Physical

Metallurgy
By:
Majid Pouranvari
pouranvari@sharif.edu
Sharif University of Technology
MSE Department
2020
 Chapter 3:
Crystal Structure
Classification of solids
 Solids can broadly be classified into two
types based on the arrangement of units
of matter.
 The units of matter may be atoms,
molecules or ions.
 They are,
 Crystalline solids and
 Non-crystalline (or) Amorphous solids
Crystal

Ordering of atomic arrangement

Crystal: Regularly repeating of 3-D patterns of atoms
Crystal
 Crystal is made of identical building blocks
Crystal: 3-D Ordering
TEM Image
of Si Atoms
Crystal
Crystal
Coordination Number
Crystal
 Regularly repeating of 3-D patterns of
atoms/ions/molecules
 Long-range order
 Coordination number
 Symmetry
Crystal vs. amorphous

Long range order vs. short range order

Crystal: Regularly repeating of 3-D patterns on atoms
Amorphous: Lack of ordering
Crystal vs. Amorphous
Anisotropy in crystals
Originating from different spacing between
atoms in different directions
Anisotropy in crystals
Anisotropy in crystals
Crystal External Form
Amorphous Materials
The lack of long-range order
The sub-units are packed together randomly.
They have short-range order: order on a scale of
the subunit size
Crystal vs. Amorphous
Amorphous Materials
The structure is such that the sub-unit arrangements can get tangled
so easily and so completely in the liquid state that they are almost
impossible to untangled once the material is solid.

If atoms have only limited mobility at the equilibrium solidification

temperature (i.e. they cannot move into lowest energy configuration,
crystalline), they formed an amorphous material.
Amorphous Materials
(1 ) the structure of the molecules is so complex
that they cannot easily rearrange themselves to
form a crystalline structure, and/or

(2) the solid forms so rapidly that the atoms or

molecules do not have time enough to rearrange
themselves in a crystalline structure
Amorphous Materials
 Polymers
 Ceramics
 Metals
Melt Spinning
X-ray Diffraction: Crystal vs. Amorphous
 Sharp peaks are obtained from crystalline materials (using parallel, monochromatic
radiation), while typically a broad peak is obtained from an amorphous material. The sharp
peak is referred to as a Bragg peak.

Note the broad peak

SAD pattern (TEM ) from the

amorphous sample

XRD pattern showing the formation of amorphous

structure in the suction cast (Cu64Zr36)96Al4 alloy
Solid Types:
Single Crystal, Polycrystalline, Amorphous

 Each type is characterized by the size of

the ordered region within the material. An
ordered region is a spatial volume in which
atoms or molecules have a regular
geometric arrangement or periodicity.
‫‪Single Crystal‬‬
‫نظم تناوبي و تكرارشوندهي كامل و بدون وقفهي آرايش اتمها در سراسر يك‬
‫جامد بلوري‬
‫• طبیعي‬
‫• مصنوعي‬
 ‫‪Polycrystal‬‬
‫تعداد زيادي بلورهاي ريز يا دانه‬ ‫‪o‬‬
‫تشكیل بلورهاي كوچك يا هستهها در جاهاي مختلف مذاب‪ ،‬با كاهش دما‬ ‫•‬
‫افزايش تدريجي اتمها از مايع به ساختار هر يك از هستهها و رشد آنها‬ ‫•‬
‫دکتر پیروز مرعشی – گروه متالورژی دانشگاه صنعتی امیرکبیر‬

‫تفاوت جهت بلوري از دانهاي به دانهي ديگر‬ ‫•‬

‫مقداري عدم تطابق اتمي در مرزدانه يعني جايي كه دو دانه به هم‬ ‫•‬
‫ميرسند‬

‫‪29‬‬
Polycrystals
Grain boundary in a polycrystal
Grains
Anisotropy in polycrsytals
For many polycrystalline materials the
grain orientations are random. Therefore,
even if the individual grains are
anisotropic, the property differences tend
to average out and, overall, the material is
isotropic .
Importance of Crystal Structure
A key to understanding of the materials
properties

To produce materials with pre-designed

properties
Example: Diamond vs. Graphite
Example: Ductility Properties
Ni Fe

How to change crystal structure?

Example: Low Temperature Properties (DBTT
Phenomenon)
Ni Fe

How to change crystal structure?

Example: Creep Properties
Ni Fe

How to change crystal structure?

Two key concepts in Crystallography

(1) Lattice and basis (motif) concept

(2) Unit cell concept.

Important Note:
Envision of the atoms as hard spheres,
Lattice (Space Lattice or Crystal lattice)

Array of points

A regular periodic arrangement of points in

space in which each point has identical surroundings to
all others.

lattice is a purely mathematical concept

Crystal Structure
 Motif is repeated by translating from one
point to another points
Crystal Structure
 The crystal can be described by a 3-D
lattice, decorated with a motif (basis)

Crystal Structure ≡ Lattice + Basis (Motif)

Motif=repeatable structural units

Crystal Structure ≡ Lattice + Basis

Lattice Crystal Structure

 Basis 

 the lattice tells us how to repeat but the motif
gives what to repeat
The Unit Cell
 The unit cell is the smallest repetitive unit
that will, by translation, produce the atomic
or molecular arrangement.
Unit Cell: a simple description of a
crystal
 A single repeat unit that, when duplicated
and translated, reproduces the entire
crystal structure.
Unit Cell
 Smallest
 Most orthogonal
 Most in line with symmetry
 Most Primitive
Crystal Systems

A crystal system is described

only in terms of the unit cell
geometry

However, at the heart of the

classification is the symmetry of the lattice.
 More a unit cell is
complex, greater is
the number of
parameters required
to specify that cell.
This complexity of
the unit cells is
determined by the
“symmetry
properties” of the
array of points in the
different types of
plane and space
lattices
 IMPORTANT
Crystals and Crystal Systems are defined
based on Symmetry
& NOT
Based on the Geometry of the Unit Cell

Exampl
e

Cubic Crystal
 Does NOT imply a = b = c &  =  = 
 It implies the existence of two 3-fold axis in the structure
 ‫‪Bravais Lattice in 3-D‬‬
‫‪1811-1863‬‬
‫‪Auguste‬‬
‫‪Bravais‬‬

‫‪14 lattices‬‬
‫با قرارگيري نقاط شبکه به شيوههاي مختلف درون سلول واحد‪ ،‬حاالت مختلف شبکه بلوري به وجود مي‬
‫آيد‪ .‬به طوريکه مفهوم شبکه براوه (تقارن انتقالي) حفظ شود‬
 ‫شبکه های سه بعدی براوه‬
‫شبکه بلوری ساده‬
‫‪Simple/Primitive‬‬

‫• به شبکه هايي که نقاط شبکه در آن ها فقط در‬

‫گوشه هاي سلول واحد حضور دارند‪ ،‬شبکه‬
‫دکتر پیروز مرعشی – گروه متالورژی دانشگاه صنعتی‬

‫بلوری ساده گفته مي شود‪ .‬مجموع نقاط شبکه‬

‫در همهي شبکههاي ساده برابر ‪ 1‬است‪ .‬مانند‬
‫شبکه ساده مکعبي‪.‬‬
‫امیرکبیر‬
 ‫شبکه بلوری مركزدار )‪(body centered‬‬

‫به شبکه هايي که نقاط شبکه عالوه بر‬ ‫‪‬‬

‫گوشه ها‪ ،‬در مراکز سلول واحد نيز‬
‫دکتر پیروز مرعشی – گروه متالورژی دانشگاه صنعتی‬

‫وجود دارد‪ ،‬شبکه بلوري مرکزدار‬

‫)‪ (body centered‬گفته ميشود‪.‬‬
‫امیرکبیر‬

‫به اين ترتيب‪ ،‬تعداد نقاط شبکه در‬ ‫‪‬‬

‫يك شبکه بلوري مرکزدار برابر ‪2‬‬
‫خواهد بود‪ .‬مانند سلول واحد مکعبي‬
‫مرکزدار‪.BCC ،‬‬
 ‫شبکه بلوری وجوه مركزدار )‪(face centered‬‬

‫به شبکه هايي که نقاط شبکه‬ ‫‪‬‬

‫عالوه بر گوشه ها‪ ،‬در مراکز‬
‫وجوه سلول واحد وجود دارند‪،‬‬
‫شبکه بلوري وجوه مرکزدار‬
‫دکتر پیروز مرعشی – گروه متالورژی دانشگاه صنعتی‬

‫گفته‬ ‫‪(face‬‬ ‫)‪centered‬‬

‫ميشود‪.‬‬
‫امیرکبیر‬

‫به اين ترتيب‪ ،‬تعداد نقاط شبکه‬ ‫‪‬‬

‫در يك شبکه بلوري وجوه‬
‫مرکزدار برابر ‪ 4‬خواهد بود‪.‬‬
 ‫شبکه بلوری قاعده مركزدار )‪(base centered‬‬

‫• به شبکه هايي که نقاط شبکه عالوه بر گوشه‬

‫دکتر پیروز مرعشی – گروه متالورژی دانشگاه صنعتی‬

‫ها‪ ،‬درمراکز قاعده هاي متوازي السطوح‬

‫وجود دارند‪ ،‬شبکه بلوري قاعده مرکزدار‬
‫)‪ (base centered‬گفته ميشود‪.‬‬
‫امیرکبیر‬

‫• به اين ترتيب‪ ،‬تعداد نقاط شبکه در يك شبکه‬

‫بلوري قاعده مرکزدار برابر ‪ 2‬خواهد بود‪.‬‬
‫(مانند اورتورمبيك قاعده مرکزدار)‬
‫شبکه های ساده‪ ،‬مرکزدار‪ ،‬وجوه مرکزدار و قاعده‬
‫مرکزدار‬
‫دکتر پیروز مرعشی – گروه متالورژی دانشگاه صنعتی‬
‫امیرکبیر‬
Arrangement of lattice points in the Unit Cell
& No. of Lattice points / Cell

Position of lattice points Effective number of Lattice points / cell

1 P 8 Corners = [8  (1/8)] = 1

8 Corners
2 I + = [1 (for corners)] + [1 (BC)] = 2
1 body centre
8 Corners
= [1 (for corners)] + [6  (1/2)]
3 F +
=1+3=4
6 face centres
A/ 8 corners
4 B/ + = [1 (for corners)] + [2  (1/2)] = 2
C 2 centres of opposite faces
 We will take up these cases one by one
14 Bravais Lattices divided into 7 Crystal Systems (hence do not worry!)

A Symmetry based concept Some guidelines apply ‘Translation’ based concept

Crystal System Shape of UC Bravais Lattices

P I F C
1 Cubic Cube   
2 Tetragonal Square Prism (general height)  
3 Orthorhombic Rectangular Prism (general height)    
4 Hexagonal 120 Rhombic Prism 
5 Trigonal Parallopiped (Equilateral, Equiangular) 
6 Monoclinic Parallogramic Prism  
7 Triclinic Parallelepiped (general) 

P Primitive
Why are some of the entries missing? I Body Centred
 Why is there no C-centred cubic lattice?
 Why is the F-centred tetagonal lattice missing? F Face Centred
 ….? C A/B/C- Centred Continued…
 P I F C
1 Cubic Cube   

I
P

abc       90

Symmetry of Cubic lattices

4 2
3
m m
F
Lattice point
 P I F C
2 Tetragonal Square Prism (general height)  

I
P

Symmetry of Tetragonal lattices abc

4 2 2       90
mmm
 P I F C
3 Orthorhombic Rectangular Prism (general height)    

One convention
abc
I
P

Note the position of

‘a’ and ‘b’
abc
      90

F Symmetry of Orthorhombic lattices C

2 2 2
mmm
Is there a alternate possible set of unit cells for OR? Why is Orthorhombic called Ortho-’Rhombic’?
 P I F C
4 Hexagonal 120 Rhombic Prism 

abc
    90,   120

A single unit cell (marked in blue)

along with a 3-unit cells forming a Symmetry of Hexagonal lattices
hexagonal prism
6 2 2
mmm

What about the HCP?

Note: there is only one type of hexagonal (Does it not have an additional atom somewhere in the middle?)
lattice (the primitive one)
 P I F C
5 Trigonal Parallelepiped (Equilateral, Equiangular) 
Rhombohedral

abc
      90

Note the position of the origin

and of ‘a’, ‘b’ & ‘c’
Symmetry of Trigonal lattices

2
3
m
 P I F C
6 Monoclinic Parallogramic Prism  

One convention
abc abc
    90  

Note the position of

‘a’, ‘b’ & ‘c’

Symmetry of Monoclinic lattices

2
m
 P I F C
7 Triclinic Parallelepiped (general) 

abc
   

Symmetry of Triclinic lattices

1
C-centered Tetragonal !
Crystal Structure Attributes
1.Number of lattice point (or motif) per unit cell
2. Coordination Number (CN)
3. Correlation between lattice parameters and
atomic/ionic radius
4. Volume of Unit Cell
5. Packing Factor
1.Number of lattice point (or motif)
per unit cell
 Inside atoms
 Corner atoms
 Face centered atoms

Hexagonal Lattice
vs.
Cubic Lattice
1.Number of lattice point (or motif) per
unit cell
For non-Hexagonal Lattices
Position of lattice points Effective number of Lattice points / cell

1 P 8 Corners = [8  (1/8)] = 1

8 Corners
2 I + = [1 (for corners)] + [1 (BC)] = 2
1 body centre
8 Corners
= [1 (for corners)] + [6  (1/2)]
3 F +
=1+3=4
6 face centres
A/ 8 corners
4 B/ + = [1 (for corners)] + [2  (1/2)] = 2
C 2 centres of opposite faces
2. Coordination Number (CN)
 The number of nearest-neighbor or
touching atoms in a crystal structure
Example: CN in Simple Cubic
Example: CN in BCC
Example: CN in FCC
Example: CN in FCC
Example: CN in HCP
Example: CN in HCP
3. Correlation between lattice parameters
and atomic/ionic radius
 Directions in the unit cell along which atoms are in
continuous contact are close-packed directions. In
simple structures, particularly those with only one atom
per lattice point, we use these directions to calculate the
relationship between the apparent size of the atom and
the size of the unit cell.
3. Correlation between lattice
parameters and atomic/ionic radius
Correlation between lattice parameters
and atomic/ionic radius: HCP
Correlation between lattice parameters
and atomic/ionic radius: HCP
Correlation between lattice parameters
and atomic/ionic radius: HCP
Correlation between lattice parameters
and atomic/ionic radius: HCP
4. Volume of unit cell
  
V  ( a  b ). c
5. Crystal Packing Factor
Crystal structure characteristics of some important
crystal structure in metals
Theoretical density of crystals

N A

N A  Vuc

Prove it!
Example
Allotropic (polymorphism) transformation

Very important
characteristics

Response to
Solid-state heat
treatment
The volume change associated with
allotropic transformation.

Thermal stress
vs.
transformation stress
Importance of volume change associated
with allotropic transformation.

 Generating stress leading to (i)

distortion or (ii) cracking
 Useful Applications!
Tin disease 5.77 gr/cm3

7.5 gr/cm3

27% Change Volume

ZrO2 Problem!
 For zirconia (ZrO2):
 the stable form at room temperature (25°C) is monoclinic. As we
increase the temperature, more symmetric crystal structures
become stable. At 1170°C, the monoclinic zirconia transforms into a
tetragonal structure. The tetragonal form is stable up to 2370°C. At
that temperature, zirconia transforms into a cubic form. The cubic
form remains stable from 2370°C to a melting temperature of
2680°C. Zirconia also can have the orthorhombic form when high
pressures are applied.

 Most ceramics are very brittle and cannot

withstand more than a 0.1% change in
volume.
The volume change associated with
allotropic transformation

 
N
 
N

N
V  V
V N
%  100
V V
Example: FCC to BCC Transformation

4
FCC  BCC
2

3 3
 4r   4r 
2   
V 2 V bcc  V fcc     100   8.1%
100  
3 2

V V fcc 3
 4r 
 
 2
Coordinates of Points
Example
Example
BCC Lattice points
 Miller Indices in crystallography
 Miller indices are used to specify directions and planes.
 These directions and planes could be in lattices or in crystals.
 (It should be mentioned at the outset that special care should be given to see if the
indices are in a lattice or a crystal).
 The number of indices will match with the dimension of the lattice or the crystal:
in 1D there will be 1 index, in 2D there will be two indices, in 3D there will be 3
indices, etc.

Miller Indices Miller Indices

Directions Planes Lattices Crystals

Note: both directions and planes are imaginary constructs

Miller indices for DIRECTIONS
 A vector r passing from the origin to a lattice point can be written as:
r = r1 a + r 2 b + r3 c
 Where, a, b, c → basic vectors (or generator vectors). r  r1 a  r2 b  r3 c
• Basis vectors are unit lattice translation vectors, which define the coordinate axis
(as in the figure below) .
• Note that their lengths are usually one lattice translation
and not 1 lengthscale unit! (this is unlike for the basis
vectors of a coordinate axis). To give an example, if a
rectangle crystal has lattice parameters a = 1 cm and b =
2.5 cm, then |a| = 1 cm and |b| = 2.5 cm (it is not 1 cm
along the axes and the scale of the unit along the two
directions are different).
• In some cases, based on convenience, we may chose the
basis vector as ‘multiple lattice translations’ (i.e. instead of
one lattice translation we may chose 2 or 3).
• We may also chose alternate basis vectors for the same
structure (which corresponds to different unit cells).
Example
Example
Example
Example
Example
Example
Draw [1 -1 0]
Note
 1. Because directions are vectors, a direction
and its negative are not identical; [100] is not
equal to [-100]. They represent the same line,
but opposite directions.

 2. A direction and its multiple are identical; [100]

is the same direction as [200].
Linear Density and Linear Packing Factor
 ‫جهات هم خانوده‬
‫براي بعضي از ساختارهاي بلوري‪ ،‬چند جهت‬ ‫‪‬‬
‫غيرموازي با انديس متفاوت‪ ،‬در واقع همخانواده‬
‫هستند‪ .‬يعني فضاي بين اتمها در امتداد هر جهت‬
‫(چگالي خطي)‪ ،‬مشابه است‪.‬‬
‫دکتر پیروز مرعشی – گروه متالورژی دانشگاه صنعتی‬

‫براي مثال‪ ،‬در بلورهاي مكعبي‪ ،‬تمام جهتهايي كه با‬ ‫‪‬‬

‫‪001 010‬‬
‫نشان داده ميشوند‪ ،‬هم‪-‬‬ ‫انديسهاي ‪  ،100‬و‬
‫خانواده هستند‪.‬‬
‫جهت هاي پاد موازي‪ 1‬نيز با هم همخانواده هستند‬ ‫‪‬‬
‫امیرکبیر‬

‫پس جهت هاي ‪ 100 ، 001‬و ‪ 010‬نيز با سه جهت گفته‬

‫‪‬‬ ‫‪‬‬ ‫‪‬‬

‫شده هم خانواده هستند‪.‬‬

‫‪ 1‬يعني داراي يک راستا ولي با جهت مخالف‬

 ‫جهات همخانواده‬

‫جهتهاي هم خانواده به صورت يک خانواده گزارش ميشوند كه به صورت‬ ‫‪‬‬

‫پرانتز زاويهاي ‪ 100‬نشان داده ميشود‪.‬‬
‫عالوه بر اين‪ ،‬جهتها در بلورهاي مكعبي‪ ،‬جهتهايي كه صرفنظر از ترتيب‬ ‫‪‬‬
‫دکتر پیروز مرعشی – گروه متالورژی دانشگاه صنعتی‬

‫يا عالمت مثبت و منفي‪ ،‬انديسهاي مشابه دارند‪ ،‬با هم هم خانواده هستند؛‬
‫مانند ‪ 123‬و ‪. 213‬‬
‫‪‬‬ ‫‪‬‬

‫‪ ‬‬
‫اما اين در حالت كلي براي ساير سيستمهاي بلوري صادق نيست‪ .‬براي مثال‪،‬‬ ‫‪‬‬
‫براي سيستمهاي با تقارن تتراگونال‪ ،‬جهتهاي ‪ 100‬و ‪ 010‬همخانواده‬
‫امیرکبیر‬

‫هستند در حالي كه ‪ 001‬همخانواده آنها نيست‪.‬‬

The concept of a family of directions
 A set of directions related by symmetry operations of the lattice or the crystal is called a
family of directions. A family is a symmetry related set.
 A family of directions is represented (Miller Index notation) as: <u v w>. Note the brackets.
 Hence one has to ask two questions before deciding on the list of the members of a family:
1 Is one considering the lattice or the crystal?
2 What is the crystal system one is talking about.

Miller indices for a direction in a lattice versus a crystal

 We have seen that crystal can have symmetry equal to or lower than that of the lattice.
 If the symmetry of the crystal is lower than that of the lattice then two members belonging
to the same family in a lattice need not belong to the same family in a crystal  this is
because crystals can have lower symmetry than a lattice
(examples which will taken up soon will explain this point).
 Family of directions

Index Members in family for cubic lattices Number

(True for cubic crystals in holohedral class, but not true for all cubic crystals)

<100> [100],[100],[010],[0 10],[001],[00 1] 32=6

<110> [110],[110],[1 10],[1 10],[101],[101],[10 1],[10 1],[011],[011],[01 1],[01 1] 6  2 = 12

<111> [111],[111],[1 11],[11 1],[1 11],[11 1],[1 1 1],[1 1 1] 42=8

the ‘negatives’ (opposite direction)

 ‫صفحات بلوري‬

‫‪ ‬تعريف صفحه‬
‫‪ ‬منظور از صفحه‪ ،‬تمام صفحات موازي با هم هستند كه فاصله‬
‫دکتر پیروز مرعشی – گروه متالورژی دانشگاه صنعتی‬

‫دو صفحه متوالي آنها مساوي مقدار ثابت ‪ d‬و با هم برابر است‪.‬‬
‫مقدار فاصله ‪ ،d‬همانطور كه بعدا توضيح داده ميشود‪ ،‬از روي‬
‫انديس ميلر‪ ،‬محاسبه ميشود و براي هر دسته صفحه با انديس‬
‫امیرکبیر‬

‫ميلر خاص‪ ،‬مقدار منحصر به فردي است‪.‬‬

 ‫صفحات بلوري‬
‫دکتر پیروز مرعشی – گروه متالورژی دانشگاه صنعتی‬
‫امیرکبیر‬

‫تمام صفحاتي كه موازي صفحهاي هستند كه محور ‪ z‬را به فاصله ‪1‬‬

‫واحد از مركز قطع ميكند و با محورهاي ‪ x‬و ‪ y‬موازي است‪ ،‬و در‬
‫فاصلهي ‪ d=a‬از هم قرار دارند‪ (001) ،‬ناميده ميشوند‬
 ‫صفحات بلوري‬
‫دکتر پیروز مرعشی – گروه متالورژی دانشگاه صنعتی‬
‫امیرکبیر‬

‫از یکدیگر‬ ‫تمام صفحات موازی که به فاصله‬

‫قرار دارند‪ (110) ،‬نامیده میشوند‬
‫صفحات بلوري‬
‫دکتر پیروز مرعشی – گروه متالورژی دانشگاه صنعتی‬
‫امیرکبیر‬
 ‫صفحات بلوري‬
‫امیرکبیر‬
‫دکتر پیروز مرعشی – گروه متالورژی دانشگاه صنعتی‬

‫از یکدیگر‬ ‫تمام صفحات موازی که به فاصله‬

‫قرار دارند‪ (110) ،‬نامیده میشوند‬
Miller Indices for PLANES
Miller indices for planes is not as intuitive as that for directions and special care must be taken
in understanding them

Illustrated here for the cubic lattice

 Find intercepts along axes → 2 3 1

 Take reciprocal → 1/2 1/3 1*
 Convert to smallest integers in the same ratio → 3 2 6
 Enclose in parenthesis → (326)
 Note: (326) does NOT represent one plane but an infinite set of parallel planes
passing through lattice points.
 Set of planes should not be confused with a family of planes- which we shall consider next.
* As we shall see later reciprocals are taken to avoid infinities in the ‘defining indices’ of planes
 ‫انديسگذاري صفحات‬
‫انديسگذاري صفحات بلوري نيز با استفاده از انديسهاي ميلر انجام‬ ‫‪‬‬
‫ميشود‪ .‬براي يافتن انديس ميلر صفحات‪ ،‬بايد مراحل زير طي شود‪:‬‬
‫الف) يک دستگاه مختصاتي مناسب و راستگرد انتخاب كنيد‪.‬‬ ‫‪‬‬
‫امیرکبیر‬
‫دکتر پیروز مرعشی – گروه متالورژی دانشگاه صنعتی‬

‫ب) صفحهي بلوري با هر يک از محورها موازي است يا آن را قطع ميكند‪ .‬طول‬ ‫‪‬‬
‫از مبدا تا محل برخورد صفحه تا محور بر حسب كسري از پارامترهاي شبكه ‪،a‬‬
‫‪ b‬و ‪ c‬تعيين ميشود‪.‬‬
‫پ) برعكس اين اعداد را در نظر ميگيريم‪ .‬فاصلهي مبدا تا محل برخورد‬ ‫‪‬‬
‫صفحهاي كه با يک محور موازي باشد را ميتوان بينهايت فرض كرد و بنابراين‬
‫انديس آن را صفر در نظر گرفت‪.‬‬
‫ت) در نهايت‪ ،‬انديسهاي صحيح‪ ،‬بدون استفاده از ويرگول بين آنها‪ ،‬درون يک‬ ‫‪‬‬
‫پرانتز به صورت (‪ )hkl‬نوشته ميشوند‪.‬‬
‫محل برخورد با محورها در جهت منفي نسبت به مبدا‪ ،‬با عالمت بار يا منها روي‬ ‫‪‬‬
‫انديس مربوط به آن مشخص ميشود‪.‬‬
 ‫انديسگذاري صفحات‬
‫تذكر‪:‬‬ ‫‪‬‬
‫‪ -1‬در صورتي كه صفحه از مبدا مختصات بگذرد‪ ،‬بايد مبدا را به يک نقطهي‬ ‫‪‬‬
‫مناسب ديگر منتقل كرد‪.‬‬
‫‪ -2‬گاهي اوقات با تغيير مبدا مختصات‪ ،‬ميتوان محل تقاطع صفحه به‬ ‫‪‬‬
‫امیرکبیر‬
‫دکتر پیروز مرعشی – گروه متالورژی دانشگاه صنعتی‬

‫محورهاي مختصات را آسانتر پيدا كرد‪.‬‬

‫‪ -3‬صفحهي )‪ (hkl‬با صفحهي )‪ n( (nh nk nl‬يک عدد صحيح و غيرصفر‬ ‫‪‬‬
‫است) يکسان نيست‪.‬‬
‫‪ -4‬برعكس كردن عالمت تمام انديسها‪ ،‬صفحهي مشابهاي با صفحهي اول‬ ‫‪‬‬
‫نشان ميدهد كه با فاصلهي مساوي در طرف ديگر مبدا قرار داشته و با صفحهي‬
‫اول موازي است‪.‬‬
‫‪ -5‬در شبكههاي مكعبي‪ ،‬انديس جهت عمود به صفحه با انديس ميلر صفحه‬ ‫‪‬‬
‫يکسان است‪.‬‬
Example
Example
What are the Miller indices of the green plane in the figure below?

 Extend the plane to intersect the x,y,z axes.

 The intercepts are: 2,2,2
 Reciprocal: ½, ½, ½
 Smallest ratio: 1,1,1
 Enclose in brackets to get Miller indices: (111)
Q&A What are the Miller indices of the green plane in the figure below?

 Extend the plane to intersect the x,y,z axes.

 The intercepts are: 2,2,2
 Reciprocal: ½, ½, ½
 Smallest ratio: 1,1,1
 Enclose in brackets to get Miller indices: (111)

 Another method.
 Move origin (‘O’) to opposite vertex (of the cube).
 Chose new axes as: x, y, z.
 The new intercepts will be: 1,1,1
‫‪Example‬‬
‫دکتر پیروز مرعشی – گروه متالورژی دانشگاه صنعتی‬
‫امیرکبیر‬
 ‫‪Example‬‬
‫انديس ميلر صفحه ‪:A‬‬ ‫‪‬‬
‫از آنجايي كه اين صفجه از مبدا مختصات ميگذرد‪ ،‬پس بايد مبدا مختصات را‬ ‫‪‬‬
‫به يک نقطه جديد منتقل كرد‪ .‬براي راحتي كار مبدا را به نقطه (‪ )010‬منتقل‬
‫ميكنيم‪ .‬در اين حالت داريم‪:‬‬
‫امیرکبیر‬
‫دکتر پیروز مرعشی – گروه متالورژی دانشگاه صنعتی‬

‫پس انديس ميلر اين صفحه به صورت ‪ 111‬است‪.‬‬ ‫‪‬‬

 ‫‪Example‬‬
‫انديس ميلر صفحه ‪:B‬‬ ‫‪‬‬
‫امیرکبیر‬
‫دکتر پیروز مرعشی – گروه متالورژی دانشگاه صنعتی‬

‫پس انديس ميلر اين صفحه به صورت ‪ 030‬است‪.‬‬ ‫‪‬‬

‫‪ ‬‬

‫‪142‬‬
 ‫‪Example‬‬
‫انديس ميلر صفحه ‪:C‬‬ ‫‪‬‬
‫از آنجايي كه براي پيدا كردن نقاط برخورد محورهاي مختصات فعلي نياز‬ ‫‪‬‬
‫به امتداد دادن صفحه و استفاده از روابط هندسي است‪ ،‬براي راحتي كار‬
‫مبدا را به نقطه )‪ (0,0,1‬منتقل ميكنيم‪ .‬در اين حالت داريم‪:‬‬
‫امیرکبیر‬
‫دکتر پیروز مرعشی – گروه متالورژی دانشگاه صنعتی‬

‫است‪.‬‬ ‫پس انديس ميلر اين صفحه به صورت‬ ‫‪‬‬

Planar Density
‫‪Closed packed direction and‬‬
‫‪planes in cubic system‬‬
‫دکتر پیروز مرعشی – گروه متالورژی دانشگاه صنعتی‬
‫امیرکبیر‬
Miller indices in Hexagonal
Hexagonal important planes
 Related to ‘l’ index
(h k i l)
Related to ‘k’ index
i = (h + k)

Miller-Bravais Indices for the Basal Plane

Related to ‘i’ index Related to ‘h’ index

Intercepts →    1
Plane → (0 0 0 1)

Basal Plane
 Intercepts → 1 1 - ½  (h k i l)
Plane → (1 12 0) i = (h + k)

a3

a2
Planes which have  intercept along c-
axis (i.e. vertical planes) are called
Prism planes
a1

The use of the 4 index notation is to bring out the equivalence between
crystallographically equivalent planes and directions (as will become clear in coming slides)
 Inclined planes which have finite intercept
along c-axis are called Pyramidal planes

Intercepts → 1 1 - ½ 1
Plane → (1 12 1)

Intercepts → 1   1 1
Plane → (1 01 1)
Example
11 01
:A

(0003) B

11 00
:C
Example
Direction in Hexagonal: M index
[u v w]=ua1+va2+wc
Direction in Hexagonal: M index
[u v w]=ua1+va2+wc
Direction in Hexagonal: M-B index

[u v t w]=ua1+va2+ta3+wc
a1+a2+a3=0
u+v+t=0
Example
Example
 One has to be careful in determining directions in the Miller-Bravais system.
 Basis vectors a1, a2 & a3 are symmetrically related by a six fold axis.
 The 3rd index is redundant and is included to bring out the equality between equivalent
directions (like in the case of planes).
 In the drawing of the directions we use an additional guide hexagon 3 times the unit basis
vectors (ai).

Guide Hexagon
Directions Drawing the [1120] direction
• Trace a path along the basis vectors as required by the direction. In the current example move
1unit along a1, 1unit along a2 and 2 units along a3.
• Directions are projected onto the basis vectors to determine the components and hence the Miller-
Bravais indices can be determined as in the table.

a1 a2 a3
Projections a/2 a/2 −a

Normalized wrt LP 1/2 1/2 −1

Factorization 1 1 −2

Indices [1 1 2 0]
We do similar exercises to draw other directions as well

Drawing the [101 0] direction

Some important directions

a1 a2 a3
Projections 3a/2 0 –3a/2
Normalized wrt
3/2 0 – 3/2
LP
Factorization 1 0 −1

Indices [1 0 –1 0]
Hexagonal directions: u+v=-t
Conversion of M indices to M-B
indices
Example
Example
Example
Important directions in hexagonal
Example: APF in (1 -1 0 0) HCP
Example: APF in (0001) HCP
Close-packed planes and
directions
 Family of directions

Index Members in family for cubic lattices Number

(True for cubic crystals in holohedral class, but not true for all cubic crystals)

<100> [100],[100],[010],[0 10],[001],[00 1] 6

<110> [110],[110],[1 10],[1 10],[101],[101],[10 1],[10 1],[011],[011],[01 1],[01 1] 12

<111> [111],[111],[1 11],[11 1],[1 11],[11 1],[1 1 1],[1 1 1] 8

Q: Family of {100} in Cubic?
(100) (-1 00)
(010) (0 -1 0)
(001) (00 -1)
Six members

abc       90
Q: Family of {100} in tetragonal?
(100) (-1 00)
(010) (0 -1 0)
Four members

abc
      90
Q: Family of {100} in orthorhombic?

(100) (-1 00)

Two members

abc
      90
{100} Families
{110} Families
Members of a family of planes in cubic crystal/lattice

Index n* n* is the No. of members in a cubic lattice

{100} 6
{110} 12
{111} 8
{210} 24
{211} 24
{221} 24
{310} 24
{311} 24
{320} 24
8 planes of {111}cubic lattice family
{321} 48 forming a regular octahedron
Plane distance
Crystal Structure of Materials:
Atomic packing
Atomic packing depends on the nature of
inter-atomic bonding, whether the bonding
is directional or non-directional.
Directional bonds
If the bonding is directional, the local
atomic arrangement is determined by the
bond angle.

Covalent bonds characteristics:

(i) discreteness and
(ii) spatial direction
S orbital
 Notice that the amount
of electron density
(here represented by
the intensity of the blue
color) doesn't depend
on direction. It does,
however, depend on
distance from the
center of the atom .
P orbital
P orbital
directional bonds
Bonding polyhedron
Non-directional bonds
If the bonding is non-directional, the
arrangement depends on relative sizes of
the atoms

Coordination number
Factors determining the crystal
structure of materials
 The most stable arrangement in a crystal will be
that which minimizes the energy per unit volume
or, in the other words, the one that:
(1) Preserves electrical neutrality
(2) Satisfy the directionality and discreetness of all
covalent bonds
(3) Minimizes strong ion-ion repulsion
(4) Packs the atoms as closely as possible,
consistent with above conditions
Crystal structure of metals
(i) Maximum packing
(ii) Directionality of bonds, if any.
One Dimensional Close Packing

 CN?
Two packing arrangements of
atoms in 2D:
closest-packed of a single layer of spheres is the
HEXAGONAL coordination of each sphere

ABABAB AAAA
Effective packing of atoms in 3-D
Closet packed planes in
crystals
 {111} in FCC and {0001} in HCP
3-D packing from 2-D square
packed layers
 AAA packing
 ‫‪3-D packing from 2-D hexagonal‬‬
‫‪closed packed layers‬‬
‫مركزهاي تمام اتمها در صفحهي فشرده با عالمت ‪ A‬نامگذاري مي شود‬ ‫‪‬‬
‫دو دسته فرورفتگي معادل هم توسط سه اتم مجاور به وجود ميآيد كه اتمهاي صفحهي بعدي‬ ‫‪‬‬
‫ميتوانند در اين حفرهها قرار بگيرند‪.‬‬

‫فرورفتگيهاي يک در ميان كه مثلث با راس رو به باال تشكيل ميدهند به صورت اختياري با‬ ‫‪‬‬
‫عالمت ‪ B‬و بقيهي فرورفتگيها كه مثلث با راس رو به پايين تشكيل ميدهند با عالمت ‪C‬‬
‫مشخص شدهاند‪ .‬صفحهي فشردهي دوم ميتواند به صورتي روي صفحهي اول قرار بگيرد كه‬
‫مراكز اتمهاي آن روي موقعيتهاي ‪ B‬يا ‪ C‬باشند‪ ،‬تا اينجا هر دو اين موقعيتها معادل هستند‪.‬‬
‫فرض كنيد كه موقعيتهاي ‪ B‬به طور دلخواه انتخاب شدهاند‪ ،‬در اين صورت ترتيب چيده‬
‫‪193‬‬ ‫شدن‪ AB ،‬ناميده ميشود‪.‬‬
 ‫‪3-D packing from 2-D hexagonal‬‬
‫‪closed packed layers: HCP‬‬
‫دکتر پیروز مرعشی – گروه متالورژی دانشگاه صنعتی‬
‫امیرکبیر‬

‫‪(c) 2003 Brooks/Cole Publishing / Thomson‬‬

‫™‪Learning‬‬

‫براي ‪ ،HCP‬مركزهاي اين اليه مستقيما روي موقعيتهاي اوليهي ‪ A‬قرار دارند‪ .‬اين‬ ‫‪‬‬
‫ترتيب چيده شدن‪ ،ABABAB… ،‬صفحههاي فشرده دائما تكرار ميشود‪.‬‬
‫البته آرايش …‪ ACAC‬نيز معادل همين است‪.‬‬ ‫‪‬‬
 ‫‪3-D packing from 2-D hexagonal‬‬
‫‪closed packed layers: FCC‬‬
‫براي ساختار بلوري ‪ ،FCC‬مركزهاي صفحهي سوم روي موقعيتهاي ‪ C‬صفحهي اول‬ ‫‪‬‬
‫قرار دارند‪ .‬اين آرايش …‪ ABCABCABC‬صفحههاي فشرده را به وجود ميآورد؛‬
‫يعني آرايش اتمي به صورت سه صفحه اتمي‪ ،‬تكرار ميشود‪.‬‬
‫دکتر پیروز مرعشی – گروه متالورژی دانشگاه صنعتی‬
‫امیرکبیر‬
 ‫‪3-D packing from 2-D hexagonal‬‬
‫‪closed packed layers: FCC‬‬
‫دکتر پیروز مرعشی – گروه متالورژی دانشگاه صنعتی‬
‫امیرکبیر‬
Nuclei of FCC Crystal during
solidification
Nuclei of HCP Crystal during
solidification
In 3D, a close packed structure is formed by
stacking Close Packed Planes:

 Two possible stacking sequences:

3-D packing from 2-D square
hexagonal closed packed layers
Crystal Structure of Metals
FCC Elements
HCP Elements
BCC Elements
Crystal Structure of Covalent
Elements
Crystal Structure of Covalent
Elements
Crystal Structure of Ionic Materials:
Ceramics
Factors to determine the crystal structure:

(1) Electrical Neutrality: Formula

(2) rC/rA : Coordination number

 CN for cations is the number of nearest

anions and vice versa.
Let us start by looking at the relative sizes of some ions in the periodic table

Be2+
Li Li+ Be
1.52 0.68 1.12 0.35

Mg2+
Na Na+ Mg
0.66
1.85 0.97 1.60

1.46 1.31 1.25 1.12 1.24

K K+ Ca Ca2+ Ti V Cr Mn Fe
2.31 1.33 1.96 0.99

Ti4+ V3+ Cr3+ Mn2+ Fe2+ Fe3+

0.68 0.74 0.63 0.83 0.64
0.74

Rb Rb+ Sr Sr2+

2.46 1.47 2.15

1.12 B3+ C4+ N3+ O2
B
0.23
C 0.2
N O F F
0.1-0.2 1.33
0.89 0.77 0.74 0.74 1.40 0.72

Cs Cs+ Ba Ba2+
Si4+ 5+
Al3+ P S6+
1.67 2.17
1.34 Al Si P S Cl Cl
2.62
0.42 0.35 0.30
1.26 0.51 1.17 1.10 1.04 1.07 1.81

Values are: Pauling-Ahrens Radii in Å

CN in Ionic Materials
 The crystal structures of ionically bonded compounds often can be
described by placing the anions at the normal lattice points of a unit
cell, with the cations then located at one or more of the interstitial
sites (or vice versa).
 CN=3

 AP rA 3 rC
cos OAP  cos 30      0.155
OA rA  rC 2 rA
 ‫مي دانيم در يک چهار وجهي منتظم زاويه بين‬ ‫‪‬‬
‫اضالعي كه اتم فرضي را با دو اتم مماس به هم‬
‫‪CN=4‬‬ ‫متصل مي كند تقريباً ˚‪ 109‬است‪ .‬بنابر قضيه‬
‫سينوس ها داريم ‪:‬‬

‫مثلث متساويالساقين است پس مقدار ‪ α‬برابر‬ ‫‪‬‬

‫˚‪35.5‬خواهد بود و از آنجا كه تمام اتم ها مماسند‬
‫داريم‪:‬‬

‫‪x=r+R‬‬ ‫‪a = 2R‬‬ ‫‪‬‬

‫در نتيجه داريم ‪:‬‬ ‫‪‬‬

‫‪(r + R) = 2Rsin 35.5‬‬ ‫‪‬‬

 Let us look at a pictorial representation of the coordination around the cation for various rc/ra.
 When we consider any coordination, e.g. CN3 (triangular coordination), the lower numerical
value corresponds to the CN3 but the higher value arises from CN4 coordination. In this
example: (i) the rc/ra cannot be smaller than 0.155 (else we will violate the ‘no rattling’ rule),
(ii) the ratio has to be larger than 0.155 so that the anions do not touch (the ‘anion-no-touch’
rule), (iii) if the ratio (rc/ra) is larger than 0.225 the preferred coordination is tetrahedral (the
higher coordination number rule).

Linear → CN2 Triangular → CN3 Tetrahedral → CN4

rc/ra  (0 - 0.155)

rc/ra  (0.155 - 0.225) rc/ra  (0.225 - 0.414)

Lower limit decided by
current coordination

Upper limit decided by next

higher possible coordination
 For even larger rc/ra the local coordination number increases to 6, 8 and then 12.

Octahedral → CN6 Cubic → CN8

rc/ra  (0.414 - 0.732) rc/ra  (0.732 - 1.0)

2rx  2ra  3a  3(2ra ) rx  ( 3  1)ra

rx
 ( 3  1)  0.732
ra
CN12 rc/ra = 1.0 Both the CCP (FCC) and HCP packing have a coordination number of 12.

FCC HCP
Rules for Ionic Materials
Rules for Ionic Materials
(ii) Electrostatic Bond Strength (EBS)

EBS for cation-anion bond=(cation charge)/(CN)C

EBS=(anion charge)/(CN)A
Rules for Ionic Materials
(iii)