Chapter 3: Structures of Metals & Ceramics

ISSUES TO ADDRESS...
• How do atoms assemble into solid structures?
• How does the density of a material depend on
its structure?
• How do the crystal structures of ceramic
materials differ from those for metals?
• When do material properties vary with the
sample (i.e., part) orientation?

Chapter 3 - 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.
Chapter 3 - 2

Materials and Packing
Crystalline materials...
• atoms pack in periodic, 3D arrays
• typical of: -metals
-many ceramics
-some polymers

crystalline SiO2
Adapted from Fig. 3.40(a),
Callister & Rethwisch 3e.

Noncrystalline materials...
• atoms have no periodic packing
• occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline

Si

Oxygen

noncrystalline SiO2
Adapted from Fig. 3.40(b),
Callister & Rethwisch 3e.
Chapter 3 - 3

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

.Electron cloud shields cores from each other • Have the simplest crystal structures. .Metallic bonding is not directional.Metallic Crystal Structures • Tend to be densely packed. Chapter 3 . only one element is present. We will examine three such structures.. • Reasons for dense packing: .Nearest neighbor distances tend to be small in order to lower bond energy.Typically.5 . .. so all atomic radii are the same.

6 . • Coordination # = 6 (# nearest neighbors) (Courtesy P.M.Simple Cubic Structure (SC) • Rare due to low packing density (only Po has this structure) • Close-packed directions are cube edges. Anderson) Chapter 3 .

Callister & Rethwisch 3e.42.7 .5a) 3 1 3 a3 volume unit cell Chapter 3 . APF = volume atom 4 (0.5a close-packed directions contains 8 x 1/8 = 1 atom/unit cell Adapted from Fig.52 atoms unit cell a R=0.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. 3.

Molybdenum • Coordination # = 8 QuickTime™ and a Cinepak decompressor are needed to see this picture. Fe (). Adapted from Fig. 3. Tantalum. the center atom is shaded differently only for ease of viewing. Callister & Rethwisch 3e.M.Body Centered Cubic Structure (BCC) • Atoms touch each other along cube diagonals. 2 atoms/unit cell: 1 center + 8 corners x 1/8 (Courtesy P.8 . --Note: All atoms are identical. Anderson) Chapter 3 . ex: Cr. W.2.

R a Close-packed directions: length = 4R = 3 a atoms volume 4  ( 3a/4) 3 2 unit cell atom 3 APF = volume a3 unit cell Chapter 3 . 3.68 3a a 2a Adapted from Fig.Atomic Packing Factor: BCC • APF for a body-centered cubic structure = 0.2(a). Callister & Rethwisch 3e.9 .

M. Ag • Coordination # = 12 QuickTime™ and a Cinepak decompressor are needed to see this picture. 3. Ni. Anderson) Chapter 3 . Au. Pb. Pt.10 .1.Face Centered Cubic Structure (FCC) • Atoms touch each other along face diagonals. Callister & Rethwisch 3e. the face-centered atoms are shaded differently only for ease of viewing. Adapted from Fig. ex: Al. Cu. 4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8 (Courtesy P. --Note: All atoms are identical.

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

.12 .FCC Stacking Sequence • ABCABC.. Stacking Sequence • 2D Projection B B C A B B B A sites C C B sites B B C sites • FCC Unit Cell A B C Chapter 3 .

. 3. Callister & Rethwisch 3e.. Ti.74 • c/a = 1.13 . Stacking Sequence • 3D Projection c a • 2D Projection A sites Top layer B sites Middle layer A sites Bottom layer Adapted from Fig.Hexagonal Close-Packed Structure (HCP) • ABAB. Zn Chapter 3 .633 6 atoms/unit cell ex: Cd.3(a). Mg. • Coordination # = 12 • APF = 0.

Theoretical Density.  Density =  =  = where Mass of Atoms in Unit Cell Total Volume of Unit Cell nA VC NA n = number of atoms/unit cell A = atomic weight VC = Volume of unit cell = a3 for cubic NA = Avogadro’s number = 6.022 x 1023 atoms/mol Chapter 3 .14 .

00 g/mol R = 0.19 g/cm3 atoms mol Chapter 3 .022 x 1023 a = 4R/ 3 = 0.  • Ex: Cr (BCC) A = 52.Theoretical Density.18 g/cm3 actual = 7.2887 nm g mol theoretical = 7. atoms unit cell = volume unit cell R a 2 52. Callister & Rethwisch 3e.15 .2(a).00 a3 6. 3.125 nm n = 2 atoms/unit cell Adapted from Fig.

Atomic Bonding in Ceramics • Bonding: -. 2. . -.16 Cornell University.% ionic character increases with difference in electronegativity of atoms. 2. 3rd edition.7 is adapted from Linus Pauling. Copyright 1939 and 1940. Callister & Rethwisch 3e.7. • Degree of ionic character may be large or small: CaF2: large SiC: small Adapted from Fig.Can be ionic and/or covalent in character. Copyright 1960 by Chapter 3 . 3rd edition. The Nature of the Chemical Bond. (Fig.

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 3 .

4. - stable Ca 2+ + cation Fanions F- A m Xp m.18 . --Reflected in chemical formula: CaF 2 : + Adapted from Fig. 3. Callister & Rethwisch 3e. p values to achieve charge neutrality Chapter 3 .Factors that Determine Crystal Structure 1. Relative sizes of ions – Formation of stable structures: --maximize the # of oppositely charged ion neighbors. - + - - - unstable 2. Maintenance of Charge Neutrality : + - - - - stable --Net charge in ceramic should be zero.

Callister & Rethwisch 3e.1.19 . NaCl (sodium chloride) Adapted from Fig.732 . Callister & Rethwisch 3e. triangular cubic ZnS (zinc blende) Adapted from Fig.5.6. 3. how many anions can surround around a cation? r cation r anion < 0. 3.3. CsCl (cesium chloride) Adapted from Fig.0 8 Adapted from Table 3.414 .7.0. Callister & Rethwisch 3e.0.Coordination # and Ionic Radii r cation • Coordination # increases with r anion To form a stable structure.225 3 0. Callister & Rethwisch 3e. Chapter 3 .155 Coord # 2 linear 0.155 .414 4 tetrahedral 0.0. 3.225 .732 6 octahedral 0.

N.414 anion   Chapter 3 .Computation of Minimum Cation-Anion Radius Ratio • Determine minimum rcation/ranion for an octahedral site (C.20 . = 6) 2ranion  2rcation  2a a  2ranion                    cation  2  1  0.

21 .5% • ~ 89% covalent bonding • Both Si and C prefer sp3 hybridization • Therefore. Si atoms occupy tetrahedral sites Chapter 3 .8 and XC = 2.5 % ionic character  100 {1 .Bond Hybridization Bond Hybridization is possible when there is significant covalent bonding – hybrid electron orbitals form – For example for SiC • XSi = 1.25( X Si  X C )2 ]}  11 .exp[-0. for SiC.

140 0.077 Fe 3+ 0.4.550 based on this ratio.133 • Answer: rcation 0. what crystal structure would you predict for FeO? Cation Ionic radius (nm) Al 3+ 0. -.crystal structure is NaCl Data from Table 3.053 Fe 2+ 0. Callister & Rethwisch 3e.Example Problem: Predicting the Crystal Structure of FeO • On the basis of ionic radii.22 .550 < 0.coord # = 6 because 0.100 Anion O2Cl F- 0.077  ranion 0.414 < 0.181 0. Chapter 3 .069 Ca 2+ 0.732 -.140  0.

Chapter 3 .23 . Example: NaCl (rock salt) structure rNa = 0.181 nm rNa/rCl = 0.564  cations (Na+) prefer octahedral sites Adapted from Fig.Rock Salt Structure Same concepts can be applied to ionic solids in general.102 nm rCl = 0.5. Callister & Rethwisch 3e. 3.

Callister & Rethwisch 3e.5.140 nm Mg2+ rMg = 0. 3. So each Mg2+ (or Fe2+) has 6 neighbor oxygen atoms Chapter 3 .514  cations prefer octahedral sites Adapted from Fig.MgO and FeO MgO and FeO also have the NaCl structure O2- rO = 0.24 .072 nm rMg/rO = 0.

Adapted from Fig.732 < 0.939 < 1.939 0.AX Crystal Structures AX–Type Crystal Structures include NaCl.181  Since 0. 3. and zinc blende Cesium Chloride structure: Cs  Cl  0. CsCl.170  0.0. cubic sites preferred So each Cs+ has 8 neighbor ClChapter 3 .25 . Callister & Rethwisch 3e.6.

ThO2. CeO2 • Antifluorite structure – positions of cations and anions reversed Adapted from Fig.AX2 Crystal Structures Fluorite structure • Calcium Fluorite (CaF2) • Cations in cubic sites • UO2.26 . Callister & Rethwisch 3e. ZrO2.8. Chapter 3 . 3.

9.ABX3 Crystal Structures • Perovskite structure Ex: complex oxide BaTiO3 Adapted from Fig. 3. Chapter 3 .27 . Callister & Rethwisch 3e.

28 .Density Computations for Ceramics Number of formula units/unit cell n(AC  AA )  VC N A 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 3 .

. • less dense packing • often lighter elements Polymers have. Ceramics have.... • intermediate values Metals/ Alloys 20 Platinum Gold. W Tantalum 10 Silver. Mo Cu. Chapter 3 . LDPE Glass fibers GFRE* Carbon fibers CFRE* Aramid fibers AFRE* Wood Data from Table B.3 Titanium Aluminum Magnesium Graphite/ Ceramics/ Semicond Composites/ fibers Polymers Based on data in Table B1. & AFRE are Glass.29 .. Callister & Rethwisch.O) Composites have.. & Aramid Fiber-Reinforced Epoxy composites (values based on 60% volume fraction of aligned fibers in an epoxy matrix). Zirconia Al oxide Diamond Si nitride Glass -soda Concrete Silicon Graphite PTFE Silicone PVC PET PC HDPE..4 0.5 0. Callister *GFRE. PS PP. 3e. Carbon.  (g/cm3 ) • close-packing (metallic bonding) • often large atomic masses • low packing density (often amorphous) • lighter elements (C. Zinc 5 4 3 2 1 0.1.Densities of Material Classes In general metals > ceramics > polymers 30 Why? Metals have.Ni Steels Tin.. CFRE.H.

30 . Callister & Rethwisch 3e crystobalite • SiO2 (silica) polymorphic forms are quartz. 3. crystobalite.Silicate Ceramics Most common elements on earth are Si & O Si4+ O2Adapted from Figs.10-11. & tridymite • The strong Si-O bonds lead to a high melting temperature (1710ºC) for this material Chapter 3 .

edges.to one another Chapter 3 .Silicates Bonding of adjacent SiO44. and 2. Mg2+. Callister & Rethwisch 3e. or faces Mg2SiO4 Ca2MgSi2O7 Adapted from Fig. maintain charge neutrality. ionically bond SiO44.12.accomplished by the sharing of common corners. 3. & Al3+ 1. Presence of cations such as Ca2+.31 .

Glass Structure • Basic Unit: 4Si0 4 tetrahedron Si 4+ O2- • Quartz is crystalline SiO2: Glass is noncrystalline (amorphous) • Fused silica is SiO2 to which no impurities have been added  • Other common glasses contain impurity ions such as Na+. and B3+  Na + Si 4+ O2- (soda glass) Adapted from Fig. 3. Callister & Rethwisch 3e.41. Chapter 3 .32 . Al3+. Ca2+.

unit Negative charge balanced by adjacent plane rich in positively charged cations Adapted from Fig. talc) – SiO4 tetrahedra connected together to form 2-D plane • • A net negative charge is associated with each (Si2O5)2. clays. 3.33 .Layered Silicates • Layered silicates (e.g.13. Callister & Rethwisch 3e.. Chapter 3 . mica.

14.Layered Silicates (cont) • Kaolinite clay alternates (Si2O5)2. Note: Adjacent sheets of this type are loosely bound to one another by van der Waal’s forces.  Chapter 3 . 3.34 . Callister & Rethwisch 3e.layer with Al2(OH)42+ layer Adapted from Fig.

35 . etc. 3. medical devices.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 • hard surface coatings – used for cutting tools.16. Callister & Rethwisch 3e. Adapted from Fig. Chapter 3 .

good lubricant Chapter 3 . 3.Polymorphic Forms of Carbon (cont) Graphite – layered structure – parallel hexagonal arrays of carbon atoms Adapted from Fig. – weak van der Waal’s forces between layers – planes slide easily over one another -.36 . Callister & Rethwisch 3e.17.

C60 – Like a soccer ball • Carbon nanotubes – sheet of graphite rolled into a tube – Ends capped with fullerene hemispheres Adapted from Figs. Chapter 3 .37 . Callister & Rethwisch 3e.Polymorphic Forms of Carbon (cont) Fullerenes and Nanotubes • Fullerenes – spherical cluster of 60 carbon atoms.18 & 3. 3.19.

(Fig.38 . 9. GE Superabrasives. -.M. 9. Used with permission. Callister & Rethwisch 3e. (Courtesy P.) -.40(c).Crystals as Building Blocks • Some engineering applications require single crystals: -. OH.40(c) courtesy of Pratt and Whitney). • Properties of crystalline materials often related to crystal structure.turbine blades Fig.Ex: Quartz fractures more easily along some crystal planes than others. Anderson) Chapter 3 . Worthington.diamond single crystals for abrasives (Courtesy Martin Deakins.

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 5e.
(Fig. K is courtesy of
Paul E. Danielson,
Teledyne Wah Chang
Albany)

Isotropic

overall component properties are not directional.

• Grain sizes typ. range from 1 nm to 2 cm
(i.e., from a few to millions of atomic layers).

Chapter 3 - 39

Single vs Polycrystals
• Single Crystals

E (diagonal) = 273 GPa
Data from Table 3.7,
Callister & Rethwisch
3e. (Source of data is
R.W. Hertzberg,
Deformation and
Fracture Mechanics of
Engineering Materials,
3rd 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 m

Adapted from Fig.
5.19(b), Callister &
Rethwisch 3e.
(Fig. 5.19(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].)

Chapter 3 - 40

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
Chapter 3 - 41

Chapter 3 .20. Callister & Rethwisch 3e. 3.42 .Crystal Systems Unit cell: smallest repetitive volume which contains the complete lattice pattern of a crystal. and c are the lattice constants Fig. 7 crystal systems 14 crystal lattices a. b.

c/2 000 a x y b Point coordinates for unit cell corner are 111  z ½½½ 2c    b y Translation: integer multiple of lattice constants  identical position in another unit cell b Chapter 3 .Point Coordinates z Point coordinates for unit cell center are 111 c a/2.43 . b/2.

Adjust to smallest integer values 4. b. 1. 2. Vector repositioned (if necessary) to pass through origin. and c 3.Crystallographic Directions Algorithm z y 1. 1 => [ 201 ] -1. ½ => 2.44 . 1 => [ 111 ] where overbar represents a negative index families of directions <uvw> Chapter 3 . Enclose in square brackets. 0. Read off projections in terms of unit cell dimensions a. no commas [uvw] x ex: 1. 0.

45 .405 nm # atoms LD  length 2 2a  3.Linear Density • Linear Density of Atoms  LD = [110] a Number of atoms Unit length of direction vector ex: linear density of Al in [110] direction a = 0.5 nm 1 Chapter 3 .

Enclose in square brackets.46 . Adjust to smallest integer values 4. Vector repositioned (if necessary) to pass a2 - a3 Adapted from Fig.HCP Crystallographic Directions z Algorithm 1. a3. no commas a2 [uvtw] -a3 a2 2 => [ 1120 ] a3 dashed red lines indicate projections onto a1 and a2 axes a1 2 a1 Chapter 3 . 0 through origin. Read off projections in terms of unit cell dimensions a1. ½.24(a). or c 3. 2. a2. ex: a1 ½. -1. Callister & Rethwisch 3e. 3.

24(a). w  w' Chapter 3 . z [ u 'v 'w ' ]  [ uvtw ] 1 (2 u ' .e.47 .v ') 3 1  v (2 v ' ..HCP Crystallographic Directions • Hexagonal Crystals – 4 parameter Miller-Bravais lattice coordinates are related to the direction indices (i.( u +v ) u a2 - a3 a1 Fig. 3. Callister & Rethwisch 3e. u'v'w') as follows.u ') 3 t  .

Crystallographic Planes Adapted from Fig.48 . Chapter 3 . 3. Callister & Rethwisch 3e.25.

c 2. • Algorithm 1. no commas i.. Take reciprocals of intercepts 3.e. cleared of fractions & common multiples. b. (hkl) Chapter 3 . Enclose in parentheses. All parallel planes have same Miller indices.49 . Read off intercepts of plane with axes in terms of a.Crystallographic Planes • Miller Indices: Reciprocals of the (three) axial intercepts for a plane. Reduce to smallest integer values 4.

50 y . Reduction a 1/2 1/½ 2 2 4.Crystallographic Planes z example 1. Intercepts 2. Reduction a 1 1/1 1 1 4. Reciprocals 3. Miller Indices (100) b 1 1/1 1 1 c  1/ 0 0 c b a x b  1/ 0 0 y z c  1/ 0 0 c a b x Chapter 3 . Miller Indices (110) example 1. Intercepts 2. Reciprocals 3.

Intercepts 2. Reduction 4. (010).51 . (001). Miller Indices a 1/2 1/½ 2 6 b 1 1/1 1 3 (634) c c 3/4 1/¾ 4/3  4 a x   b y Family of Planes {hkl} Ex: {100} = (100). (010). Reciprocals 3. (001) Chapter 3 .Crystallographic Planes z example 1. (100).

Crystallographic Planes (HCP) • In hexagonal unit cells the same idea is used z example 1. Chapter 3 . Miller-Bravais Indices (1011) a1 Adapted from Fig.24(b).52 . Intercepts 2. Reduction a1 1 1 1 1 a2  1/ 0 0 a3 -1 -1 -1 -1 c 1 1 1 1 a2 a3 4. Reciprocals 3. Callister & Rethwisch 3e. 3.

a) Draw (100) and (111) crystallographic planes for Fe. The atomic packing of the exposed planes is important.Crystallographic Planes • • We want to examine the atomic packing of crystallographic planes Iron foil can be used as a catalyst. Chapter 3 .53 . b) Calculate the planar density for each of these planes.

atoms 2D repeat unit a R atoms atoms 19 = 1. 2D repeat unit (100) Planar Density = area 2D repeat unit 1 a2 = 1 4 3 3 4 3 R 3 Radius of iron R = 0.Planar Density of (100) Iron Solution: At T < 912C iron has the BCC structure.2 x 10 2 = 12. Callister & Rethwisch 3e.1241 nm Adapted from Fig.54 . 3.1 2 nm m2 Chapter 3 .2(c).

70 x 1019 atoms m2 Chapter 3 .Planar Density of (111) Iron Solution (cont): (111) plane 1 atom in plane/ unit surface cell 2a atoms in plane nit atoms above plane r ep ea tu atoms below plane 2D  4 3  area  2 ah  3 a  3  R   3  2 atoms 2D repeat unit Planar Density = area 2D repeat unit 1 16 3 3 atoms = = 7.55 .0 2 R 2 3 a 2 h nm 2  16 3 2 R 3 0.

• Can’t resolve spacings   • Spacing is the distance between parallel planes of atoms.56 . Chapter 3 .X-Ray Diffraction • Diffraction gratings must have spacings comparable to the wavelength of diffracted radiation.

X-Rays to Determine Crystal Structure ” “2  ” extra distance travelled by wave “2” o g ut ng i o ys a r X-  et ec to r “2 ” “1 g in m co s in ray X- “1 ” • Incoming X-rays diffract from crystal d planes.37. reflections must be in phase for a detectable signal Adapted from Fig.57 . d. 3. allows computation of planar spacing. c.  d Measurement of critical angle. spacing between planes X-ray intensity (from detector) d n 2 sin c  c Chapter 3 . Callister & Rethwisch 3e.

58 y . Chapter 3 . 3.20.z X-Ray Diffraction Pattern z c Intensity (relative) c a x b y (110) a x z c b y a x b (211) (200) Diffraction angle 2 Diffraction pattern for polycrystalline -iron (BCC) Adapted from Fig. Callister 5e.

cation-anion radii ratios.g. BCC.. and crystal geometry (e. • Interatomic bonding in ceramics is ionic and/or covalent. FCC. atomic radius. Coordination number and atomic packing factor are the same for both FCC and HCP crystal structures. BCC. • Common metallic crystal structures are FCC. • Ceramic crystal structures are based on: -.SUMMARY • Atoms may assemble into crystalline or amorphous structures. HCP). • We can predict the density of a material. and HCP. Crystallographic directions and planes are related to atomic linear densities and planar densities.maintaining charge neutrality -. Chapter 3 .59 . • Crystallographic points. directions and planes are specified in terms of indexing schemes. provided we know the atomic weight.

This is referred to as polymorphism (or allotropy).60 .e.SUMMARY • Materials can be single crystals or polycrystalline. • Some materials can have more than one crystal structure.. but are generally non-directional (i.e. they are anisotropic). Material properties generally vary with single crystal orientation (i.. • X-ray diffraction is used for crystal structure and interplanar spacing determinations. Chapter 3 . they are isotropic) in polycrystals with randomly oriented grains.

ANNOUNCEMENTS Reading: Core Problems: Self-help Problems: Chapter 3 .61 .

.39.041.....$.908 43/341.42243.08 $  .3.7030:97.94388:.0  !70803.42580/-90 8.8.7341..$ /..8907  #098.3/  43.590/1742    .-43/$  94430.34907 .9 .     2..039$  ..473078 0/08 471./.5907  .

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