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Prof.P. Ravindran,

Department of Physics, Central University of Tamil

Nadu, India

http://folk.uio.no/ravi/PMAT2013

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

2

Diffusion:

(1) motion of one or more particles of a system relative to

other particles (Onsager, 1945)

above the absolute zero

is not necessary for diffusion

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

3

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

4

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

5

Diffusion (conduction)

or molecules--by random motion

by random motion.

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

6

Diffusion

Mechanisms

Gases & Liquids random (Brownian) motion

Concentration gradient

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

7

At time t = 0, add some drops of ink to one end

of the tube.

Measure the diffusion distance, x, over some time.

x (mm)

time (s)

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

8

Mass Transfer

Mass transfer occurs when a component in a mixture goes from one point to

another.

concentration gradient.

fluid or between relatively immiscible moving fluids.

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

9

Example of Mass Transfer

Mass transfer can occur by either diffusion or by convection.

a spoon creates forced

convection.

molecules to transfer to

the bulk water much

faster.

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

10

sugar, why do we stir our

coffee?

Diffusion is slow!

distances in the same amount of time, which can

accelerate the diffusion process.

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

11

Example of Mass Transfer

Air Blood

Oxygen

Low carbon dioxide concentration High carbon dioxide concentration

Carbon dioxide

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

12

Diffusion

is a net transport of molecules from a region of

higher concentration to a region of lower

concentration by random molecular motion.

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

13

Diffusion

A B Liquids A and B are separated from each other.

Separation removed.

A B concentration of A.

B goes from high concentration of B to low

concentration of B.

everywhere in the vessel purely due to the

DIFFUSION.

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

14

in all directions. A concentration of ink particles will

disperse.

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

15

Concentrated Region

Molecules in a concentrated

region will disperse into the

rest of the medium. C1

x

The difference in

concentrations is the

concentration gradient.

C2

C C1 C2

x x

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

16

Diffusion Constant

through an area at C1

different rates.

x

Depends on concentrate

A

Depends on medium D

DNA in water: D = 1.3 x 10-12 m2/s

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

17

Temperature Diffusivity

(C) (cm2/s)

CO2-N20 0 0.096

(gas)

Ar-O2 20 0.2

Ethanol(5%)-Water 25 1.13E-05

(liquid)

Water(13%)-Butanol 30 1.24E-05

H2-Ni 85 1.16E-08

(solid)

Al-Cu 20 1.30E-30

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

Diffusion & Transport 18

a balance or equality is established. This tendency is often referred to as the driving force,

which is the mechanism behind many naturally occurring transport phenomena.

redistribution, and thus the flow is a diffusion

process. The rate of flow of the commodity is

proportional to the concentration gradient dC/dx,

which is the change in the concentration C per unit

length in the flow direction x, and the area A normal

to flow direction.

kdiff is the diffusion coefficient of the medium, which is a measure of how fast a commodity diffuses

in the medium, and the negative sign is to make the flow in the positive direction a positive

quantity (note that dC/dx is a negative quantity since concentration decreases in the flow

direction).

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

19

The diffusion coefficients and thus diffusion rates of gases depend strongly on

temperature.

The diffusion rates are higher at higher temperatures.

The larger the molecular spacing, the higher the diffusion rate.

Diffusion rate: gases > liquids > solids

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

20

effort by simply drawing parallels between heat and mass transfer.

Temperature

The driving force for mass transfer is

the concentration difference.

Both heat and mass are transferred

from the more concentrated regions to

the less concentrated ones.

If there is no difference between the

concentrations of a species at different

parts of a medium, there will be no

mass transfer.

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

Gradient 21

Ficks Law

( , , )

x y z

During diffusion we assume particles move in the

direction of least density. They move down the

concentration gradient

assume

J Du

Where D is a constant of

proportionality called the Diffusion

Adolph Fick Coefficient

Born: 1829

Cassel, Germany

Died: 1879

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

22

Ficks Law

area (A) , and diffusion constant (D).

C1 C2

J DA

t

J measures mol/m3.

There is a diffusion time t for diffusion in one direction over

a distance Dx.

x 2

t

2D

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

23

are moving down a gradient!

concentration)

dci

Ficks Law: Ji D

dz

(l 2 )(t )

l2

D is called the diffusion coefficient. It has units of

t

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

24

Mass is transferred by conduction (called diffusion) and convection only.

Rate of mass Ficks law of

diffusion diffusion

DAB is the diffusion coefficient (or

mass diffusivity) of the species in the

mixture

CA is the concentration of the species

in the mixture

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

25

5) Influenza epidemics

6) Chemical reactions

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

26

Unsteady state diffusion

Back to a drop of ink in a glass

of water If consider diffusion in the z-

direction only:

How does the concentration profile

change with time?

t=0

(add ink drop all

ink located at z =

t

0)

z

z=0

A measure of the spread due to diffusion is the diffusion length

Ld = (4Dt)0.5, where D is the diffusivity coefficient and t is time.

Note: for small time, spreading is quick, but for long times it

slows down. Thats why you stir your coffee after adding

cream. Diffusion doesnt work fast enough over long distances.

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

27

c

dc

J D 0

dx

dc x

J D

dx

D diffusion coefficient

c

dc

J D 0

dx

x

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

28

Continuum description of diffusion

j+

j

x-L x x+L

j: flux of particles (number of particles per unit area per unit time)

c: concentration of particles (number of particles per unit volume)

Random walk in 1D; half of particles in each bin move to the left and

half to the right.

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

29

Right, left and total fluxes at x are given by

c( x L / 2) AL

1 1

c( x L / 2) AL

j 2

, j 2

At At

j j j

L

c( x L / 2) c( x L / 2)

2t

L L dc L dc

j c ( x ) c ( x )

2t 2 dx 2 dx

L2 dc dc

D , Fick' s law

2t dx dx

Generalise to 3D: j D c

Flux direction: particles move from high concentration to low concentration

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

30

Conservation laws:

Total number of particles is conserved.

If there is a net flow of particles inside a bin, j j

c(x,t)

the concentration inside must increase by

the same amount.

x-L/2 x x+L/2

c( x, t t ) c( x, t )AL j ( x L / 2) j ( x L / 2)At

c L dj L dj

L j ( x) j ( x)

t 2 dx 2 dx

dc dj

dt dx

dc

j

Generalise to 3D: dt

(similar to charge conservation)

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

31

Integrate the conservation equation over a closed volume V with N parts

dc

dt dV j dV

V V

d

dt V

c dV j n da (Divergence theorem)

S

dN

(rate of change of N = - total flux out)

dt

We can use the conservation equation to eliminate flux from Ficks eqn.

dc dj d 2c dc d 2c

j D , D 2 D 2 nd

dx dx dt Ficks 2 law

dx dx Diffusion eq.

dc

Generalise to 3D: D 2c (analogy with the Schroedinger Eq.)

dt

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

32

Once the initial conditions are specified, the diffusion equation can be

solved numerically using a computer.

Special cases:

No time dependence, dc 0,

dj

0, j const.

dt dx

dc j

j D , c xb

dx D

j c L c0

c0 b, c L L c0 j D

D L

cL c0

c x c0 for 0 x L

L

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

33

Ficks second law: mass balance of fluxes

Your salary ($$ per month) - what you spend ($$ per month)

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

34

Ficks second law: mass balance of fluxes

analytical solution (e.g., Crank, 1975) or (b) numerical methods

straightforward for exercise cases, less so in nature.

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

35

c x

c x

time

x

How can we find out c(x,t) ?

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

36

Flux in 1 dimension:

A

J(x+x)

J (x) J (x+x) J

V

J(x)

x x

x

N

J ( x) A J ( x x) A A[ J ( x x) J ( x)] A J

t

dJ dJ dc d ( N / V ) dJ

A x V

dx dx dt dt dx

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

37

dc dJ

dt dx 2

dc d c

D 2

dc dt dx

J D

dx

Fick' s law We can find out c(x,t) !

Ficks second law

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

38

Ficks Laws

law, we obtain Ficks second law:

c c 2

D 2

t x

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

39

boundary conditions.

Assumptions

D is independent of concentration

Semiconductor is a semi-infinite slab with either

Continuous supply of impurities that can move into

wafer

Fixed supply of impurities that can be depleted

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

40

steady state and there is no

variation of the concentration

c 2

D 2 0

with time

Concentration of diffusing

impurities is linear over

distance

x

This was the solution for the

flow of oxygen from the

c( x ) a bx

surface to the Si/SiO2

interface.

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

41

of atoms at the surface

x

c( x, t ) co erfc

2 Dt

The dose is

Q cx, t dx 2c0 Dt

0

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

42

erfc(x) = 1 - erf(x)

The error function is defined as

exp d

z

2

erf ( z ) 2

0

This is a tabulated function. There are several

approximations. It can be found as a built-in

function in MatLab, MathCad, and Mathematica

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

43

or liquid phase source

Typical solutions have the following shape

c0

Impurity concentration, c(x)

c ( x, t )

1 2 3

cB

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

44

x2

Constant source diffusion has Q

a solution of the form c( x, t ) e 4 Dt

Dt

Here, Q is the dose or the

total number of dopant

atoms diffused into the Si

Q c( x, t )dx

0

Q

The surface concentration is c(0, t )

given by: Dt

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

45

c01

c ( x, t )

Impurity concentration, c(x)

c02

1 2 3

cB

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

Ficks Second Law: The Diffusion 46

Equation

Consider a small region of space (volume

for 3D, area for 2D)

molecules flow out (per unit area or distance

per unit time).

N

J x x J x x dx dy

t

N

c J x x J x x dx

sincec N / dxdy

t dx

J

J x x J x x dx x definition of the derivative

x

c 2 c c

D 2 sinceJ x D

t x x

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

47

dc d 2c

Flux in 1 dimension: D 2

dt dx

dc d 2c d 2c

Flux in 2 dimensions: D 2 2

dt dx dy

dc d 2

c d 2

c

F

number of particles produced

F D 2 2

volumetime dt dx dy

dp d p d p

2 2

For biological populations: F ( p) D 2 2

dt dx dy

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

48

from regions of high concentration of

mobile species to regions of low

concentration. It occurs at all temperatures,

but the diffusivity has an exponential

dependence on T.

Predeposition: doping often proceeds by

an initial predep step to introduce the

"Predep" Drive-in required dose of dopant into the substrate.

controlled dose constant dose

Silicon Drive-In: a subsequent drive-in anneal

then redistributes the dopant giving the

required xJ and surface concentration.

Advantages Room temperature mask No damage created by doping

Precise dose control Batch fabrication

1011 - 1016 atoms cm-2 doses

Accurate depth control

diffusion

Dislocations caused by damage Low surface concentration hard

may cause junction leakage to achieve without a long drive-

in

Implant channeling may affect Low dose predeps very difficult

profile

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

49

up to a maximum value before they

precipitate into another phase.

solubility that is different than the

solid solubility defined above.

One example - As4V - electrically

inactive complex.

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

50

Types of diffusion

Vacancy diffusion

Self diffusion, tracer diffusion - healing of defects, time-

dependent mechanical phenomena

Chemical diffusion - diffusion of one element through

another, solid state chemical reactions

Bulk diffusion

Diffusion in grain boundaries, lattice defects

Surface diffusion

random motion of atoms.

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

51

process, resulting in an exponential

temperature dependence:

D = D0 exp(-Q/kT)

to the crystal axes.

substitutional impurities and matrix atoms.

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

52

Phenomenological description

c

Continuity: jD 0

t

c

Combined: Dc

t

c To be solved for c(x,t) or c(r,t)

If D = const. D 2c

t

Typical 1/2

solution depends on x/(Dt) .

One can define a diffusion front that travels as x2 ~ 6Dt

If defined that way, about 99% of the diffusing element is still

behind the diffusion front.

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

53

Rough correlations

HD / Tm ~ 1.5*10-3 eV/K

HD / Lm ~ 15

available. Typically estimates of diffusion are quite

rough, there is a huge variation, high accuracy is not

needed. Also, defects and impurities influence diffusion

very much, it is difficult to control it.

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

54

Examples

Temperature is uniformly T = 912C, the alpha-gamma transition of iron.

Diffusion time t = 1 h =3600 s, distance x2 = 6Dt

D = 2.0 exp(-2.5/8.6*10-5*11850) = 4.4*10-11 cm2/s, x ~ 10 m

Self diffusion in gamma Fe: D0 = 0.4 cm2/s, HD = 2.8 eV

D = 4.6*10-13 cm2/s, x ~ 1 m

60Co in alpha Fe: D = 0.2 cm2/s, H = 2.4 eV

0 D

D = 1.2*10-11 cm2/s, x ~ 5 m

C in alpha Fe: D0 = 0.004 cm2/s, HD = 0.83 eV

D = 1.2*10-6 cm2/s, x ~ 1.6 mm

C in gamma Fe: D0 = 0.67 cm2/s, HD = 1.6 eV

D = 1.0*10-7 cm2/s, x ~ 0.5 mm

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

55

dislocation climb due to capturing vacancies

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

56

More open, diffusion can take place faster. In fact, dislocations provide

routes for fast diffusion also. Diffusion in grain boundaries makes

predicting the behavior of polycrystals difficult.

Activation energy is lowest for surface diffusion, larger for grain

boundary diffusion, and the highest for bulk diffusion. Therefore, bulk

diffusion dominates at high temperature (larger number of possible

sites) but grain boundary and surface diffusion takes over at lower

temperature.

Technological importance: Thin film deposition, weakening of grain

boundaries by impurities, shape changes of particles, etc.

Diffusion can be accelerated by introducing grain boundaries and other

lattice defects. This is an important benefit from MA (mechanical

alloying).

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

57

Interdiffusion

Interdiffusion: in alloys, atoms tend to migrate from regions

of large concentration.

Initially After some time

100%

0

Concentration Profiles

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

58

Self diffusion

C

A

D

B

with scanning tunneling microscopy

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

59

Vacancy diffusion or interstitial diffusion

applies to substitutional impurities

atoms exchange with vacancies

Concentration of Vacancies

rate depends on

at temp T

(1) number of vacancies

(2) activation energy to exchange. E

ni

ci e KBT

Vacancy

an activation energy

(eV/atom).

Interstitial

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

60

Substitution-diffusion

Vacancy Diffusion:

applies to substitutional impurities

atoms exchange with vacancies

rate depends on (1) number of vacancies;

(2) activation energy to exchange.

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

61

Interstitial diffusion

diffusion

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

62

Case Hardening:

-Diffuse carbon atoms into the

host iron atoms at the surface.

-Example of interstitial diffusion

is a case hardened gear.

-hard to deform: C atoms

"lock" planes from shearing.

-hard to crack: C atoms put

the surface in compression.

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

63

Processing using Diffusion

Doping Silicon with P for n-type semiconductors:

Process:

1. Deposit P rich

layers on surface.

silicon

2. Heat it.

3. Result: Doped

semiconductor

regions.

silicon

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

64

Flux:

1 d

Qm

A dt

- vacancies

- host (A) atoms

- impurity (B) atoms

A = Area of flow

Empirically determined:

Make thin membrane of known surface area

Impose concentration gradient

Measure how fast atoms or molecules diffuse

through the membrane

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

65

Steady-state Diffusion

Concentration Profile, C(x): [kg/m3]

Cu flux Ni flux

Concentration Concentration

of Cu [kg/m3] of Ni [kg/m3]

Position, x

Fick's First Law:

dC

Qm,x D

dx D = m2/s

D=diffusion coefficient

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

66

Steady-State Diffusion

Steady State: concentration profile not changing with time.

C(x)

dC

Apply Fick's First Law: Qm,x D

dx

dx left dx right

The slope, dC/dx, must be constant (i.e., doesn't vary with position)

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

67

Steady-State Diffusion

dC

Qm,x D

Rate of diffusion independent of time dx

C1 C1

dC C C2 C1

C2 if linear

C2 dx x x2 x1

x1 x2

x

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

68

Example: C Diffusion in steel plate

Steel plate at 7000C with

geometry shown:

700 C

Knowns:

C1= 1.2 kg/m3 at 5mm

(5 x 103 m) below surface.

(1 x 102 m) below surface.

In steady-state, how much carbon transfers from the rich to the deficient

side?

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

69

Example: Chemical Protection Clothing

Methylene chloride is a common ingredient of paint removers. Besides

being an irritant, it also may be absorbed through skin. When using,

protective gloves should be worn.

If butyl rubber gloves (0.04 cm thick) are used, what is the diffusive flux of

methylene chloride through the glove?

glove

paint C1

2

tb

6D

C2 skin

remover x1 x2

Data:

D in butyl rubber: D = 110 x10-8 cm2/s

surface concentrations: C1 = 0.44 g/cm3 C2 = 0.02 g/cm3

Diffusion distance: x2 x1 = 0.04 cm

C2 - C1 g

Jx = -D = 1.16 x 10-5

x 2 - x1 cm2 s

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

70

Example: Diffusion of radioactive atoms

0

Surface of Ni plate

63 at 1000 C contains

50% Ni (radioactive)

63 and 50% Ni (non-radioactive).

4 microns below surface Ni /Ni = 48:52

Lattice constant of Ni at 1000 C is 0.360 nm. -9 2

Experiment shows that self-diffusion of Ni is 1.6 x 10 cm /sec

63

What is the flux of Ni atoms through a plane 2 m below surface?

C1 C2

(0.36x 109 m )3 / cell (0.36x 109m )3 / cell

42.87x 1027 Ni 63 / m 3 41.15x 1027 Ni 63 / m 3

(1.6x 10 m /sec)

6 (4 0)x 10 m

0.69x 1020 Ni 63 / m 2 s

How many Ni

63

atoms/second through cell? J (0.36nm )2 9 Ni 63 / s

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

71

Non-Steady-State Diffusion

Concentration profile,

C(x), changes w/ time.

Governing Eqn.:

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

72

Non-Steady-State Diffusion: another look

Concentration profile,

C(x), changes w/ time.

C C J x J x

dx J x J xdx dx J x (J x dx) dx

t t x x

D

t x x x 2nd Law

2

c c c

If D is constant: Fick's Second "Law" D D

2

t x x

x

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

73

Non-Steady-State Diffusion: C = c(x,t)

concentration of diffusing species is a function of both time and position

2

c

Fick's Second "Law" c D

2

t

x

Cs

B.C. at t = 0, C = Co for 0 x

at t > 0, C = CS for x = 0 (fixed surface conc.)

C = Co for x =

Callister & Rethwisch 3e.

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

74

Non-Steady-State Diffusion

Cu diffuses into a bar of Al. CS

C(x,t)

2

c c

Fick's Second "Law": D

2 Co

t

x

Solution:

2 z

erf (z)

0

e y 2

dy

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

75

Example: Non-Steady-State Diffusion

FCC iron-carbon alloy initially containing 0.20 wt% C is carburized at an elevated

temperature and in an atmosphere that gives a surface C content at 1.0 wt%.

If after 49.5 h the concentration of carbon is 0.35 wt% at a position 4.0 mm below

the surface, what temperature was treatment done?

Solution

C( x, t ) Co 0.35 0.20 x

1 erf 1 erf ( z ) erf(z) = 0.8125

Cs Co 1.0 0.20 2 Dt

Using Table 6.1 find z where erf(z) = 0.8125. Use interpolation. z erf(z)

0.90 0.7970

z 0.90 0.8125 0.7970 z 0.8125

So, z = 0.93

0.95 0.90 0.8209 0.7970 0.95 0.8209

x x2

Now solve for D z D

2 Dt 4z 2t

x2 (4 x 103 m)2 1h 11

D 2 2.6 x 10 m2

/s

4z t (4)(0.93) (49.5 h) 3600 s

2

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

76

Solution (cont.):

To solve for the temperature at which D Qd

has the above value, we use a T

rearranged form of Equation (6.9a); R(ln Do ln D)

D=D0 exp(-Qd/RT)

148,000 J/mol

T

(8.314 J/mol-K)(ln 2.3x105 m2 /s ln 2.6x1011 m2 /s)

T = 1300 K = 1027C

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

Example: Processing 77

10 hours processed at 600 C gives desired C(x).

How many hours needed to get the same C(x) at 500 C?

Key point 2: Both cases have the same Co and Cs.

C( x, t ) Co x

1 erf

Cs Co 2 Dt

Note

D(T) are T dependent!

Values of D are provided.

Answer:

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

78

conc.).

EACT

D Do exp

R T

Do = pre-exponential [m2/s]

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

79

Experimental Data:

1000

1500

600

300

T(C)

10-8

D (m2/s)

Dinterstitial >> Dsubstitutional

C in -Fe Cu in Cu

10-14 C in -Fe Al in Al

Fe in -Fe

Fe in -Fe

Zn in Cu

10-20

0.5 1.0 1.5 1000K/T

from E.A. Brandes and G.B. Brook (Ed.) Smithells Metals Reference Book, 7th ed.,

Butterworth-Heinemann, Oxford, 1992.)

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

80

Is C in fcc Fe diffusing faster than C in bcc Fe?

1000

1500

600

300

T(C)

fcc-Fe: D0=2.3x105 (m2/s) 10-8

EACT=1.53 eV/atom

T = 900 C D=5.9x1012(m2/s) D (m2/s)

EACT=0.83 eV/atom

T = 900 C D=1.7x1010(m2/s)

10-20

0.5 1.0 1.5 1000 K/T

FCC Fe has both higher activation energy EACT and D0 (holes larger in FCC).

BCC and FCC phase exist over limited range of T (at varying %C).

Hence, at same T, BCC diffuses faster due to lower EACT.

Cannot always have the phase that you want at the %C and T you want!

which is why this is all important.

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

81

regions is shifting, often difficult to define.

at interfaces via diffusion. The products form

intermediate layers that often act as diffusion barriers.

Decreasing the particle size - e.g. by ball milling -

accelerates the reactions.

etc.

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

82

system. As a result, the Cu - brass

interface shifts, the Mo wires

marking the interface drift toward

each other.

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

83

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

84

w = frequency of a jump to an adjacent site

l = distance of the jump

f = related to symmetry, coordination number

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

85

Diffusion coefficient: multicomponent

1979) for ideal system, elements with the

same charge and exchanging in the same

site

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

86

Diffusion coefficient

determine D* or DFeMg

volume, P = pressure in Pascals, R is the gas constant,

and Do = pre-exponential factor.

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

87

Diffusion coefficient

D at the conditions (P, T, fO2, ai) relevant for the magmatic

processes without need to extrapolation

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

88

Continuum Concept

number of blue circles moving right.

We think of concentration as being a point value, but it is

averaged over space.

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

89

Diffusion Coefficient

Probability of a jump is

Pj Pv Pm e E f kT

e Em kT

jump probability

E D kT

D D0e

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

90

Diffusion Coefficient

Typical diffusion coefficients in silicon

B 10.5 3.69

Al 8.00 3.47

Ga 3.60 3.51

In 16.5 3.90

P 10.5 3.69

As 0.32 3.56

Sb 5.60 3.95

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

91

Arrhenius plots of diffusion in silicon

o

Temperature ( C) o

Temperature ( C)

-9 1400 1300 1200 1100 1000

10 -4 1200 1100 1000 900 800 700

10

-10

10

-5

10

-11

10

Diffusion coefficient, D (cm /sec)

Li

-6

2

10

2

Fe

Cu

-12

10

-7

10

Al

Au

-13 Ga

10

In

-8

B,P 10

Sb 0.6 0.7 0.8 0.9 1.0 1.1

As -1

-14 Temperature, 1000/T (K )

10

-1

Temperature, 1000/T (K )

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

92

1018/cm3 at 1000 oC

If NA and ND are <ni, the material will behave as if

it were intrinsic; there are many practical

situations where this is a good assumption

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

93

slow diffusers (As, Sb)

As we develop shallow junction devices, slow

diffusers are becoming very important

B is the only p-type dopant that has a high

solubility; therefore, it is very hard to make

shallow p-type junctions with this fast diffuser

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

94

Successive Diffusions

and p-type dopants

Impurities will move as succeeding dopant or

oxidation steps are performed

The effective Dt product is

( Dt ) eff D1 (t1 t 2 ) D1t1 D1t 2

No difference between diffusion in one step or in

several steps at the same temperature

If diffusions are done at different temperatures

( Dt ) eff D1t1 D2t2

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

95

Successive Diffusions

The effective Dt product is given by

Dt eff Di ti

i

Di and ti are the diffusion coefficient and time for ith step

Assuming that the diffusion constant is only a

function of temperature.

The same type of diffusion is conducted (constant or

limited source)

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

96

Interstitial diffusion

Li diffusion in transition metal oxide host

O diffusion on Pt-(111) surface

which is externally imposed by a host or substrate

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

97

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

98

Intercalation Oxide as Cathode in

Rechargeable Lithium Battery

LixCoO2

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

99

E B

E B

* exp

kT

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

100

Lithium

Cobalt

Oxygen

mechanism Mechanism

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

101

Lithium

Cobalt

Oxygen

Single vacancy hop Divacancy hop

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

102

Irreversible thermodynamics:

interstitial diffusion of one

component

J L

d

DL

dC

J DC

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

103

Notation

N = number of diffusing atoms

vs = volume per lattice site

x = N/M

C=x/vs

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

104

Kubo-Green relations

(linear response statistical mechanics)

D L

Thermodynamic factor

C

N 2

Kinetic coefficient L

1 R t

(2d)tMvsk T i

i1

A. Van der Ven, G. Ceder,

Handbook of Materials Modeling, chapt. 1.17, Ed.

S. Yip, Springer (2005).

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

~ 105

D DJ

Diffusion coefficient Thermodynamic

at 300 K factor

A. Van der Ven, G. Ceder, M. Asta, P.D. Tepesch, Phys Rev. B 64 (2001) 064112

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

106

Interstitial diffusion

(two components)

Li & Na diffusion in transition metal oxide

host

O & S diffusion on Pt-(111) surface

In all examples, diffusion occurs on a rigid lattice

which is externally imposed by a host or substrate

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

107

Diffusion in an alloy: substitutional diffusion

Instead, diffusing atoms form the lattice

Dilute concentration of vacancies

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law

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