Lec 2 - Nanomaterials

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Lec 2 - Nanomaterials

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CHEE 4301

Nanomaterials and

their characterisation

Traditionally, metals and ceramics are crystals and

their crystalline nature affects their properties.

The earliest crystallographers discovered that the

naturally developed external facets of substance

were related to the regularity of their internal

structures.

Lecture 2

Crystal Structure 1

Professor Jin Zou

Contact details: Office Room 75-108

Telephone: 3346 3195

Email: j.zou@uq.edu.au

Lithium Pegmatite

of one or more atoms, which are regularly and

periodically arranged in three dimensions. This

regularity extends over thousands and millions of

molecular dimensions.

crystal structure = lattice + basis

Note:

The smallest building

basis

blocks of a crystal are

referred to as the basis,

the periodic arrangement

is described by the lattice.

lattice

points

crystal structure

and to focus on the lattice.

The lattice is a three-dimensional array of points (lattice

points), each of which has identical surroundings.

Notes on Unit Cells:

[a Unit Cell represents a small

volume of a lattice

[the whole lattice can be

reconstructed by repeating this unit

cell without empty space in

between

[the unit cell is defined by three

independent unit vectors, a, b, and c

[the direction of the unit vectors a, b,

and c defines the direction of the x, y

and z axes, called the crystal axes

Primitive Cells

Multiple Cells

multiple. In general, there are infinite

number of parallelogram cells for a given

lattice.

described by the relative lengths of three

independent unit vectors (a, b, and c) and

three independent angles between them (,

, and ).

is angle between b and c

is angle between c and a

is angle between a and b

In 2D case

b 3 variables

0

6 variables

27/07/16

For a given lattice, an Unit Cell is defined as the

smallest parallelogram cell that contains less

variables (representing the highest symmetry of

the lattice). - 90 and 120 do not count as

variables.

Lattice parameters a & b are lengths of independent

sides of an Unit Cell.

Triclinic System

Seven distinct Unit Cells can be recognised

for all possible crystalline materials. The

seven Unit Cells are associated with seven

systems of crystal axes called the seven

Crystal Systems.

z

Triclinic system

Monoclinic system

Orthorhombic system

Tetragonal system

Cubic system

Hexagonal system y

Rhombohedral system

Monoclinic System

6 variables

4 variables

Orthorhombic System

Tetragonal System

3 variables

2 variables

27/07/16

Cubic System

Hexagonal System

In the hexagonal system,

a b c, 90 and 120.

c

b

1 variable

2 variables

Crystal

systems

Triclinic

Monoclinic

Orthorhombic

Tetragonal

Cubic

Hexagonal

Rhombohedral

Necessary

conditions

a b c,

a b c, 90

a b c, 90

a b c, 90

a b c, 90

a b c, 90, 120

a b c, ( 90)

2 variables

14 Bravais lattices

types are possible to represent the highest

symmetry of the lattice. These types are

Why cubic

does not

have a Ccentred

lattice?

P = primitive

I = body-centred

F = face-centred

C = base (one pair of parallel sides)-centred

distributing lattice points to make 3D lattices.

27/07/16

Each atom has neighbours

The coordination number (Z) is the number of first

nearest neighbours

In the case of the 2D square lattice, Z = 4

In turn, second nearest neighbours can be

determined

Lattice Parameter

In the simple case, the lattice parameter of an

unit cell is determined by the size of atom

In the square lattice, the lattice parameter is the

length of the side of the unit cell a=2Ratom

a

First nearest

neighbours

Second nearest

neighbours

unit cell occupied by atoms

Assume that atoms are spheres with a specific

radius, the APF can be calculated.

For the case of (2-D) simple

squared unit cell

APF( area ) =

2

Ratom

1 4

4

a2

and a = 2 Ratom

Ratom

APF( area ) =

= 0.79 = 79%

Simple Cubic

Z= 6

a = 2R

V =a3 = 8R3

APF=0.57=57%

1 atom/unit cell

Z= 8

a = (4/ 3)R

V =a3 = (64/3 3 )R3

APF=0.68=68%

2 atom/unit cell

Ratom

8 corner atoms = 81/8 = 1,

6 face atoms = 61/2 = 3,

so that total number of atoms = 4 atoms

Volume of unit cell = a3=(2 2 r)3

4 3 1

r

8 + 1 6

8

2

APF( vol ) = 3

a3

and a = 2 2r

APF( vol ) =

3 2

= 0.74 = 74%

Packing Structures

What is the APF

of close-packed

layer (assuming

2D)?

Z= 12

a = (2 2)R

V =a3 = (16 2)R3

APF=0.74=74%

4 atom/unit cell

Z= 12

a = 2R

V = (8 2)R3

APF=0.74=74%

2 atom/unit cell

c/a=1.633

Simple Cubic

Simple

Hexagonal

27/07/16

Face-centred cubic

structure

Hexagonal close-packed

structure

B

A

http://www.physics-in-a-nutshell.com/article/11#the-hcp-structure

Chemical bonding

Size of atoms in structure (especially in

compounds)

Temperature

The crystal structure is the lowest energy

configuration of atoms.

As temperature varies, this can change

For example - Fe (Iron)

Concept of lattices and unit cell

7 crystal systems and 14 Bravais lattices

Concepts of

nearest neighbours

coordination number (Z)

lattice parameters (a)

atomic packing fraction (APF)

For 912C < T < 1394C, Fe structure is FCC: -Fe

For T < 912C, Fe structure is BCC (again): -Fe

Below 600C, -Fe becomes magnetic

Homework

Many elements, such as C, Si and Ge, have a

special structure Diamond structure, a special FCC

structure containing 8 atoms (of the same kind) in

each unit cell. As a result, there are two atoms relate

to each lattice point.

Do your literature search (from internet) to find out

and draw the diamond structure.

Based on the obtained structure, determine

the numbers of first and second nearest neighbours

the lattice parameter (assume r is the radius of the

atom)

the atomic packing fraction

Books

Crystallography, W. Borchardt-Ott

Crystallography and Crystal Defects, A. Kelly, G.W.

Groves, and P. Kidd

The Basics of Crystallography and Diffraction, C.

Hammond

The Structure of Materials, S.M. Allen and E.L.

Thomas

Websites

http://www.matter.org.uk/matscicdrom/manual/xl.html

http://www.msm.cam.ac.uk/phase-trans/2001/

intro.cryst.pdf

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