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Metals and Ceramics II:

Solid State Diffusion

Prof. Wendy Liu

BME111  Design  of  Biomaterials  Spring  2015    April  7    Lecture  3    Slide  1    


•  Natural vs. synthetic

–  Collagen
–  Alumina

•  Planar densities

•  Book stocked by April 9

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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
–  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  

Inters@@al  site  filled  with  ion  of  opposite  charge  

Ca@ons  usually  smaller    

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Coordination # and ionic radii
r  ca@on   Coord    
•  Coordination # increases r  anion   #  
with ratio of radii
<  0.155     2     linear
between cation and
anion 0.155  -­‐  0.225     3     triangular

0.225  -­‐  0.414   4   tetrahedral

0.414  -­‐  0.732     6   octahedral

0.732  -­‐  1.0   8   cubic

Adapted  from  Table  12.2,  
Callister  &  Rethwisch  8e.  

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AX Structure: NaCl (rock salt structure)

rNa = 0.102 nm

rCl = 0.181 nm

rNa/rCl = 0.564

∴  cations (Na+) prefer octahedral sites

Adapted  from  Fig.  12.2,  

Callister  &  Rethwisch  8e.  

BME111  Design  of  Biomaterials  Spring  2015    April  7    Lecture  3    Slide  5     5

AX structure: CsCl
•  “interpenetrating simple cubic”
•  Coordination number is 8

rCs + 0.170
= = 0.939
rCl− 0.181

∴ Since 0.732 < 0.939 < 1.0,

cubic sites preferred
So  each  Cs  has  8  neighbor  Cl
Adapted  from  Fig.  12.3,  
Callister  &  Rethwisch  8e.  

BME111  Design  of  Biomaterials  Spring  2015    April  7    Lecture  3    Slide  6    

AX2 structure: CaF2

•  2 F- for every Ca2+

•  CsCl structure with half of the cation sites occupied

BME111  Design  of  Biomaterials   Spring  

Adapted   21015  
from  Fig.   2.5,    April  7    Lecture  3    Slide  7    
Silicate ceramics
Most common elements on earth are Si & O



Adapted  from  Figs.  

12.9-­‐10,  Callister  &  
Rethwisch  8e  

•  SiO2 (silica) polymorphic forms are quartz,

crystobalite, & tridymite
•  The strong Si-O bonds lead to a high melting
temperature (1710ºC) for this material

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Imperfections in the Crystal Lattice
•  Vacancy
•  Intersitital atoms
Point defects 10-10m
•  Substitutional atoms

•  Dislocations Line defects

–  Edges, Screws, Mixed

•  Grain boundaries
•  Stacking Faults Planar defects
•  Twin Boundaries

•  Void, Inclusions 3-dimensional defects 10-2m

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Point defects: vacancies and interstitials

•  Vacancy Missing  atom    

in  structure  
Causes  extra  space  

•  Self-Interstitials
Extra  atom    
in  structure  
Causes  crowding  

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Point defects: impurities
•  Substitution defect or impurity
Atom  subs@tuted  

•  Hume-Rothery rules help to determine solubility of   metals:
–  Atomic radii of the solvent and solute must be similar (less than 15%
–  Solute and solvent have identical crystal structures
–  A metal prefers to dissolve into a solution with higher valency over a
solution with lower valency
–  Solute and solvent have similar electronegativities

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Hume Rothery Rules – additional notes

•  Hume Rothery rules determine whether 2 elements will form a

solid solution, where the crystal structure remains unchanged.
Compounds (materials with different crystal structures) may
still form independent of the rules.

•  As a general rule of thumb:

–  If all 4 rules are obeyed, a substitutional solid with complete
solubility will result
–  If some (1, 2, maybe 3) of the rules are broken, there will be limited
or incomplete solubility

•  Interstitial solid solutions form if the size of the interstitial atom

is much smaller than the host atom and fits into the interstitial

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Alloys used as biomaterials
•  Stainless steel (316L)

Element   Atomic   Crystal   Valency   Electrone

Radius   Structure   ga9vity  
Iron  (Fe)   0.124   BCC   2+   1.8  

Carbon  (C)   0.071   Hex   4+   2.5   Inters@@al  

Chromium   0.125   BCC   3+   1.6   ~16%  
Nickel  (Ni)   0.125   BCC   2+   1.8   ~10%  

Molybden 0.136   BCC   4+   1.8   ~2%  

um  (Mo)   (~10%  diff)  

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Point defects in ceramics:
vacancies and interstitials
•  Electrical neutrality should be maintained
•  Shottky defect Missing  anion  
–  vacancy in both cation and anion to maintain neutrality
–  Defects can be far apart

Missing  ca@on  
•  Frenkel defect
–  A vacancy and interstitial pair is created to maintain Extra  ca@on  
–  Usually cations, because they are smaller

Missing  ca@on  
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Point defects in ceramics: impurities
•  Anions generally form substitutional solutions because they are
relatively large, cations can form substitutional or interstitial solutions
because they are smaller
inters@@al  ca@on  
  subs@tuted  ca@on  

Subs@tuted  anion  

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Diffusion in solids
•  In gases and liquids, diffusion occurs by random Brownian motion
•  In the solid state, diffusion of atoms occurs by jumping to
neighboring lattice points or positions

•  Self diffusion:

A   B  
B   A  

C   @me   C  

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Mechanisms of diffusion
•  In order for diffusion to occur, a free position (vacancy or interstitial
site) must be present nearby, and the atom must have sufficient
energy to break the bonds with its neighbors (vibrational energy)
•  Vacancy diffusion – atom jumps to neighboring position with a
diffusing  atom  

diffusing  atom  

vacancy   new  vacancy  

•  Interstitial diffusion – interstitial atom jumps to nearby interstitial site

inters@@al  atom  in  new  

inters@@al  atom  
inters@@al  site  
Which  is  faster?    Most  likely  inters@@al  because  it  does  not  require  the  existence  of  a  vacancy  

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Diffusion in solids

•  Interdiffusion or impurity diffusion

Diffusion  Couple  

Metal  1   Metal  2   Metal  1   Metal  2  

Diffusion  of  Metal  1  

Diffusion  of  Metal  2  

2  different  metals  (ex.  Copper  and  nickel)  placed  next  to  each  other  at  elevated    
temperature,  but  below  mel@ng  temperature  

BME111  Design  of  Biomaterials  Spring  2015    April  7    Lecture  3    Slide  18    
•  The diffusivity of an atom is described by the diffusion coefficient, D
D = D0 exp(− )
•  D0 is a temperature-independent constant (m2/s)
•  Qd is the activation energy for diffusion (J/mol, cal/mol, eV/atom)
•  R is a gas constant (8.31 J/mol-K, 1.987 cal/mol-K or 8.62 x 10-5 eV/
•  D depends on the temperature and the activation energy for
diffusion, QD
–  The larger the activation energy, the smaller the diffusion
–  The higher the temperature, the higher the diffusion coefficient

BME111  Design  of  Biomaterials  Spring  2015    April  7    Lecture  3    Slide  19    
Modeling diffusion: flux

Movement  of  atoms  

•  Flux, J, is the rate of change in mass or number of atoms across an
area over a given time
1 dM
A dt
•  Units for J are kg/m2-s or atoms/m2-s
•  Flux can be for vacancies, host atoms, or impurities

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Steady-state diffusion
•  At steady state, the flux does not change with time or is constant.
•  Flux is related to the concentration profile:
Nega@ve  sign  suggests  that  the  
dC direc@on  of  diffusion  is  down  the  
J = −D Fick’s First Law concentra@on  gradient  
A   B   dC CA − CB
dx x A − xB
C A − CB
J = −D( )
x A − xB
CB   The steeper the concentration
xA   xB   gradient, the greater the flux

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Non steady-state diffusion
•  If diffusion is very slow (as can be the case in solids), it may take a
long time to reach steady state - concentration profiles will change
with time
•  Conservation of mass: the rate of change of concentration C in the
box is equal to the flux into the box minus the flux out of the box

dJ J B − J A dC
= =−
dx dx dt
dJ d 2C
@me   = −D 2
JA   JB   dx dx

∂C ∂2 C
=D 2 Fick’s  Second  Law  
xA   xB  
∂t ∂x
BME111  Design  of  Biomaterials  Spring  2015    April  7    Lecture  3    Slide  22    
Solution to Fick’s Second Law
•  For the following boundary conditions (a semi-infinite solid)
–  At t=0, C throughout the material equals C0
–  At t>0, C at the surface (x=0) is Cs and C at x=∞ is C0


C(x, t) − C0 x
@me   = 1− erf ( )
Cs − C0 2 Dt

C0   error  func@on  values  need  to  be  looked  

up  from  a  table  
x=0   X∞  

BME111  Design  of  Biomaterials  Spring  2015    April  7    Lecture  3    Slide  23