You are on page 1of 23

Metals and Ceramics II:

Defects
Solid State Diffusion

Prof. Wendy Liu

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


Announcements/notes

•  Natural vs. synthetic


–  Collagen
–  Alumina

•  Planar densities

•  Book stocked by April 9

BME111  Design  of  Biomaterials  Spring  2015    April  7    Lecture  3    Slide  2    


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  

Inters@@al  site  filled  with  ion  of  opposite  charge  


Ca@ons  usually  smaller    

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


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.  

BME111  Design  of  Biomaterials  Spring  2015    April  7    Lecture  3    Slide  4    


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

Si4+

O2-

Adapted  from  Figs.  


12.9-­‐10,  Callister  &  
Rethwisch  8e  
crystobalite

•  SiO2 (silica) polymorphic forms are quartz,


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

BME111  Design  of  Biomaterials  Spring  2015    April  7    Lecture  3    Slide  8     8


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

BME111  Design  of  Biomaterials  Spring  2015    April  7    Lecture  3    Slide  9    


Point defects: vacancies and interstitials

•  Vacancy Missing  atom    


in  structure  
Causes  extra  space  

•  Self-Interstitials
Extra  atom    
in  structure  
Causes  crowding  
 

BME111  Design  of  Biomaterials  Spring  2015    April  7    Lecture  3    Slide  10    
Point defects: impurities
•  Substitution defect or impurity
Atom  subs@tuted  
(solute)  
 

solvent  
•  Hume-Rothery rules help to determine solubility of   metals:
–  Atomic radii of the solvent and solute must be similar (less than 15%
difference)
–  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

BME111  Design  of  Biomaterials  Spring  2015    April  7    Lecture  3    Slide  11    
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
sites

BME111  Design  of  Biomaterials  Spring  2015    April  7    Lecture  3    Slide  12    
Alloys used as biomaterials
•  Stainless steel (316L)

Element   Atomic   Crystal   Valency   Electrone


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

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


~0.03%  
Chromium   0.125   BCC   3+   1.6   ~16%  
(Cr)  
Nickel  (Ni)   0.125   BCC   2+   1.8   ~10%  

Molybden 0.136   BCC   4+   1.8   ~2%  


um  (Mo)   (~10%  diff)  

BME111  Design  of  Biomaterials  Spring  2015    April  7    Lecture  3    Slide  13    
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  
electroneutrality  
–  Usually cations, because they are smaller

Missing  ca@on  
 
BME111  Design  of  Biomaterials  Spring  2015    April  7    Lecture  3    Slide  14    
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  
 

BME111  Design  of  Biomaterials  Spring  2015    April  7    Lecture  3    Slide  15    
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  

BME111  Design  of  Biomaterials  Spring  2015    April  7    Lecture  3    Slide  16    
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  
vacancy

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  

BME111  Design  of  Biomaterials  Spring  2015    April  7    Lecture  3    Slide  17    
Diffusion in solids

•  Interdiffusion or impurity diffusion


Diffusion  Couple  

Metal  1   Metal  2   Metal  1   Metal  2  

Concentra@on  
Diffusion  of  Metal  1  

Diffusion  of  Metal  2  

Posi@on  
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    
Diffusivity
•  The diffusivity of an atom is described by the diffusion coefficient, D
Qd
D = D0 exp(− )
RT
•  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/
atom)
•  D depends on the temperature and the activation energy for
diffusion, QD
–  The larger the activation energy, the smaller the diffusion
coefficient
–  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  

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

BME111  Design  of  Biomaterials  Spring  2015    April  7    Lecture  3    Slide  20    
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  
dx
A   B   dC CA − CB
=
dx x A − xB
CA  
C A − CB
J = −D( )
x A − xB
CB   The steeper the concentration
xA   xB   gradient, the greater the flux

BME111  Design  of  Biomaterials  Spring  2015    April  7    Lecture  3    Slide  21    
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

Cs  

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