Class 6

Structures of Crystalline Materials

READING
Chapters 17 in DeGraef and McHenry, pp. 463-466, 476-489 REFERENCE: Ch. 2 in Rohrer; relevant material on ceramic and metallic structures from any Introduction to Materials book.

Prof. M.L. Weaver

Crystalline Structures The Basics

Crystal structure of a material is way in which atoms, ions, molecules are spatially arranged in 3-D space. Crystal structure = lattice + motif. A lattice is a 3-D array of points in space. Every lattice point must have identical surroundings. Unit cell: smallest repetitive volume which Each crystal structure is built by stacking contains the complete lattice pattern of a unit cells and placing identical objects crystal. y A unit cell is chosen to represent p (motifs, basis) ( ) on each lattice p point. the highest level of geometric symmetry of the crystal structure. Its the basic structural unit or building block of f crystal t l structure. t t
7 crystal systems in 3-D 14 crystal lattices in 3-D
a, b, and c are the lattice constants are the interaxial angles

Metallic Crystal Structures

(the simplest) ( p )
Recall, that (a) coulombic attraction between delocalized valence electrons and positively charged cores is isotropic (non-directional); (b) typically, only one element is present, so all atomic radii are the same; (c) nearest neighbor distances tend to be small; and (d) electron cloud shields cores from each other. For these reasons, metallic bonding leads to close packed, dense crystal structures that maximize space filling and coordination number (number of nearest neighbors). Most elemental metals crystallize in the FCC (face-centered cubic), BCC (body-centered cubic, or HCP (hexagonal (h l close l packed) structures.
Room temperature crystal structure Crystal structure just before it melts

Stacking of Metallic Crystal Structures

How can we stack metal atoms to minimize empty space? Which plane is more close-packed? 2 dimensions 2-dimensions
vs.

N stack Now k these h 2-D 2 Dl layers to make k 3-D 3 D structures

Prof. M.L. Weaver

Atomic structures are close-packed in three dimensions

Close-packed hexagonal: ABABAB stacking sequence Face-centered cubic: ABCABC stacking g sequence q Packing fraction for CPH and FCC structures is 0.74 meaning spheres occupy 74% of all available space

Prof. M.L. Weaver

Materials: engineering, science, processing and design, 2nd edition Copyright (c)2010 Michael Ashby, Hugh Shercliff, David Cebon

Figure 4.8

Non Close-Packed Structures

Body-centered y cubic: ABABAB packing sequence Packing fraction = 0.68

Figure gu e 4.9 9

Amorphous structure: Packing fraction 0.64

Figure 4.10
Prof. M.L. Weaver
Materials: engineering, science, processing and design, 2nd edition Copyright (c)2010 Michael Ashby, Hugh Shercliff, David Cebon

Metal Unit Cells

Red lines define the cell while spheres represent individual atoms Shaded regions represent close or closest packed plane

Figure 4.11
Prof. M.L. Weaver
Materials: engineering, science, processing and design, 2nd edition Copyright (c)2010 Michael Ashby, Hugh Shercliff, David Cebon

FCC Stacking Sequence (continued)

2D Projections: B A sites B sites C sites A B C B C B B C B B

Prof. M.L. Weaver

Comparing HCP and FCC

The similarity of packing in these 2 FCC: structures is noteworthy, both have 12 CN, APF=0.74 and identical densities. The only significant difference between the structures is in the stacking sequence (ABCAB), i.e. where the third close packed layer in FCC is positioned. Example, cobalt undergoes martensitic transformation from FCC to HCP at ~695 K. The lattice constant of FCC Co is 3.5446 , with a nearest-neighbor distance of 2.5064 . While for HCP Co, the lattice Equivalent constants a and c are 2.5071 and to above but 4 0695 , respectively, 4.0695 respectively its nearestnearest rotated neighbor distance is 2.4971 , and the ratio c/a equals 1.623.
Prof. Note that AB in FCC would be equivalent to AB in HCP, without the third close packed layer. M.L. Weaver

HCP:

Interstitial Sites
In the spaces between the sites of the closest packed lattices (planes), (planes) there are a number of well defined interstitial positions:

The CCP (FCC) structure in (a) has 4 octahedral interstitial sites per cell; one site is at the cell ll center t [shown [h in i (a) ( ) and d the th rest t are at t the th midpoints id i t of f all ll the th cell ll edges d (121/4)]. (12 1/4)] There are also 8 tetrahedral, 4-coordinate sites per unit cell at the (1/4, 1/4, 1/4) positions entirely within the cell. Alternative view of CCP (FCC) structure in (a):

Although similar sites occur in the BCC lattice in (b), they do not possess ideal tetrahedral or octahedral symmetry. Primitive Hexagonal lattice?
Prof. M.L. Weaver

Interstitial Sites (continued)

It is important to understand how the sites are configured with respect to the closest The 4 coplanar atoms in the octahedral packed layers:
symmetry are usually called the inplane or equatorial ligands, while the top and bottom atoms are the axial or apical ligands. ligands This representation is convenient since it emphasizes the arrangement of px, py and pz orbitals that form chemical bonds (see pp. 15&16, Class 1 notes).

Of the six nearest neighbors to the octahedral site in the CCP structure, three are in one close packed layer and the remaining three are in the adjacent layer. The most symmetric octahedral position is, thus, midway between the 2 close-packed planes. l For the tetrahedral positions, three of the atoms that make up the tetrahedron lie in the same close packed plane and the fourth (the apex of the tetrahedron) lies in another another. We expect the interstitial atom to occupy a position equidistant between the 4 ligands. Because this position is not halfway between the 2 close-packed planes, as the octahedral site is, the sites above (T+) and below ( T-) a central reference plane are distinct. It is useful to remember that for each close packed site in the FCC and HCP structures, there is one 6-coordinate octahedral site and two 4-coordinate tetrahedral sites (1 T+ site and 1 T- site).
Prof. M.L. Weaver