Structure of Crystalline Solids

Crystalline Structures
Have long range order, ie. the atoms are orderly arranged in a repeating or periodic array over large atomic distances The crystal structure of a solid is determined by the manner in which atoms, ions, and molecules are spatially arranged.

 Unit-Cells and Crystal Systems

Unit cells are the smallest repeating units within a crystal structure. The geometry of a unit cell is described in terms of six lattice or cell-parameters:
Cell-lengths: a, b, c Cell-angles: , ,

All crystalline solids can be described by one of the seven crystal systems: cubic, tetragonal, hexagonal, orthorhombic, rhombohedral, monoclinic, triclinic.

Metallic Crystal Structures

Face-Centred Cubic (FCC)
Atoms are located at the corners and the centres of all the cube faces. The atoms touch one another across a face diagonal. Each corner atom is shared among eight unit cells, whereas a face-centred atom belongs to only two. Therefore, there are four whole atoms in the unit cell, ie. 6(1/2) + 8(1/8)

 The cell length a and The packing density of the atomic radius R are atoms in the unit cell related by or atomic packing a = 2R2 factor (APF) is 0.74 Each atom has a APF = volume of coordination number atoms in a unit cell / (CN) of 12, ie. there total unit cell volume are 12 touching atoms surrounding it. Common metals with the FCC structure are: CN indicates how tightly and efficiently Cu, Al, Ag, Au, Ni, Pt atoms are packed together

Example Problem
Show that in an FCC unit cell, its cell length a is related to the atomic radius R by a = 2R2. Hence calculate the volume of the unit cell. The length of a face-diagonal is 4R The cell volume is a3. From the right triangle on the face, a2 + a2 = (4R)2 a = 2R2 Hence, the cell volume (Vc) is: Vc = a3 = (2R2)3 = 16R32

Example Problem

Show that the atomic packing factor (APF) for the FCC crystal structure is 0.74.
APF = total volume of spheres in a unit cell / total unit cell volume = Vs/Vc Volume of each sphere is (4/3)R3 and there are four atoms per FCC unit cell

Vs = (4)(4/3)R3 = (16/3)R3 Vc = 16R32 Therefore APF = Vs/Vc = (4/3)R3 / 16R32 = 0.74

 Body-Centred Cubic Crystal Structure (BCC)

Atoms not as densely packed as FCC Centre and corner atoms touch one another along the cube diagonals The cell length a and the atomic radius R are related by: a = 4R/3

 There are two whole atoms in each unit cell ie. 1 + 8(1/8). The coordination number of each atom is eight, ie. it has 8 surrounding neighbour atoms.. The atomic packing density or APF is 0.68. Common metals with the BCC structure are: Cr, Fe, W, Mo, Ba, Li

Example Problem Show that in an BCC unit cell, its cell length a is related to the atomic radius R by: a = 4R/3. The length of the cube diagonal is 4R From the right triangle on the bottom face, a2 + a2 = 2(a2) From the right triangle on the diagonal face, a2 + 2a2 = (4R)2 3a2 = (4R)2 a = 4R/3 Cell volume = a3 = (4R/3)3 = (64R3)/(33) 12.3R3

 Hexagonal Close-Packed Crystal Structure (HCP) Three interior midplane atoms are sandwiched between the top and bottom hexagonal basal planes. The coordinator number of each atom is 12. The atomic packing factor is 0.74. Common metals with the HCP structure are: Ti, Mg, Cd, Zn

 There are six whole atoms in the unit cell, ie. 3 + 2[6(1/6) + 1(1/2)] = 6 Usually, the c/a ratio is 1.633. The cell length a and the atomic radius R are related by: a = 2R

Stacking Sequences of Closed-Packed Structures

Both FCC and HCP are closed-packed structures but have a very different stacking sequence of atoms.

(a) A portion of a close-packed plane of atoms; A, B, and C positions are indicated. (b) The AB stacking sequence for close-packed atomic planes

 FCC has a stacking sequence of ABCABC whereas it is ABABfor HCP

(a) Close-packed plane stacking sequence for FCC. (b) A corner has been removed to show the relation between the stacking of close-packed planes of atoms and the FCC structure; the heavy triangle outlines a (111) plane

 Both structures have closed-packed planes where the sphere-packing density along these planes is the maximum. Presence of closed-packed planes makes a metal easier to deform, ie. more ductile.

Close-packed plane stacking sequence for HCP

Density Calculations
Knowing the crystal structure of a solid allows its theoretical or true density () to be calculated. n = number of atoms associated with each unit cell A = atomic weight Vc = volume of the unit cell NA = Avogadros number (6.023 1023 atoms/mol)

nA = Vc N A

Example Problem
Copper has an atomic radius of 0.128 nm (1.28 ), an FCC crystal structure, and an atomic weight of 63.5 g/mol. Compute its density and compare the answer with its measured density (8.94 g/cm3). Known values for Cu: n = 4; A = 63.5 g/mol; Vc = 16R3; R = 0.128 nm.

nA = Vc N A

nA
=

(16 R 3 2 ) N A
= (4)(63.5) [16 2 (1.28 10 8 )](6.023 10 23 )

= 8.89 g/cm3