Metals and Ceramics I:

Material Structure

Prof. Wendy Liu

BME111  Design  of  Biomaterials  Spring  2014      April  4    Lecture  3    Slide  1    

 Last Time

•  Interatomic bonding is determined by the interactions of

valence electrons
•  Ionic bonds characterize ceramic materials, and involve
the interaction between charged atoms after transfer of
electrons
•  Covalent bonds characterize polymeric materials and
involve sharing of valence electrons

BME111  Design  of  Biomaterials  Spring  2014      April  4    Lecture  3    Slide  2    

 Polymers are characterized by covalent
bonds
–  Bonds are strong, but ability to rotate atoms around single bonds
generates flexibility, materials are easily deformed
–  Ways to prevent movement, for example crosslinking, so a wide
range of properties are possible
–  Electrons held in place, so not good conductors

Polymer   Applica.on  
Polyethylene   Total  joint  replacements  
 
Polytetrafluorethylene   Vascular  graGs  
(teflon)    
Polydimethyl  siloxane   Contact  lens,  breast  implants  
(silicone)  
Poly(lacLc  co-­‐glycolic)  acid   Resorbable  sutures,  stents  
(PLGA)  
Collagen   Tissue  engineered  scaffolds,  cosmeLc  agents  
BME111  Design  of  Biomaterials  Spring  2014      April  4    Lecture  3    Slide  3    
 Metallic Bonding

•  All elements are

electropositive, no
electronegative elements
•  Entire structure shares
electrons, which are mobile
and surround the cation
cores of each atom
•  Valence electrons are
delocalized
•  Attractive force is between
the positive cores and
negative electron “cloud”

BME111  Design  of  Biomaterials  Spring  2014      April  4    Lecture  3    Slide  4    

 Metals are characterized by metallic bonds
–  Atoms are closely packed in ordered arrays – crystalline
–  Highly mobile electrons so materials are conductive
–  Strong, but since atoms can move past each other, materials are
easily formed and processed
–  Susceptible to corrosion, so passivation is required

Metal   Applica.on  
Stainless  steel  (iron,  carbon,   Fracture  fixaLon  devices,  
chromium  alloy)   stents,  dental  implants  
 
Cobalt  chrome   Total  joint  replacements  
 
Titanium  and  alloys   Total  joint  replacements,  
dental  implants  
NiLnol   stents  
BME111  Design  of  Biomaterials  Spring  2014      April  4    Lecture  3    Slide  5    
 Secondary bonding
•  Van der Waals interaction – electrostatic interactions
between transient dipoles
H H H H
δ- δ+ δ- δ+
H C C H H C C H

H H H H induced dipole

•  Hydrogen bonding – electrostatic interaction between

polar molecules δ-
O  
δ+ H   H  
hydrogen bond
δ- O   O  
H   H   H   H  
BME111  Design  of  Biomaterials  Spring  2014     δ+  April  4    Lecture  3    Slide  6    
 Crystal Structure of Metals
•  A crystalline material is any material that has long-range
orderly arrangement of atoms or ions that can be
described by a unit cell
•  The unit cell is the smallest repeating unit
•  Atomic hard sphere model: each atom is a hard sphere
with fixed volume
•  Simple Cubic:

BME111  Design  of  Biomaterials  Spring  2014      April  4    Lecture  3    Slide  7    

 Atomic Packing Factor

•  Atomic Packing Factor volume

fraction that is occupied by atoms

•  APF = volume of atoms in a unit cell

total unit cell volume

•  For simple cubic:

r  =  radius  of  atom   –  1/8 of each atom in unit cell x 8 atoms = 1
  atom volume per unit cell = (4/3 pi r^3)
a  =  length  of  edge  of  unit  cell  
–  Volume of unit cell = a3 = (2r)3
–  APF = 1/6 pi = .52

BME111  Design  of  Biomaterials  Spring  2014      April  4    Lecture  3    Slide  8    

 Other cubic examples
•  Body centered cubic •  Face centered cubic
(BCC): (FCC):

•  An additional atom in the center •  An atom at the center of each

of the cube face of the cube
•  Examples include iron, •  Very common crystal structure
chromium •  APF is highest of all cubic
structures
•  Examples include aluminum,
copper, gold, lead, platinum

BME111  Design  of  Biomaterials  Spring  2014      April  4    Lecture  3    Slide  9    

 Coordination Number

•  Coordination number or coordinates refers to the number

of nearest neighbors,

CoordinaLon  number  of  the  center   CoordinaLon  number  is  12    

atom  is  8   (highest  possible)  

BME111  Design  of  Biomaterials  Spring  2014      April  4    Lecture  3    Slide  10    
 Crystal systems
z  
z  

β α
α
β c  
c   y  
y  
γ a  
γ a  
b  
b  
x  
x  

•  Coordinate system is used to describe crystal structures

•  Each lattice point (vertices of the unit cell) has identical surroundings
•  In SC, BCC and FCC, a = b = c, and α = β = γ = 90 degrees
•  Others shown in your text book (14 possible Bravais lattices)

BME111  Design  of  Biomaterials  Spring  2014      April  4    Lecture  3    Slide  11    
 Lattice points and directions
•  Coordinate system used to describe specific points,
directions, or planes in a crystal structure
Point  coordinates   z   Crystallographic    z  
direcLons  

1  1  1   [1  1  1]  

y   y  

x   x   [1  1  0]  
1  1  0  

•  Vector is positioned such that it passes through the

•  Positional coordinate is specified in origin of the coordinate system
terms of its coordinates as fractional •  Length of vector on each axis is determined, measured
in terms of unit cell dimensions, and reduced to
multiples of the unit cell edge lengths smallest integer values
•  Three indices, not separated by commas, enclosed in
•  No commas or punctuation brackets

BME111  Design  of  Biomaterials  Spring  2014      April  4    Lecture  3    Slide  12    
 Lattice Planes (Miller Indices)
•  Find intercepts along the three axes of
the crystal system
–  Plane intercepts z at z = 1, does not z  
intercept x or y axis (intercept = ∞) a  =  b  =  c  =  1  
•  Take the reciprocals
•  Multiply reciprocals by smallest integer
(n) necessary to convert to a set of
integers y  
•  Miller Indices represented by (h k l)
where h = n/xint , k = n/yint and l =n/zint
•  Plane in blue shown to the right is: x  
(0 0 1)

BME111  Design  of  Biomaterials  Spring  2014      April  4    Lecture  3    Slide  13    
 Miller Indices – more practice
z  

c   y  
a  
b  
x  
•  Intercepts are at x = 1, y = ∞, and z = 1
•  Miller Indices: (1 0 1)

BME111  Design  of  Biomaterials  Spring  2014      April  4    Lecture  3    Slide  14    
 Miller Indices… a few additional comments

•  All parallel planes at similar staggered distances have the same

Miller index
•  If a plane intercepts the origin, then you must shift to a parallel plane
in order to obtain the Miller Index
–  Otherwise the Miller index would be 1/0 or ∞
–  See discussion questions for practice
•  Negative indices are notated with a line over the index

BME111  Design  of  Biomaterials  Spring  2014      April  4    Lecture  3    Slide  15    
 Linear and Planar Densities
•  LD = number of atoms
centered on a direction
vector/length of the
vector
–  LD of [110] = 2 atoms / 4R
= 1/2R

•  PD = number of atoms
centered on a plane/area
of plane
–  PD of (110) = 2 atoms /
(4Rx2Rsqrt(2))= 1/
(4R2sqrt(2))

BME111  Design  of  Biomaterials  Spring  2014      April  4    Lecture  3    Slide  16    
 Coordinates and intercepts are relative to
the unit cell
•  Coordinate 1,1,1 is a,b,c
•  Plane (111) shown below

z  

β α
c   y  
γ a  
b  
x  

BME111  Design  of  Biomaterials  Spring  2014      April  4    Lecture  3    Slide  17    
 Ceramic crystal structures
•  Ceramics are mostly made up by ionic bonding of electronegative
and electropositive atoms
•  Crystal structure is affected by the size of the atoms (like metals)
and the charge of the ions (unlike metals)
•  General form: AmXp, where m and p are determined by charge
neutrality
–  NaCl: 1 Na+ for every 1 Cl-
–  CaF2: 2 F- for every 1 Ca2+
•  Stable structures have maximum # of nearest oppositely charged
neighbors and are closely packed Unstable    
Electron  clouds  overlap  

IntersLLal  site  filled  with  ion  of  opposite  charge  

CaLons  usually  smaller    

BME111  Design  of  Biomaterials  Spring  2014      April  4    Lecture  3    Slide  18