Crystal Structure

Introduction

Atomic Structure
Nomor atom = jumlah proton= jumlah netron dalam suatu atom Massa atom(nomor massa) = massa proton + masa neutron Massa proton= massa netron= 1,67x10 -27 kg Massa elekron = 9.11 X 10-31 kg The atomic mass unit (amu) sebagai satuan berat atom, sebagai standart adalah 1/12 berat atom 12C =1.66 X 10 -24 gr = 1 amu Berat atom sering dinyatakan per mol (gr/mol) Satu mol menyatakan jumlah partikel yang yang mempunyai massa dalam gram Jumlah atom dalam satu mol dinyatakan dengan Avogadro number, N = 6.023 x 1023

Atomic Structure
ATOM = (PROTON+NEUTRON) + ELECTRON
Bohr atom model

Wave-mechanical model

Periodic Table

Atomic Bonding
Primary bonding Secondary bonding Influences the physical properties of material

Atomic Bonding - Primary

Ionic bonding Composed of both metallic and nonmetallic elements Created between two unlike atoms with different electronegativities, or Strong Coulomb interaction among negative atoms (have an extra electron each) and positive atoms (lost an electron).

Atomic Bonding - Primary

Ionic bonding NaCl. When sodium donates its valence electron to chlorine, each becomes an ion; attraction occurs, and the ionic bond is formed

Atomic Bonding - Primary

Covalent bonding Stable electron configurations are assumed by the sharing of electrons between adjacent atoms Two atoms that are covalently bonded will each contribute at least one electron to the bond, and the shared electrons may be considered to belong to both atoms Directional; that is, it is between specific atoms and may exist only in the direction between one atom and another that participates in the electron sharing.

Atomic Bonding - Primary

Example: H2, Cl2, CH4, SiC diamond, H2O, Number of covalent bonds (NCB) that is possible for a particular atom is determined by the number of valence electrons. NCB = 8 N; N is valence electrons

Atomic Bonding - Primary

Metallic bonding Metals and their alloys. Valence electrons are not bound to any particular atom in the solid and are more or less free to drift throughout the entire metalforming sea of electrons The remaining nonvalence electrons and atomic nuclei form what are called ion cores, which possess a net positive charge equal in magnitude to the total valence electron charge per atom

Atomic Bonding - Primary

Metallic bonding Nondirectional free electrons act as a glue to hold the ion cores together

Atomic Bonding - Secondary

Van der waals bonding Physical bond Weak Secondary bonding exists between virtually all atoms or molecules, but its presence may be obscured if any of the three primary bonding types is present Secondary bonding forces arise from atomic or molecular dipoles. In essence, an electric dipole exists whenever there is some separation of positive and negative portions of an atom or molecule.

Atomic Bonding - Secondary

Van der waals bonding The bonding results from the coulombic attraction between the positive end of one dipole and the negative region of an adjacent Dipole interactions occur between induced dipoles, between induced dipoles and polar molecules (which have permanent dipoles), and between polar molecules

Atomic Bonding - Secondary

Van der waals bonding Hydrogen bond: a special type of secondary bonding, is found to exist between some molecules that have hydrogen as one of the constituents Example: HF, HCl

Bonding Forces & Energies

Force: attractive and repulsive Magnitude is a function of the separation or interatomic distance The bonding energy for two atoms, E0, corresponds to the energy at minimum point; it represents the energy that would be required to separate these two atoms to an infinite separation Furthermore, a number of material properties depend on E0, the curve shape, and bonding type

Bonding Forces & Energies

Crystal Structure
Properties of material directly related to crystal structure Classification of solid materials: the regularity with which atoms or ions are arranged with respect to one another

Crystal Structure
Crystalline: The atoms are situated in a repeating or periodic array over large atomic distances; Long-range order exists, such that upon solidification, The atoms will position themselves in a repetitive threedimensional pattern, in which each atom is bonded to its nearest-neighbor atoms Metals, many ceramic materials, certain polymer

Crystal Structure
Non crystalline Amorphous No crystallization Absence of long range order

Crystal Structure
Illustration of some structure of materials

Crystal Structure

Crystal Structure
Atomic hard sphere model Lattice: three-dimensional array of points coinciding with atom positions (or sphere centers). Lattice: A collection of points that divide space into smaller equally sized segments or 3D network of imaginary lines connecting the atoms

Crystal Structure: Unit Cells

Subdivision of crystall structure consist of small repeat entities A subdivision of the lattice that still retains the overall characteristics of the entire lattice parallelepipeds or prisms having three sets of parallel faces; one is drawn within the aggregate of spheres which in this case happens to be a cube Basic structural unit or building block of the crystal structure and defines the crystal structure by virtue of its geometry and the atom positions within

Crystal Structure: Unit Cells

Unit cell

Metallic Crystal Structures

Face centered cubic (FCC) Body centered cubic (BCC) Hexagonal close-packed (HCP)

Metallic Crystal Structures: FCC

Atoms located at each of the corners and the centers of all the cube faces Al, Cu, Ag, Au Total atom : 4 per unit cell a = 2Re2 Coordination number: nearest-neighbor or touching atoms: 12 APF: Atomic packing factor: 0.74

Metallic Crystal Structures: BCC

Atoms located at all eight corners and a single atom at the cube center Relation between unit cell length a and atomic radius R: a= 4R/e3 Total atom per unit cell 2 Cr, Fe, W Coordination number 8 APF = 0.68

Metallic Crystal Structures: HCP

Unit cell : hexagonal form Total atoms 6 per unit cell c/a ratio = 1.633 Coordination number 12 APF = 0.74 Mg, Zn, Ti, Cd

Metallic Crystal Structures

Thoretical density:
nA VC N A

n = number of atoms associated with each unit cell A = atomic weight VC = volume of the unit cell NA = Avogadros number (6.023 x1023 atoms/mol)

Polymorphism
The characteristic of some metals or nonmetals for being able to exist in more than one crystal structure Depends on temperature and external pressure Allotropy: polymorphism in elemental solids, reversible polymorphism Fe, C

Crystal Systems
Division of crystal structure based on the combination of lattice parameters Lattice parameters: unit length (a, b, c) and interaxial angle (, , ) 7 possible crystal system

Crystal Systems

Crystalographic
Points Directions Planes The basis for determining index values is the unit cell, with a right-handed coordinate system consisting of three (x, y, and z) axes situated at one of the corners and coinciding with the unit cell edges

Crystalographic Poin Coordinates

The position of any point located within a unit cell may be specified in terms of its coordinates as fractional multiples of the unit cell lengths i.e. a, b, c.

Crystalographic Poin Coordinates

Locate the coordinate of 1 Unit cell length: a=0.48 nm, b=0.46 nm, c=0.40 nm Fractional length: q=1/4, r=1, s=1/2 Then qa=1/4x0.48=0.12 nm along x, rb=1x0.46=o.46 nm along y, sc=1/2x0.40=0.20 nm along z. Sketch the position according to the last calculation fig. (b)

Crystalographic Poin Coordinates

Point coordinates of all atom positions for a BCC

Crystalographic Directions
Line between two points or a vector A vector of convenient length is positioned such that it passes through the origin of the coordinate system. Any vector may be translated throughout the crystal lattice without alteration, if parallelism is maintained. The length of the vector projection on each of the three axes is determined; these are measured in terms of the unit cell dimensions a, b, and c. These three numbers are multiplied or divided by a common factor to reduce them to the smallest integer values. The three indices, not separated by commas, are enclosed in square brackets, thus: [uvw]. The u, v, and w integers correspond to the reduced projections along the x, y, and z axes, respectively

Crystalographic Directions
Determine the indices for the direction shown in the accompanying figure

Crystalographic Directions
Draw a [110] direction This problem is solved by reversing the procedure of the preceding example. The projections along the x, y, and z axes are a, and 0a, respectively.This direction is defined by a vector passing from the origin to point P, which is located by first moving along the x axis a units, and from this position, parallel to the y axis units, as indicated in the figure. There is no z component to the vector, since the z projection is zero

Crystalographic Directions
Direction A 1. Two points are 1, 0, 0, and 0, 0, 0 2. 1, 0, 0, -0, 0, 0 = 1, 0, 0 3. No fractions to clear or integers to reduce 4. [100] Direction B 1. Two points are 1, 1, 1 and 0, 0, 0 2. 1, 1, 1, -0, 0, 0 = 1, 1, 1 3. No fractions to clear or integers to reduce 4. [111] Direction C 1. Two points are 0, 0, 1 and 1/2, 1, 0 2. 0, 0, 1 -1/2, 1, 0 = -1/2, -1, 1 3. 2(-1/2, -1, 1) = -1, -2, 2 4. [ 1 2 2]

Crystalographic Directions
Several nonparallel directions with different indices are actually equivalent the spacing of atoms along each direction is the same. Equivalent directionsfamilybrackets <> <100>: [100], [100 ], [010], [010], [001], and [001]

Crystalographic HCP Directions

Four axis / Miller-Bravais Conversion from 3 index system to 4 index system
[u ' v ' w ' ] [uvtw ] Formulas 1 u ( 2 u ' v ' ) 3 1 v ( 2 v ' u ' ) 3 t (u v ) w w'

Crystalographic HCP Directions

Determine direction in fig (a) Projection: a(a1 axis), a(a2 axis) and c(z axis) u=1 v=1 w=1 Converting 3 index to 4 index using the formulas 1,1,-2,3 [1123]

Crystalographic Planes
Crystallographic planes are specified by three Miller indices as (hkl) except in HCP If the plane passes through the selected origin, either another parallel plane must be constructed within the unit cell by an appropriate translation, or a new origin must be established at the corner of another unit cell. At this point the crystallographic plane either intersects or parallels each of the three axes; the length of the planar intercept for each axis is determined in terms of the lattice parameters a, b, and c. The reciprocals of these numbers are taken. A plane that parallels an axis may be considered to have an infinite intercept, and, therefore, a zero index. If necessary, these three numbers are changed to the set of smallest integers by multiplication or division by a common factor Finally, the integer indices, not separated by commas, are enclosed within parentheses, thus: (hkl).

Crystalographic Planes
Determine the miller indices of fig (a)

Crystalographic Planes
Construct a (011) plane within a cubic Carry out the procedure used in the preceding example in reverse order the indices are removed from the parentheses, and reciprocals are taken, which yields , -1, 1. x=paralel, y=-1, z=1 Draw it as per fig (b)

Crystalographic Planes
Plane A 1. x = 1, y = 1, z = 1 2.1/x = 1, 1/y = 1,1 /z = 1 3. No fractions to clear 4. (111) Plane B 1. The plane never intercepts the z axis, so x = 1, y = 2, and z = 2. 1/x = 1, 1/y =1/2, 1/z = 0 3. Clear fractions: 1/x = 2, 1/y = 1, 1/z = 0 4. (210) Plane C 1. We must move the origin, since the plane passes through 0, 0, 0. Lets move the origin one lattice parameter in the ydirection. Then, x = , y = -1, and z = 2. 1/x = 0, 1/y = -1, 1/z = 0 3. No fractions to clear 4. (0 1 0)

Crystalographic Planes
One interesting and unique characteristic of cubic crystals is that planes and directions having the same indices are perpendicular to one another Reversing the directions of all indices specifies another plane parallel to, on the opposite side of and equidistant from, the origin Equivalent planes (above definition) family of planes { } s

Crystalographic Planes

Crystalographic HCP Planes

Miller-Bravais index Four-index (hkil) i = -(h+k)

Crystalographic HCP Planes

Determine the MillerBravais indices for the plane shown in the figure Consider the plane in the figure referenced to the parallelepiped labeled with the letters A through H at its corners Intersections: a1=a, a2=-a, z=c 1, -1, 1 h= 1, k= -1, l= 1 Calculate i, i= 0 Thus, [1110] parallel to a3 axis

Crystalographic HCP Planes

Plane A 1. a1 = , a2 = , a3 = , c = 1 2. 1/a1 = 0, 1/a2 = 0, 1/a3 = 0, 1/c = 1 3. No fractions to clear 4. (0001) Plane B 1. a1 = 1, a2 = 1, a3 = -1/2, c = 1 2. 1/a1 = 1, 1/a2 = 1, 1/a3 = -2, 1/c = 1 3. No fractions to clear 4. (1121) Direction C 1. Two points are 0, 0, 1 and 1, 0, 0. 2. 0, 0, 1, -1, 0, 0 = 1, 0, 1 3. No fractions to clear or integers to reduce. ] or [2113] 4. [1 01 Direction D 1. Two points are 0, 1, 0 and 1, 0, 0. 2. 0, 1, 0, -1, 0, 0 = -1, 1, 0 3. No fractions to clear or integers to reduce. 4. [ 1 10] or [ 1 100]