The Structure of Crystalline Solids ISSUES TO ADDRESS

The Structure of Crystalline Solids ISSUES TO ADDRESS. . . • How do atoms assemble into solid structures? • How does the density of a material depend on its structure? • When do material properties vary with the sample (i. e. , part) orientation? 1

Energy and Packing • Non dense, random packing Energy typical neighbor bond length typical neighbor bond energy • Dense, ordered packing r Energy typical neighbor bond length typical neighbor bond energy r Dense, ordered packed structures tend to have lower energies. 2

Materials and Packing Crystalline materials. . . • atoms pack in periodic, 3 D arrays • typical of: -metals -many ceramics -some polymers crystalline Si. O 2 Adapted from Fig. 3. 23(a), Callister & Rethwisch 8 e. Noncrystalline materials. . . • atoms have no periodic packing • occurs for: -complex structures -rapid cooling "Amorphous" = Noncrystalline Si Oxygen noncrystalline Si. O 2 Adapted from Fig. 3. 23(b), Callister & Rethwisch 8 e. 3

Metallic Crystal Structures • How can we stack metal atoms to minimize empty space? 2 -dimensions vs. Now stack these 2 -D layers to make 3 -D structures 4

Metallic Crystal Structures • Tend to be densely packed. • Reasons for dense packing: - Typically, only one element is present, so all atomic radii are the same. - Metallic bonding is not directional. - Nearest neighbor distances tend to be small in order to lower bond energy. - Electron cloud shields cores from each other • Have the simplest crystal structures. We will examine three such structures. . . 5

Simple Cubic Structure (SC) • Rare due to low packing density (only Po has this structure) • Close-packed directions are cube edges. • Coordination # = 6 (# nearest neighbors) Click once on image to start animation (Courtesy P. M. Anderson) 6

Atomic Packing Factor (APF) Volume of atoms in unit cell* APF = Volume of unit cell *assume hard spheres • APF for a simple cubic structure = 0. 52 atoms unit cell a R=0. 5 a close-packed directions contains 8 x 1/8 = 1 atom/unit cell Adapted from Fig. 3. 24, Callister & Rethwisch 8 e. APF = volume atom 4 p (0. 5 a) 3 1 3 a 3 volume unit cell 7

Body Centered Cubic Structure (BCC) • Atoms touch each other along cube diagonals. --Note: All atoms are identical; the center atom is shaded differently only for ease of viewing. ex: Cr, W, Fe ( ), Tantalum, Molybdenum • Coordination # = 8 Click once on image to start animation (Courtesy P. M. Anderson) Adapted from Fig. 3. 2, Callister & Rethwisch 8 e. 2 atoms/unit cell: 1 center + 8 corners x 1/8 8

Atomic Packing Factor: BCC • APF for a body-centered cubic structure = 0. 68 3 a a 2 a Adapted from Fig. 3. 2(a), Callister & Rethwisch 8 e. R a Close-packed directions: length = 4 R = 3 a atoms volume 4 p ( 3 a/4) 3 2 unit cell atom 3 APF = volume 3 a unit cell 9

Face Centered Cubic Structure (FCC) • Atoms touch each other along face diagonals. --Note: All atoms are identical; the face-centered atoms are shaded differently only for ease of viewing. ex: Al, Cu, Au, Pb, Ni, Pt, Ag • Coordination # = 12 Adapted from Fig. 3. 1, Callister & Rethwisch 8 e. Click once on image to start animation (Courtesy P. M. Anderson) 4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8 10

Atomic Packing Factor: FCC • APF for a face-centered cubic structure = 0. 74 maximum achievable APF 2 a a Adapted from Fig. 3. 1(a), Callister & Rethwisch 8 e. Close-packed directions: length = 4 R = 2 a Unit cell contains: 6 x 1/2 + 8 x 1/8 = 4 atoms/unit cell atoms volume 4 3 p ( 2 a/4) 4 unit cell atom 3 APF = volume 3 a unit cell 11

FCC Stacking Sequence • ABCABC. . . Stacking Sequence • 2 D Projection B B C A B B B A sites C C B sites B B C sites • FCC Unit Cell A B C 12

Hexagonal Close-Packed Structure (HCP) • ABAB. . . Stacking Sequence • 3 D Projection c a • 2 D Projection A sites Top layer B sites Middle layer A sites Bottom layer Adapted from Fig. 3. 3(a), Callister & Rethwisch 8 e. • Coordination # = 12 • APF = 0. 74 • c/a = 1. 633 6 atoms/unit cell ex: Cd, Mg, Ti, Zn 13

Theoretical Density, Density = = = Mass of Atoms in Unit Cell Total Volume of Unit Cell n A V C NA where n = number of atoms/unit cell A = atomic weight VC = Volume of unit cell = a 3 for cubic NA = Avogadro’s number = 6. 022 x 1023 atoms/mol 14

Theoretical Density, • Ex: Cr (BCC) A = 52. 00 g/mol R = 0. 125 nm n = 2 atoms/unit cell Adapted from Fig. 3. 2(a), Callister & Rethwisch 8 e. atoms unit cell = volume unit cell R a 2 52. 00 a 3 6. 022 x 1023 a = 4 R/ 3 = 0. 2887 nm g mol theoretical = 7. 18 g/cm 3 actual atoms mol = 7. 19 g/cm 3 15

Densities of Material Classes In general metals > ceramics > polymers 30 Why? Ceramics have. . . 3 (g/cm ) Metals have. . . • close-packing (metallic bonding) • often large atomic masses • less dense packing • often lighter elements Polymers have. . . • low packing density (often amorphous) • lighter elements (C, H, O) Composites have. . . • intermediate values Metals/ Alloys 20 Platinum Gold, W Tantalum 10 Silver, Mo Cu, Ni Steels Tin, Zinc 5 4 3 2 1 0. 5 0. 4 0. 3 Graphite/ Ceramics/ Semicond Polymers Composites/ fibers Based on data in Table B 1, Callister *GFRE, CFRE, & AFRE are Glass, Carbon, & Aramid Fiber-Reinforced Epoxy composites (values based on 60% volume fraction of aligned fibers in an epoxy matrix). Zirconia Titanium Al oxide Diamond Si nitride Aluminum Glass -soda Concrete PTFE Silicon Magnesium Graphite Silicone PVC PET PC HDPE, PS PP, LDPE Glass fibers GFRE* Carbon fibers CFRE* Aramid fibers AFRE* Wood Data from Table B. 1, Callister & Rethwisch, 8 e. 16

Crystals as Building Blocks • Some engineering applications require single crystals: -- diamond single crystals for abrasives (Courtesy Martin Deakins, GE Superabrasives, Worthington, OH. Used with permission. ) -- turbine blades Fig. 8. 33(c), Callister & Rethwisch 8 e. (Fig. 8. 33(c) courtesy of Pratt and Whitney). • Properties of crystalline materials often related to crystal structure. -- Ex: Quartz fractures more easily along some crystal planes than others. (Courtesy P. M. Anderson) 17

Polycrystals • Most engineering materials are polycrystals. 1 mm • Nb-Hf-W plate with an electron beam weld. • Each "grain" is a single crystal. • If grains are randomly oriented, Anisotropic Adapted from Fig. K, color inset pages of Callister 5 e. (Fig. K is courtesy of Paul E. Danielson, Teledyne Wah Chang Albany) Isotropic overall component properties are not directional. • Grain sizes typically range from 1 nm to 2 cm (i. e. , from a few to millions of atomic layers). 18

Single vs Polycrystals • Single Crystals E (diagonal) = 273 GPa Data from Table 3. 3, Callister & Rethwisch 8 e. (Source of data is R. W. Hertzberg, Deformation and Fracture Mechanics of Engineering Materials, 3 rd ed. , John Wiley and Sons, 1989. ) -Properties vary with direction: anisotropic. -Example: the modulus of elasticity (E) in BCC iron: • Polycrystals -Properties may/may not vary with direction. -If grains are randomly oriented: isotropic. (Epoly iron = 210 GPa) -If grains are textured, anisotropic. E (edge) = 125 GPa 200 mm Adapted from Fig. 4. 14(b), Callister & Rethwisch 8 e. (Fig. 4. 14(b) is courtesy of L. C. Smith and C. Brady, the National Bureau of Standards, Washington, DC [now the National Institute of Standards and Technology, Gaithersburg, MD]. ) 19

Polymorphism • Two or more distinct crystal structures for the same material (allotropy/polymorphism) iron system titanium liquid , -Ti 1538ºC -Fe BCC carbon 1394ºC diamond, graphite -Fe FCC 912ºC BCC -Fe 20

X-Ray Diffraction • Diffraction gratings must have spacings comparable to the wavelength of diffracted radiation. • Can’t resolve spacings • Spacing is the distance between parallel planes of atoms. 21

z X-Ray Diffraction Pattern z Intensity (relative) c a x z c b y (110) a x c b y a x (211) y b (200) Diffraction angle 2 q Diffraction pattern for polycrystalline -iron (BCC) Adapted from Fig. 3. 22, Callister 8 e. 22

SUMMARY • Atoms may assemble into crystalline or amorphous structures. • Common metallic crystal structures are FCC, BCC, and HCP. Coordination number and atomic packing factor are the same for both FCC and HCP crystal structures. • We can predict the density of a material, provided we know the atomic weight, atomic radius, and crystal geometry (e. g. , FCC, BCC, HCP). • Crystallographic points, directions and planes are specified in terms of indexing schemes. Crystallographic directions and planes are related to atomic linear densities and planar densities. 23

SUMMARY • Materials can be single crystals or polycrystalline. Material properties generally vary with single crystal orientation (i. e. , they are anisotropic), but are generally non-directional (i. e. , they are isotropic) in polycrystals with randomly oriented grains. • Some materials can have more than one crystal structure. This is referred to as polymorphism (or allotropy). • X-ray diffraction is used for crystal structure and interplanar spacing determinations. 24