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Structure of Crystalline Solids

Types of Solids
Crystalline Material
Atoms self-organize in a periodic Atoms arranged in repetitive 3Dimensional pattern, in long range order (LRO) give rise to crystal structure.

Crystalline Structure

Amorphous (Non-Crystalline)
Lacks a systematic atomic arrangement Atoms are arranged in short range order
Non-Crystalline Structure

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Single Crystals and Polycrystalline Materials

Single Crystal
Atoms are in a repeating or periodic array over the entire extent of material

Polycrystalline material
Comprised of many small crystals or grains The grains have different crystallographic orientation Atomic mismatch where grains meet (grain boundaries)

Crystal Structure
When describing crystalline structures, atoms (or ions) are thought of as being solid spheres with welldefined diameters.

Atomic hard sphere model

Spheres representing nearest-neighbor atoms touch one another.
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Unit Cell
Space Lattice
An imaginary network of lines, with atoms at intersection of lines, representing the arrangement of atoms

Unit Cell
The smallest structural unit or building block that can describe the crystal structure Repetition of the unit cell generates the entire crystal

Space Lattice
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Unit Cell

Crystal Systems and Bravais Lattice

Different types of unit cells can be constructed, depending on values of the lattice parameters.

Lattice parameters (or Lattice Constants) axial lengths: a, b, c interaxial angles: , ,

In general:

abc

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Crystal Systems and Bravais Lattice

Only seven different types of unit cells are necessary to create all space lattices. Many of the seven crystal systems have variation of the basic unit cells:
Bravais (1811 -1863) showed that fourteen standard unit cells can describe all possible lattice networks These Bravais lattices are illustrated in the next few slides.

The Four basic types of unit cells are:

1. 2. 3. 4. Simple Body Centered Face Centered Base Centered

Types of Unit Cells

1.

1.

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Types of Unit Cells

3.

4.

Types of Unit Cells

5.

6.

7.
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Principal Metallic Crystal Structures

Metals tend to be densely packed Typically, only one element is present, so all atomic radii are the same Metallic bonding is not directional No restriction on number or positions of nearest neighbour atoms: large number of nearest neighbours and dense atomic packing. The densely packed structures are in lower and more stable energy. Energy is released as the atoms come closer together and bond more tightly with each other
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Have simplest crystal structures

Principal Metallic Crystal Structures

90% of the metals have either Body Centered Cubic (BCC), Face Centered Cubic (FCC) or Hexagonal Close Packed (HCP) crystal structure HCP is denser version of simple hexagonal crystal structure
The unit cell is shown by solid lines

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Body Centered Cubic (BCC) Crystal Structure

Represented as one atom at each corner of cube and one at the center of cube Each atom has 8 nearest neighbors Therefore, coordination number is 8

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Atomic-site unit cell

Hard-sphere unit cell

Isolated unit cell

Body Centered Cubic (BCC) Crystal Structure

In isolated unit cell, each of these cells has the equivalent of two atoms per unit cell. Each unit cell has eight atom at corners and 1 full atom at the center
(8 ) + 1 = 2 atoms

Atoms contact each other at cube diagonal. Therefore, lattice constant:

3 a = 4R

or

a=

4R 3

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Atomic Packing Factor of BCC Structure

If the atoms in the BCC are considered to be spherical:
Atomic Packing Factor = Volume of atoms in unit cell Volume in unit cell

Since there are two atom per BCC unit cell:

Volume of the BCC unit cells is:

Therefore:

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Face Centered Cubic (FCC) Crystal Structure

Represented as one atom each at the corner of cube and at the center of each cube face Coordination number for FCC structure: 12 Atomic Packing Factor is 0.74

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Atomic-site unit cell

Hard-sphere unit cell

Isolated unit cell

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Face Centered Cubic (FCC) Crystal Structure

In isolated unit cell, each of these cells has the equivalent of four atoms per unit cell. Each unit cell has eight atom at corners and six atoms at the center of six faces.
(8 ) + (6 ) = 4 atoms

Atoms contact each other across cubic face diagonal Therefore, lattice constant:
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2 a = 4R

Or

4R a= 2

Hexagonal Close-Packed (HCP) Crystal Structure

Represented as an atom at each of 12 corners of a hexagonal prism, 2 atoms at top and bottom face and 3 atoms in between top and bottom face Atoms attain higher APF (0.74) by attaining HCP Structure than simple hexagonal structure The coordination number: 12

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Atomic-site unit cell

Hard-sphere unit cell

Isolated unit cell

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Hexagonal Close-Packed (HCP) Crystal Structure

In isolated unit cell, each of these cells has the equivalent of six atoms per unit cell. Each unit cell has six atoms at each of top and bottom layer, two half atoms at top and bottom layer and 3 full atoms at the middle layer. (2 6 ) + (2 ) + 3 = 6 atoms Ideal c/a ratio is 1.633
Ratio of the height c of the hexagonal prism of the HCP structure to its basal side a.
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HCP Crystal Structure (Example)

Calculate the volume of the zinc crystal structure unit cell by using the following data: pure zinc has the HCP structure with lattice constant a = 0.2665 nm and c = 0.4947. Solution: Volume of Zn HCP unit cell = Area of the base height

Area of base = Area of ABDEFG

Area of ABDEFG: Total areas of 6 equivalent triangles of area ABC

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Atom Positions in Cubic Unit Cells

Cartesian coordinate system is use to locate atoms (x, y, z) In a cubic unit cell
y-axis: direction to the right x-axis: direction coming out of the paper z-axis: direction towards top Negative directions are to the opposite of positive directions

Atom positions are located using unit distances along the axes.

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Directions in Cubic Unit Cells

In cubic crystals, Direction Indices [uvw] are vector components of directions resolved along each axes, resolved to smallest integers. Direction indices are position coordinates of unit cell where the direction vector emerges from cell surface, converted to integers. Some directions in cubic unit cells:

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Procedure to Find Direction Indices

Produce the direction vector till it emerges from the surface of cubic cell

For Cubic Unit Cells

Determine the coordinates of point of emergence and origin

Subtract coordinates of point of emergence by that of origin NO Are all are integers? YES Are any of the direction vectors negative? YES Represent the indices in a square bracket without comas with a bar (_) over a negative index NO 23 Represent the indices in a square bracket without comas Convert them to smallest possible integer by multiplying by an integer

Direction Indices Cubic Unit Cells(Example)

Determine direction indices of the given vector.
Origin coordinates are (3/4, 0, 1/4) Emergence coordinates are (1/4, 1/2, 1/2) Solution: Subtracting origin coordinates from emergence coordinates:

Multiply by 4 to convert all fractions to integers:

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Miller Indices in Cubic Unit Cells

Used to refer to specific lattice planes of atoms They are reciprocals of the fractional intercepts (with fractions cleared) that the plane makes with the crystallographic x, y and z axes of three non-parallel edges of the cubic unit cell.

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Procedure to Find Miller Indices

Choose a plane that does not pass through origin

For Cubic Unit Cells

Determine the x, y, and z intercepts of the plane

Find the reciprocals of the intercept Yes Fractions? No Place a bar over the negative indices Clear fractions by multiplying by an integer to determine smallest set of whole numbers

Enclose in parenthesis (hkl) where h, k, l are miller indices of cubic crystal place for x, y and z. Eg: (111)

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Miller Indices for Cubic Unit Cells(Example)

1.

Intercepts of the plane at x, y and z are 1, and Taking reciprocals we get (1, 0, 0) Miller indices are (100):
one-zero-plane

2.

Intercepts are 1/3, 2/3 and 1 Taking reciprocals we get (3, 3/2, 1) Multiplying by 2 to clear fractions, we get (6,3,2) Miller indices are (632)

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Miller Indices for Cubic Unit Cells (Example)

3. Plot the plane (101) Taking reciprocals of the indices we get (1, , 0) The intercepts of the plane are x = 1, y = (parallel to y) and z = 1

4. Plot the plane (221) Taking reciprocals of the indices we get (1/2, 1/2, 1) The intercepts of the plane are x = , y = and z = 1

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Miller Indices for Cubic Unit Cells(Example)

_

5. Plot the plane (1 1 0) Taking reciprocals of the indices we get (1, -1, ) The intercepts of the plane are x = 1, y = -1 and z = (parallel to z axis)

To show this plane in a single unit cell, the origin is moved along the positive direction of y axis by 1 unit
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Miller Indices (Important Relationship)

This is only for the CUBIC SYSTEM:
Direction indices of a direction perpendicular to a crystal plane are same as miller indices of the plane.

Example:

Interplanar spacing (dhkl) between parallel closest planes with same miller indices is given by
a = lattice constant h, ,k, l = miller indices of cubic planes being considered)

dhkl =

a h2 + k 2 + l 2

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Indices for Crystal Hexagonal (HCP) Unit Cells

Planes

in

Four indices are used (hkil) called as Miller-Bravals indices. Four axes are used (a1, a2, a3 and c) Reciprocal of the intercepts that a crystal plane makes with the a1, a2, a3 and c axes give the h, k, i and l indices respectively.

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Indices for Crystal Planes in HCP Unit Cells (Examples)

Basal Planes:

Prism Planes: For plane ABCD

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Comparison of FCC and HCP Crystals

Both FCC and HCP are close packed and have APF 0.74 FCC crystal is close packed in (111) plane while HCP is close packed in (0001) plane.

FCC Crystal Structure showing a close-packed (111) plane

HCP Crystal Structure showing a close-packed (0001) plane

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Structural Difference between HCP and FCC

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Volume Density
Since the entire crystal can be generated by the repetition of the unit cell, the density of a crystalline material Mass / Unit cell v = Volume / Unit cell Example: Copper (FCC) has atomic mass of 63.54 g/mol and atomic radius of 0.1278 nm.

Volume of unit cell,

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Densities of Material Classes

In general metals > ceramics > polymers Reasons:
Metals have close-packing (metallic bonding) and often large atomic masses. Ceramics have less dense packing and often lighter elements Polymers have low packing density (often amorphous) and lighter elements (C, H, O)
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Polymorphism or Allotropy
Polymorphism
Materials exist in more than one crystalline form under different conditions of temperature and pressure. If the material is an elemental solid, it is called allotropy

Example: Iron exists in both BCC and FCC form depending on the temperature.

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Polymorphism or Allotropy
Another example: Carbon, which can exist as diamond, graphite and amorphous carbon.

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Non-Crystalline (Amorphous) Solids

Solids lack of a systematic and regular arrangement of atoms over relatively large atomic distances. Two-dimensional schematic diagrams for:
Crystalline SiO2 Non Crystalline SiO2

Much more disordered and irregular

Rapid cooling of metals (108 K/s) can give rise to amorphous structure since little time is allowed for ordering process.

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