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.

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

Anderson) Chapter 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) (Courtesy P.6 .M.

7 .42. Callister & Rethwisch 3e.52 atoms unit cell a R=0. 3.5a close-packed directions contains 8 x 1/8 = 1 atom/unit cell Adapted from Fig.Atomic Packing Factor (APF) Volume of atoms in unit cell* APF = Volume of unit cell *assume hard spheres • APF for a simple cubic structure = 0.5a) 3 1 3 a3 volume unit cell Chapter 3 . APF = volume atom 4 (0.

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

Atomic Packing Factor: BCC • APF for a body-centered cubic structure = 0. 3.9 .2(a).68 3a a 2a Adapted from Fig. 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 . Callister & Rethwisch 3e.

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

Atomic Packing Factor: FCC • APF for a face-centered cubic structure = 0.74 maximum achievable APF 2a a Adapted from Fig.11 .1(a). 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 . 3. Callister & Rethwisch 3e.

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 ..

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

 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.Theoretical Density.14 .022 x 1023 atoms/mol Chapter 3 .

Theoretical Density. atoms unit cell = volume unit cell R a 2 52.125 nm n = 2 atoms/unit cell Adapted from Fig.19 g/cm3 atoms mol Chapter 3 .00 a3 6. Callister & Rethwisch 3e.18 g/cm3 actual = 7.15 .2(a).  • Ex: Cr (BCC) A = 52.022 x 1023 a = 4R/ 3 = 0.2887 nm g mol theoretical = 7.00 g/mol R = 0. 3.

2. Copyright 1939 and 1940.16 Cornell University.7. . -. Copyright 1960 by Chapter 3 .Atomic Bonding in Ceramics • Bonding: -.% ionic character increases with difference in electronegativity of atoms.7 is adapted from Linus Pauling. 3rd edition.Can be ionic and/or covalent in character. 3rd edition. (Fig. 2. The Nature of the Chemical Bond. Callister & Rethwisch 3e. • Degree of ionic character may be large or small: CaF2: large SiC: small Adapted from Fig.

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 .17 .

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

3. how many anions can surround around a cation? r cation r anion < 0.3. Callister & Rethwisch 3e.732 6 octahedral 0.414 .Coordination # and Ionic Radii r cation • Coordination # increases with r anion To form a stable structure. Callister & Rethwisch 3e. NaCl (sodium chloride) Adapted from Fig.1.225 3 0. Callister & Rethwisch 3e.0.155 Coord # 2 linear 0.414 4 tetrahedral 0.0 8 Adapted from Table 3. Callister & Rethwisch 3e. triangular cubic ZnS (zinc blende) Adapted from Fig.19 .6.0.7. 3. 3. Chapter 3 .5.732 .155 .225 . CsCl (cesium chloride) Adapted from Fig.0.

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

8 and XC = 2.exp[-0. Si atoms occupy tetrahedral sites Chapter 3 .25( X Si  X C )2 ]}  11 .5% • ~ 89% covalent bonding • Both Si and C prefer sp3 hybridization • Therefore.21 .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. for SiC.

053 Fe 2+ 0.100 Anion O2Cl F- 0.22 .140  0.077 Fe 3+ 0.414 < 0.coord # = 6 because 0.crystal structure is NaCl Data from Table 3.140 0. Chapter 3 .077  ranion 0.4.550 based on this ratio.732 -.181 0. what crystal structure would you predict for FeO? Cation Ionic radius (nm) Al 3+ 0. Callister & Rethwisch 3e.069 Ca 2+ 0. -.133 • Answer: rcation 0.Example Problem: Predicting the Crystal Structure of FeO • On the basis of ionic radii.550 < 0.

Example: NaCl (rock salt) structure rNa = 0.Rock Salt Structure Same concepts can be applied to ionic solids in general.23 .5. 3.564  cations (Na+) prefer octahedral sites Adapted from Fig.181 nm rNa/rCl = 0. Chapter 3 . Callister & Rethwisch 3e.102 nm rCl = 0.

24 .140 nm Mg2+ rMg = 0. So each Mg2+ (or Fe2+) has 6 neighbor oxygen atoms Chapter 3 . Callister & Rethwisch 3e. 3.5.514  cations prefer octahedral sites Adapted from Fig.MgO and FeO MgO and FeO also have the NaCl structure O2- rO = 0.072 nm rMg/rO = 0.

Callister & Rethwisch 3e. Adapted from Fig.939 < 1.170  0. 3.25 . CsCl.6.181  Since 0.732 < 0.AX Crystal Structures AX–Type Crystal Structures include NaCl.0. and zinc blende Cesium Chloride structure: Cs  Cl  0.939 0. cubic sites preferred So each Cs+ has 8 neighbor ClChapter 3 .

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

Callister & Rethwisch 3e. 3.27 .9. Chapter 3 .ABX3 Crystal Structures • Perovskite structure Ex: complex oxide BaTiO3 Adapted from Fig.

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 .28 .

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

& tridymite • The strong Si-O bonds lead to a high melting temperature (1710ºC) for this material Chapter 3 . crystobalite.10-11.Silicate Ceramics Most common elements on earth are Si & O Si4+ O2Adapted from Figs. 3.30 . Callister & Rethwisch 3e crystobalite • SiO2 (silica) polymorphic forms are quartz.

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

Al3+. 3. Chapter 3 . and B3+  Na + Si 4+ O2- (soda glass) Adapted from Fig.32 .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+. Ca2+.41. Callister & Rethwisch 3e.

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)2.33 .g.13. mica.Layered Silicates • Layered silicates (e. Chapter 3 .. Callister & Rethwisch 3e. 3. clays.

Callister & Rethwisch 3e. Note: Adjacent sheets of this type are loosely bound to one another by van der Waal’s forces.14.Layered Silicates (cont) • Kaolinite clay alternates (Si2O5)2.  Chapter 3 .34 .layer with Al2(OH)42+ layer Adapted from Fig. 3.

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. Chapter 3 . Callister & Rethwisch 3e. etc. medical devices. Adapted from Fig. 3.16.35 .

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

37 . Chapter 3 .18 & 3. C60 – Like a soccer ball • Carbon nanotubes – sheet of graphite rolled into a tube – Ends capped with fullerene hemispheres Adapted from Figs.19.Polymorphic Forms of Carbon (cont) Fullerenes and Nanotubes • Fullerenes – spherical cluster of 60 carbon atoms. Callister & Rethwisch 3e. 3.

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

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

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

b/2. 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. 1 => [ 201 ] -1. Enclose in square brackets. 0.Crystallographic Directions Algorithm z y 1. ½ => 2. and c 3. 0. Read off projections in terms of unit cell dimensions a. Adjust to smallest integer values 4. 1. 2. 1 => [ 111 ] where overbar represents a negative index families of directions <uvw> Chapter 3 . no commas [uvw] x ex: 1. Vector repositioned (if necessary) to pass through origin.44 .

5 nm 1 Chapter 3 .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 = 0.45 .

Enclose in square brackets. a2. no commas a2 [uvtw] -a3 a2 2 => [ 1120 ] a3 dashed red lines indicate projections onto a1 and a2 axes a1 2 a1 Chapter 3 . 3. 0 through origin. Adjust to smallest integer values 4. Vector repositioned (if necessary) to pass a2 - a3 Adapted from Fig. a3. 2.HCP Crystallographic Directions z Algorithm 1. Callister & Rethwisch 3e. ex: a1 ½.46 . ½. or c 3. Read off projections in terms of unit cell dimensions a1. -1.24(a).

u ') 3 t  . Callister & Rethwisch 3e. u'v'w') as follows.HCP Crystallographic Directions • Hexagonal Crystals – 4 parameter Miller-Bravais lattice coordinates are related to the direction indices (i. w  w' Chapter 3 ..( u +v ) u a2 - a3 a1 Fig. z [ u 'v 'w ' ]  [ uvtw ] 1 (2 u ' .v ') 3 1  v (2 v ' .24(a). 3.47 .e.

Chapter 3 .25.48 . Callister & Rethwisch 3e.Crystallographic Planes Adapted from Fig. 3.

c 2.. (hkl) Chapter 3 .e. cleared of fractions & common multiples. Enclose in parentheses. Take reciprocals of intercepts 3.49 . no commas i. Reduce to smallest integer values 4. All parallel planes have same Miller indices. b. • Algorithm 1.Crystallographic Planes • Miller Indices: Reciprocals of the (three) axial intercepts for a plane. Read off intercepts of plane with axes in terms of a.

Intercepts 2.Crystallographic Planes z example 1. Miller Indices (110) example 1. Intercepts 2. 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 . Reduction a 1/2 1/½ 2 2 4. Reciprocals 3.50 y . Reduction a 1 1/1 1 1 4.

(100). (010).Crystallographic Planes z example 1. (001). (001) Chapter 3 . Reduction 4. 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).51 . (010). Intercepts 2. Reciprocals 3.

24(b). Reciprocals 3. Callister & Rethwisch 3e.Crystallographic Planes (HCP) • In hexagonal unit cells the same idea is used z example 1. 3.52 . Chapter 3 . Intercepts 2. Miller-Bravais Indices (1011) a1 Adapted from Fig. Reduction a1 1 1 1 1 a2  1/ 0 0 a3 -1 -1 -1 -1 c 1 1 1 1 a2 a3 4.

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

1241 nm Adapted from Fig. 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 = 0.1 2 nm m2 Chapter 3 .2 x 10 2 = 12.54 .2(c). 3.Planar Density of (100) Iron Solution: At T < 912C iron has the BCC structure. Callister & Rethwisch 3e.

0 2 R 2 3 a 2 h nm 2  16 3 2 R 3 0.55 .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 = = 7.70 x 1019 atoms m2 Chapter 3 .

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

57 .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.  d Measurement of critical angle. Callister & Rethwisch 3e. 3. d. reflections must be in phase for a detectable signal Adapted from Fig. spacing between planes X-ray intensity (from detector) d n 2 sin c  c Chapter 3 . c. allows computation of planar spacing.37.

Callister 5e. Chapter 3 .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.20. 3.58 y .

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

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

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

.039$  .$.7030:97.3.8..7341.041.8907  #098.9 ..590/1742    .-43/$  94430.94388:..0  !70803.42580/-90 8.908 43/341.$ /.34907 ../.42243..3/  43..     2.5907  .39.473078 0/08 471..08 $  ..

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