Hf = 1 eV/vacancy
concentration
= 0.16 x 1018 J/vacancy

n (number of vacancies)

Certain equilibrium number of vacancies are preferred at T > 0K

EQUIL. CONCENTRATION:
POINT DEFECTS
Equilibrium concentration varies with temperature!

No. of defects Activation energy

ND Q
exp
D

N kT
No. of potential Temperature
defect sites. Boltzmann's constant
(1.38 x 10 -23 J/atom K)
(8.62 x 10 -5 eV/atom K)
Each lattice site
is a potential
vacancy site
4
MEDICION DE LA ENERGIA DE ACTIVACIN
We can get Q from
an experiment.

Measure this... Replot it...

ND slope
1
ln
N
-QD/k

1/T

5
Example
Calculate the equilibrium number of vacancies per cubic meter for copper at 1000C. 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.
Find the value of N, number of atomic sites per cubic meter for copper, from its
atomic weight Acu, its density, and Avogadros number NA.

N A (6.023 x10 23 atoms / mol )(8.4 g / cm 3 )(10 6 cm 3 / m3 )

N
ACu 63.5 g / mol
8.0x10 28 atoms / m3
Thus, the number of vacancies at 1000 C (1273 K ) ie equal to
Q
N v N exp v
kT
(0.9eV
(8.0x10 28 3
atoms / m ) exp
(8.62 x10 5 eV / K )(1273 K )

2.2x10 25 vacancies/m 3
Estimate number of vacancies in Cu at room T
Q
N v N exp D
k T

k = 1.38 10-23 J/atom-K = 8.62 10-5 eV/atom-K

T = 27o C + 273 = 300 K.
kT = 300 K 8.62 10-5 eV/K = 0.026 eV
QD = 0.9 eV/atom
N = NA/Acu
NA = 6.023 1023 atoms/mol
= 8.4 g/cm3
Acu = 63.5 g/mol

6.023 10 23 atoms 8.4 g 3

mol cm
Ns 8 10 22 atoms 3
63.5 g cm
mol

N v 8 10 22
atoms 0.9 eV atom
exp 0.026 eV atom
cm 3

7.4 10 7 vacancies cm3

 Ionic Crystals

Overall electrical neutrality has to be maintained

Frenkel defect

Cation (being smaller get displaced to interstitial voids

E.g. AgI, CaF2
Schottky defect

Pair of anion and cation vacancies

E.g. Alkali halides
Other defects due to charge balance

If Cd2+ replaces Na+ one cation vacancy is created

Defects due to off stiochiometry

ZnO heated in Zn vapour ZnyO (y >1)

The excess cations occupy interstitial voids
The electrons (2e) released stay associated to the interstitial cation
 FeO heated in oxygen atmosphere FexO (x <1)
Vacant cation sites are present
Charge is compensated by conversion of ferrous to ferric ion:
Fe2+ Fe3+ + e
For every vacancy (of Fe cation) two ferrous ions are converted to
ferric ions provides the 2 electrons required by excess oxygen
Defectos Lineales
Are called Dislocations:
And:
slip between crystal planes result when dislocations move,
this motion produces permanent (plastic) deformation.

Schematic of Zinc (HCP):

before deformation after tensile elongation

slip steps which are

the physical evidence
of large numbers of
dislocations slipping
along the close
packed plane {0001}
Adapted from Fig. 7.8, Callister 7e.
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 (the bergers vector) is (perpendicular) to dislocation line
Screw dislocation:
spiral planar ramp resulting from shear deformation
b is (parallel) to dislocation line

Burgers vector, b: is a measure of lattice distortion and is measured

as a distance along the close packed directions in the lattice
Dislocacion borde
Edge Dislocation

Fig. 4.3, Callister 7e.

Definition of the Burgers vector, b, relative to
an edge dislocation. (a) In the perfect crystal,
an m n atomic step loop closes at the starting
point. (b) In the region of a dislocation, the
same loop does not close, and the closure
vector (b) represents the magnitude of the
structural defect. For the edge dislocation, the
Burgers vector is perpendicular to the
dislocation line.
Gestin Ambiental MSc. Hebert Vizconde Pomape
Dislocacin de tornillo o helicoidal.
The spiral stacking of crystal planes leads to the Burgers vector
being parallel to the dislocation line.
Gestin Ambiental MSc. Hebert Vizconde Pomape
Dislocacin mixta
This dislocation has both edge and screw character with a single Burgers vector
consistent with the pure edge and pure screw regions.
Burgers vector for the aluminum
oxide structure. The large repeat
distance in this relatively complex
structure causes the Burgers vector
to be broken up into two (for O2) or
four (for Al3+) partial dislocations,
each representing a smaller slip
step. This complexity is associated
with the brittleness of ceramics
compared with metals. (From W. D.
Kingery, H. K. Bowen, and D. R.
Uhlmann, Introduction to Ceramics,
2nd ed., John Wiley & Sons, Inc.,
New York, 1976.)
Imperfections in Solids
Dislocations are visible in (T) electron micrographs

Adapted from Fig. 4.6, Callister 7e.

Dislocations & Crystal Structures
Structure: close-packed view onto two
planes & directions close-packed
planes.
are preferred.
close-packed directions
close-packed plane (bottom) close-packed plane (top)

Comparison among crystal structures:

FCC: many close-packed planes/directions;
HCP: only one plane, 3 directions;
BCC: none super-close many near close
Specimens that Mg (HCP)
were tensile
tested. tensile direction
Al (FCC)
Defectos planos en Slidos
One case is a twin boundary (plane)
Essentially a reflection of atom positions across the twinning plane.

Adapted from Fig. 4.9, Callister 7e.

Stacking faults
For FCC metals an error in ABCABC packing sequence
Ex: ABCABABC
Simple view of the surface of a crystalline material.
A more detailed model of the elaborate ledgelike structure of the
surface of a crystalline material. Each cube represents a single atom.
[From J. P. Hirth and G. M. Pound, J. Chem. Phys. 26, 1216 (1957).]
Typical optical micrograph of a
grain structure, 100. The
material is a low-carbon steel.
The grain boundaries have been
lightly etched with a chemical
solution so that they reflect light
differently from the polished
grains, thereby giving a
distinctive contrast. (From
Metals Handbook, 8th ed., Vol.
7: Atlas of Microstructures of
Industrial Alloys, American
Society for Metals, Metals Park,
OH, 1972.)
Simple grain-boundary structure.
This is termed a tilt boundary
because it is formed when two
adjacent crystalline grains are tilted
relative to each other by a few
degrees (). The resulting structure
is equivalent to isolated edge
dislocations separated by the
distance b/, where b is the length
of the Burgers vector, b. (From W. T.
Read, Dislocations in Crystals,
McGraw-Hill Book Company, New
York, 1953. Reprinted with
permission of the McGraw-Hill Book
Company.)
The ledge Growth leads to structures with Grain Boundaries The shape and
average size or diameter of the grains for some polycrystalline specimens are
large enough to observe with the unaided eye. (Macrosocipic examination)
Specimen for the calculation of the grain-size number, G is defined at a magnification
of 100. This material is a low-carbon steel similar to that shown in Figure 4.18.
(From Metals Handbook, 8th ed., Vol. 7: Atlas of Microstructures of Industrial Alloys,
American Society for Metals, Metals Park, OH, 1972.)
52

Interfacial Defects

External Surfaces
Surface atoms unsatisfied bonds
higher energies than bulk atoms
Surface energy, (J/m2)

Surface areas try to minimize (e.g. liquid drop)

Solid surfaces can reconstruct to satisfy atomic bonds at surfaces.

Grain Boundaries
Polycrystalline: many small crystals or grains. Grains have different crystallographic orientation.
Mismatches where grains meet.

1. Surfaces and interfaces are reactive

2. Impurities tend to segregate there.
3. Extra energy associated with interfaces
larger grains tend to grow by diffusion of atoms at expense of smaller grains, minimizing energy.
53

High and Low Angle Grain Boundaries

Misalignments of atomic planes between grains Distinguish low and high angle grain boundaries
54

Tilt and Twist Grain Boundaries

Tilt boundary Low angle grain boundary: an array of aligned edge dislocations (like joining two wedges)

Transmission electron microscope

image of a small angle tilt
boundary in Si. The red lines mark
the edge dislocations, the blue
lines indicate the tilt angle

Twist boundary - boundary region consisting of arrays of screw dislocations (like joining two halves of a cube
and twist an angle around the cross section normal)
55
Bulk or Volume Defects

Pores: affect optical, thermal, mechanical properties

Cracks: affect mechanical properties
Foreign inclusions: affect electrical, mechanical, optical properties

Cluster of microcracks in a
melanin granule irradiated
by a short laser pulse.
Computer simulation by L.
V. Zhigilei and B. J.
Garrison.
Gestin Ambiental MSc. Hebert Vizconde Pomape
Gestin Ambiental MSc. Hebert Vizconde Pomape