Chapter 4: The Structure of Crystalline Solids

ISSUES TO ADDRESS...
• What are common crystal structures for
metals and ceramics?

• What features of a metal’s/ceramic’s atomic
structure determine its density?

• How do the crystal structures of ceramic
materials differ from those for metals?

Chapter 4 - 1

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

Chapter 4 - 2

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.
• Metals have the simplest crystal structures.

We will examine three such structures...

Chapter 4 - 3

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)

Fig. 4.2, Callister & Rethwisch 9e.

Chapter 4 - 4

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
volume
atoms atom
a 4
unit cell 1 π (0.5a) 3
3
R = 0.5a APF =
a3 volume
close-packed directions
unit cell
contains 8 x 1/8 =
1 atom/unit cell
Adapted from Fig. 4.2 (a),
Callister & Rethwisch 9e.
Chapter 4 - 5

Fe ().1. Molybdenum • Coordination # = 8 Adapted from Fig. Tantalum.6 . 4. Callister & Rethwisch 9e. --Note: All atoms are identical. ex: Cr. W. 2 atoms/unit cell: 1 center + 8 corners x 1/8 Chapter 4 . the center atom is shaded differently only for ease of viewing.Body Centered Cubic Structure (BCC) • Atoms touch each other along cube diagonals.

VMSE Screenshot – BCC Unit Cell Chapter 4 .7 .

8 . Callister & a Rethwisch 9e.68 3a a 2a Close-packed directions: Adapted from R length = 4R = 3 a Fig. atoms volume 4 unit cell 2 π ( 3a/4 ) 3 3 atom APF = 3 volume a unit cell Chapter 4 . 4. Atomic Packing Factor: BCC • APF for a body-centered cubic structure = 0.1(a).

9 . --Note: All atoms are identical. Cu. ex: Al. Pt. Callister & Rethwisch 9e. Ni. 4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8 Chapter 4 . the face-centered atoms are shaded differently only for ease of viewing. 3. Face Centered Cubic Structure (FCC) • Atoms touch each other along face diagonals.1. Pb. Ag • Coordination # = 12 Adapted from Fig. Au.

3.74 maximum achievable APF Close-packed directions: length = 4R = 2 a 2a Unit cell contains: 6 x 1/2 + 8 x 1/8 = 4 atoms/unit cell a Adapted from Fig. Atomic Packing Factor: FCC • APF for a face-centered cubic structure = 0. Callister & atoms volume Rethwisch 9e.1(a). 4 3 unit cell 4 π ( 2a/4 ) 3 atom APF = 3 volume a unit cell Chapter 4 .10 .

11 ... Stacking Sequence • 2D Projection B B C A A sites B B B C C B sites B B C sites A • FCC Unit Cell B C Chapter 4 . FCC Stacking Sequence • ABCABC.

Ti. • Coordination # = 12 6 atoms/unit cell • APF = 0. Hexagonal Close-Packed Structure (HCP) • ABAB.633 Chapter 4 .3(a). Zn • c/a = 1. Mg. Stacking Sequence • 3D Projection • 2D Projection A sites Top layer c B sites Middle layer A sites Bottom layer a Adapted from Fig.12 .74 ex: Cd. Callister & Rethwisch 9e.. 4..

VMSE Screenshot – Stacking Sequence and Unit Cell for HCP Chapter 4 .13 .

Theoretical Density.022 x 1023 atoms/mol Chapter 4 .14 . r Mass of Atoms in Unit Cell Density = r = Total Volume of Unit Cell nA r = VC NA where n = number of atoms/unit cell A = atomic weight VC = Volume of unit cell = a3 for cubic NA = Avogadro’s number = 6.

19 g/cm3 a 3 6.00 ρtheoretical = 7.125 nm n = 2 atoms/unit cell R Adapted from a a = 4R/ 3 = 0. atoms g unit cell 2 52.15 .022 x 1023 volume atoms unit cell mol Chapter 4 .2887 nm Fig.00 g/mol R = 0. Theoretical Density.1(a).18 g/cm3 mol r= ρactual = 7. ρ • Ex: Cr (BCC) A = 52. Callister & Rethwisch 9e. 4.

Can be ionic and/or covalent in character.16 . -. Atomic Bonding in Ceramics • Bonding: -. • Degree of ionic character may be large or small: CaF2: large SiC: small Chapter 4 .% ionic character increases with difference in electronegativity of atoms.

17 . Ceramic Crystal Structures Oxide structures – oxygen anions larger than metal cations – close packed oxygen in a lattice (usually FCC) – cations fit into interstitial sites among oxygen ions Chapter 4 .

Relative sizes of ions – Formation of stable structures: --maximize the # of oppositely charged ion neighbors.18 . Callister & Rethwisch 9e. . p values to achieve charge neutrality Chapter 4 . 4. Maintenance of Charge Neutrality : F- CaF 2 : Ca 2+ + --Net charge in ceramic cation anions should be zero.4. . . . . . --Reflected in chemical F- formula: A m Xp m. . . - + + + Adapted from Fig. . . Factors that Determine Crystal Structure 1. - unstable stable stable 2.

0.414 . Callister & Rethwisch 9e.155 2 linear Callister & Rethwisch 9e. Coordination Number and Ionic Radii r cation • Coordination Number increases with r anion To form a stable structure. < 0.414 4 tetrahedral chloride) Adapted from Fig. Callister & Rethwisch 9e.0.1.225 .225 3 triangular NaCl (sodium 0. Chapter 4 . how many anions can surround around a cation? r cation Coord. 4.0.19 . Adapted from Table 4.7.5.3. 4.6.732 . 4. 0. 0. Callister & Rethwisch 9e.155 . ZnS r anion Number (zinc blende) Adapted from Fig.732 6 octahedral CsCl (cesium chloride) 0.0 8 cubic Adapted from Fig.

= 6) a = 2ranion 2ranion + 2rcation = 2 2ranion ranion + rcation = 2ranion rcation = ( 2 -1)ranion rcation = 2 .20 .N.1 = 0.414 ranion Chapter 4 . Computation of Minimum Cation-Anion Radius Ratio • Determine minimum rcation/ranion for an octahedral site (C.

for SiC. Si atoms occupy tetrahedral sites Chapter 4 . Bond Hybridization Bond Hybridization is possible when there is significant covalent bonding – hybrid electron orbitals form – For example for SiC • XSi = 1.5 • ~ 89% covalent bonding • Both Si and C prefer sp3 hybridization • Therefore.21 .8 and XC = 2.

053 rcation 0.140 -.181 Data from Table 4. Chapter 4 .550 Ca 2+ 0. F.414 < 0. 0.22 .crystal structure is NaCl Cl . what crystal structure would you predict for FeO? Cation Ionic radius (nm) • Answer: Al 3+ 0. 0.550 < 0.100 based on this ratio.732 O2. -. Example Problem: Predicting the Crystal Structure of FeO • On the basis of ionic radii. 0.077 = Fe 2+ 0.133 Callister & Rethwisch 9e.coord # = 6 because Anion 0.140 Fe 3+ 0.069 = 0.4.077 ranion 0.

102 nm rCl = 0.564  cations (Na+) prefer octahedral sites Adapted from Fig.181 nm rNa/rCl = 0. Example: NaCl (rock salt) structure rNa = 0. Rock Salt Structure Same concepts can be applied to ionic solids in general. 4.23 . Callister & Rethwisch 9e. Chapter 4 .5.

Callister & Rethwisch 9e.072 nm rMg/rO = 0.140 nm Mg2+ rMg = 0. MgO and FeO MgO and FeO also have the NaCl structure O2.5. rO = 0.514  cations prefer octahedral sites Adapted from Fig. So each Mg2+ (or Fe2+) has 6 neighbor oxygen atoms Chapter 4 . 4.24 .

So each Cs+ has 8 neighbor Cl- Chapter 4 .732 < 0.0. 4. and zinc blende Cesium Chloride structure:  Since 0. CsCl. Callister & Rethwisch 9e.25 .939 < 1. AX Crystal Structures AX–Type Crystal Structures include NaCl.6. cubic sites preferred Fig.

Callister & Rethwisch 9e. ThO2. Chapter 4 . AX2 Crystal Structures Fluorite structure • Calcium Fluorite (CaF2) • Cations in cubic sites • UO2. ZrO2.26 . 4.8. CeO2 • Antifluorite structure – positions of cations and anions reversed Fig.

4. ABX3 Crystal Structures • Perovskite structure Ex: complex oxide BaTiO3 Fig.27 . Chapter 4 . Callister & Rethwisch 9e.9.

28 .VMSE Screenshot – Zinc Blende Unit Cell Chapter 4 .

29 .Density Computations for Ceramics Number of formula units/unit cell Avogadro’s number Volume of unit cell = sum of atomic weights of all cations in formula unit = sum of atomic weights of all anions in formula unit Chapter 4 .

Tantalum Carbon. 20 Gold.4 Wood • intermediate values 0. Magnesium Graphite Silicone CFRE* Aramid fibers PVC • low packing density PET PC AFRE* 1 HDPE. Densities of Material Classes In general Metals/ Graphite/ Composites/ ρ metals > ρ ceramics > ρ polymers Alloys Ceramics/ Semicond Polymers fibers 30 Why? Platinum Based on data in Table B1.30 .. Callister *GFRE.3 Data from Table B. 0.1.H.5 Composites have.. PS (often amorphous) PP.. 4 Titanium Al oxide • less dense packing 3 Diamond Si nitride Aluminum Glass -soda • often lighter elements Concrete Silicon PTFE Glass fibers GFRE* 2 Carbon fibers Polymers have. LDPE • lighter elements (C. Callister & Rethwisch.. W Metals have. & Aramid Fiber-Reinforced Epoxy composites (values based on • close-packing 60% volume fraction of aligned fibers 10 Silver. Mo in an epoxy matrix)... Chapter 4 . 9e. CFRE. (metallic bonding) Cu.O) 0.. Zinc Zirconia ρ (g/cm3 ) 5 Ceramics have. & AFRE are Glass..Ni Steels • often large atomic masses Tin.

& tridymite • The strong Si-O bonds lead to a high melting temperature (1710ºC) for this material Chapter 4 .11. crystobalite. Callister & Rethwisch 9e crystobalite • SiO2 (silica) polymorphic forms are quartz.10 & 4. Silicate Ceramics Most common elements on earth are Si & O Si4+ O2- Figs. 4.31 .

Mg2+.32 . maintain charge neutrality. Callister & Rethwisch 9e. 4.13.accomplished by the sharing of common corners. edges. ionically bond SiO44. or faces Adapted from Fig. & Al3+ 1. Silicates Bonding of adjacent SiO44. Mg2SiO4 Ca2MgSi2O7 Presence of cations such as Ca2+.to one another Chapter 4 . and 2.

12. Chapter 4 . 4. Al3+. Callister & Rethwisch 9e. • Fused silica is SiO2 to which no Si0 4 tetrahedron impurities have been added Si 4+ • Other common glasses contain O2. impurity ions such as Na+.33 . and B3+ • Quartz is crystalline Na + SiO2: Si 4+ O2- (soda glass) Adapted from Fig. Ca2+. Glass Structure • Basic Unit: Glass is noncrystalline (amorphous) 4.

.14. Layered Silicates • Layered silicates (e. Callister & Rethwisch 9e. clays. 4.unit • Negative charge balanced by adjacent plane rich in positively charged cations Fig.34 . talc) – SiO4 tetrahedra connected together to form 2-D plane • A net negative charge is associated with each (Si2O5)2. Chapter 4 .g. mica.

layer with Al2(OH)42+ layer Fig. 4. Note: Adjacent sheets of this type are loosely bound to one another by van der Waal’s forces. Callister & Rethwisch 9e.35 . Chapter 4 .15. Layered Silicates (cont) • Kaolinite clay alternates (Si2O5)2.

36 . medical devices. 4.17. Chapter 4 . Callister & • hard surface coatings – Rethwisch 9e. Polymorphic Forms of Carbon Diamond – tetrahedral bonding of carbon • hardest material known • very high thermal conductivity – large single crystals – gem stones – small crystals – used to grind/cut other materials – diamond thin films Fig. etc. used for cutting tools.

18. – weak van der Waal’s forces between layers – planes slide easily over one another -. 4.37 . Callister & Rethwisch 9e.good lubricant Chapter 4 .Polymorphic Forms of Carbon (cont) Graphite – layered structure – parallel hexagonal arrays of carbon atoms Fig.

38 . • Ordered atomic arrangements involving molecular chains • Crystal structures in terms of unit cells • Example shown – polyethylene unit cell Chapter 4 . Crystallinity in Polymers Fig. 4.19. Callister & Rethwisch 9e.

) • Properties of crystalline materials often related to crystal structure. Anderson) Chapter 4 .Ex: Quartz fractures more easily along some crystal planes than others.M.39 . Worthington. Used with permission. GE Superabrasives.diamond single -.turbine blades crystals for abrasives (Courtesy Martin Deakins. OH. (Courtesy P. Crystals as Building Blocks • Some engineering applications require single crystals: -. -.

color inset pages of Callister 5e. Teledyne Wah Chang Albany) 1 mm • Nb-Hf-W plate with an electron beam weld. Fig. Isotropic • Each "grain" is a single crystal. (Courtesy of Paul E. from a few to millions of atomic layers). overall component properties are not directional. Danielson..e. Chapter 4 . K. • Grain sizes typically range from 1 nm to 2 cm (i. • If grains are randomly oriented. Polycrystals Anisotropic • Most engineering materials are polycrystals.40 .

(Source of data is R. John Wiley and Sons.C. 6. Smith and C. Brady.W.3. anisotropic. 3rd ed. Standards. Washington.41 . Deformation and Fracture Mechanics of -Example: the modulus Engineering Materials. Hertzberg. Callister & vary with direction. (Epoly iron = 210 GPa) Gaithersburg.) of elasticity (E) in BCC iron: E (edge) = 125 GPa • Polycrystals -Properties may/may not 200 μm Adapted from Fig. Chapter 4 . 6.19(b) is courtesy of -If grains are randomly L.. MD).19(b). the National Bureau of oriented: isotropic. Rethwisch 9e. Single vs Polycrystals • Single Crystals E (diagonal) = 273 GPa Data from Table 3. -Properties vary with Callister & Rethwisch 9e. 1989.] -If grains are textured. DC (now the National Institute of Standards and Technology. [Fig. direction: anisotropic.

graphite 1394° FCC C γ-Fe 912°C BCC α-Fe Chapter 4 . Polymorphism • Two or more distinct crystal structures for the same material (allotropy/polymorphism) iron system titanium liquid α. β -Ti 1538° BCC C δ-Fe carbon diamond.42 .

1(a). 3.43 .5 nm-1 Adapted from Fig.405 nm # atoms a 2 LD = = 3. Linear Density Number of atoms • Linear Density of Atoms  LD = Unit length of direction vector [110] ex: linear density of Al in [110] direction a = 0. length 2a Callister & Rethwisch 9e. Chapter 4 .

4.2 x 10 a2 4 3 nm 2 m2 area R 3 2D repeat unit Chapter 4 . Reprinted by permission of John Wiley & Sons. W. New York.44 . Pearsall. Wulff. Copyright © 1964 by John Wiley & Sons. p. Vol. G.2(c). The Structure and Properties of Materials. 51. and J. G.1 = 1. 2D repeat unit (100) 4 3 a= R 3 Fig. Inc. Structure. Callister & Rethwisch 9e [from W. Planar Density of (100) Iron Solution: At T < 912°C iron has the BCC structure.1241 nm atoms 2D repeat unit 1 1 atoms atoms 19 Planar Density = = 2 = 12. Moffatt.] Radius of iron R = 0. I.

45 .0 0.70 x 1019 nm 2 m2 area 16 3 2 R 2D repeat unit 3 Chapter 4 . Planar Density of (111) Iron Solution (cont): (111) plane 1 atom in plane/ unit surface cell 2a atoms in plane atoms above plane atoms below plane 3 h= a 2 2 4 3 16 3 2 area = 2 ah = 3 a 2 = 3 R = R atoms 3 3 2D repeat unit 1 atoms = atoms Planar Density = = 7.

46 .VMSE Screenshot – Atomic Packing – (111) Plane for BCC Chapter 4 .

47 . • Can’t resolve spacings  λ • Spacing is the distance between parallel planes of atoms. X-Ray Diffraction • Diffraction gratings must have spacings comparable to the wavelength of diffracted radiation. Chapter 4 .

48 . intensity d= (from 2 sin θc allows computation of detector) planar spacing. by wave “2” spacing d between planes Measurement of X-ray nλ critical angle. X-Rays to Determine Crystal Structure • Incoming X-rays diffract from crystal planes. θ θc Chapter 4 . travelled θ θ Callister & Rethwisch 9e.  c. reflections must be in phase for a detectable signal extra distance λ Adapted from Fig. d. 4.29.

Chapter 4 .22. 3. Callister 8e. X-Ray Diffraction Pattern z z z c c c y (110) y y a b a b a b Intensity (relative) x x x (211) (200) Diffraction angle 2θ Diffraction pattern for polycrystalline α-iron (BCC) Adapted from Fig.49 .

. Summary • Common metallic crystal structures are FCC. • Interatomic bonding in ceramics is ionic and/or covalent. • Ceramic crystal structures are based on: -. Chapter 4 . This is referred to as polymorphism (or allotropy). HCP).cation-anion radii ratios. provided we know the atomic weight. and HCP. BCC. • Some materials can have more than one crystal structure. • We can predict the density of a material. atomic radius.50 . FCC.g. • X-ray diffraction is used for crystal structure and interplanar spacing determinations. and crystal geometry (e. BCC. Coordination number and atomic packing factor are the same for both FCC and HCP crystal structures.maintaining charge neutrality -.

ANNOUNCEMENTS Reading: Core Problems: Self-help Problems: Chapter 4 .51 .