2023.10.
11
1
MS 211
Introduction to Materials Science and Engineering
Diffusion
(In class lecture 7)
Dong-Hwa Seo
Department of Materials Science and Engineering
Korea Advanced Institute of Science and Technology (KAIST)
Notice 2
Midterm exam
Time: 10/18 Wed 13:00~15:45
Place: (E11)Creative Learning Bldg. [ (E11)창의학습관 ] (401)
Homework 2
Due: October 15th (Sunday) before 24:00
Quiz3 results 3
Counts
Score
Diffusion 4
Heating the wafer at a high temperature in an atmosphere containing dopant atoms causes some of the atoms to be
incorporated into the top surface of the wafer.
[Link]
Arrhenius Equation
5
The process rate rises exponentially with temperature, and is described by Arrhenius Equation.
𝑟𝑎𝑡𝑒 = 𝐶𝑒 −𝑄/𝑅𝑇
Process rate examples: diffusion of atoms, chemical reactions,
mechanical deformation.
C: pre-exponential constant independent of temperature
Q: activation energy per mole
R: Universal gas constant
T: absolute temperature in Kelvins
𝑄1
ln 𝑟𝑎𝑡𝑒 = − + 𝑙𝑛𝐶
𝑅𝑇
y y-intercept
slope x
Arrhenius equation 6
The process rate rises exponentially with temperature, and is described by Arrhenius Equation.
[Link]
[Link]?simulation=reactions-and-rates
Diffusion of Particles
7
• Diffusion is due to random motion of particles.
• This causes net movement of particles from high to low concentration.
Diffusion of Particles
8
• Diffusion is due to random motion of particles.
• This causes net movement of particles from high to low concentration.
Random Walk
9
Diffusion of Particles 10
[Link]
First and Second Fick’s Law
11
2
′
𝜕𝑐 ′
𝜕𝑐 𝜕 𝑐
1𝑠𝑡 𝐹𝑖𝑐𝑘 𝑠 𝑙𝑎𝑤: 𝐽𝑥 = −𝐷 2𝑛𝑑 𝐹𝑖𝑐𝑘 𝑠 𝑙𝑎𝑤: = 𝐷 2
𝜕𝑥 𝜕𝑡 𝜕𝑥
Fick’s First Law
12
Fick’s First Law Concentration Gradient: cm-4
𝜕𝑐
𝐽𝑥 = −𝐷 Described the flux of atoms in the presence of concentration gradient
𝜕𝑥
Diffusion Coefficient: cm2/s
Flux of atoms moving in the x-direction
(number of particles per unit area per unit
time: cm-2s-1)
First and Second Fick’s Law
13
Atoms move with equal probability
to the right or left.
16 8 4 2 concentration
4 4 1 1 to
8 8 2 2
𝑑𝑥 𝑑𝑥 positive x
J=4 J=2 J = 1 Net movement of atoms/area*time
𝑑𝑐Τ = -8/dx -4/dx -2/dx
𝑑𝑥
1𝑠𝑡 𝐿𝑎𝑤: 𝐽 ∝ − 𝑑𝑐ൗ𝑑𝑥
𝜕𝑐
1𝑠𝑡 𝐿𝑎𝑤: 𝐽 = −𝐷
𝜕𝑥
First and Second Fick’s Law (Intuitive Description)
14
Atoms move with equal probability
to the right or left.
16 8 4 2 concentration 8 4 Concentration (t0)
4 4 1 1 to to+dt
4 2 1
8 8 2 2
𝑑𝑥 𝑑𝑥 positive x
4-2=2 2-1=1
10 5 Concentration (t0+dt)
J=4 J=2 J = 1 Net movement of atoms/area*time
1𝑠𝑡 𝐿𝑎𝑤: 𝐽 ∝ − 𝑑𝑐ൗ𝑑𝑥
𝜕𝑐
1𝑠𝑡 𝐿𝑎𝑤: 𝐽 = −𝐷
𝜕𝑥
First and Second Fick’s Law (Intuitive Description)
15
Atoms move with equal probability 𝑑𝐽ൗ
to the right or left. 2-4=-2 1-2=-1 𝑑𝑥
16 8 4 2 concentration 10 5 concentration
4 4 𝑑𝑥 𝑑𝑥
1 1 to to+dt
4 2 1
8 8 2 2
Fick's
𝑑𝑥
second 𝑑𝑥
law describespositive x how concentration gradients evolve positive x
over time due to the process of diffusion. The greater the
curvature (second derivative) of the concentration profile, the 𝑑𝑐ൗ
10-8=2 5-4=1 𝑑𝑡
faster the change in concentration over time.
J = 4 J = 2 J = 1 Net movement of atoms/area*time
1𝑠𝑡 𝐿𝑎𝑤: 𝐽 ∝ − 𝑑𝑐ൗ𝑑𝑥 2𝑛𝑑 𝐿𝑎𝑤: 𝑑𝑐ൗ𝑑𝑡 = − 𝑑𝐽ൗ𝑑𝑥
𝜕𝑐 𝜕𝑐 𝜕2𝑐
1𝑠𝑡 𝐿𝑎𝑤: 𝐽 = −𝐷 2𝑛𝑑 𝐿𝑎𝑤: = 𝐷 2
𝜕𝑥 𝜕𝑡 𝜕𝑥
Hands-on-session: Diffusion in solids 16
The mole percentage of a solute in a semi-infinite solid block is calculated as a function of distance from the surface.
[Link]
Practice: Fick’s law
17
𝑐𝑥 −𝑐0 𝑥
The diffusion result described by = 1 − erf( ) equation can apply to the carburization process. The
𝑐𝑠 −𝑐0 2 𝐷𝑡
carbon environment (a hydrocarbon gas) is used to set the surface-carbon content(𝑐𝑠 ) at 1.0 wt %. The initial
carbon content of the steel(𝑐0 ) is 0.2 wt %. Using error function table, calculate how long it would take at 1,000⁰C
to reach a carbon content of 0.6 wt % [i.e., (𝑐 − 𝑐0 )/ 𝑐𝑠 − 𝑐0 = 0.5] at a distance of 1mm from the surface.
(D in iron at 1000 C = 2.98 x 10 -11 m2/s)
erf(z)
1
0.8
erf(z)
0.6
0.4
0.2
0
0 0.5 1 1.5 2
z
Practice: Fick’s law
18
𝑐𝑥 −𝑐0 𝑥
The diffusion result described by = 1 − erf( ) equation can apply to the carburization process. The
𝑐𝑠 −𝑐0 2 𝐷𝑡
carbon environment (a hydrocarbon gas) is used to set the surface-carbon content(𝑐𝑠 ) at 1.0 wt %. The initial
carbon content of the steel(𝑐0 ) is 0.2 wt %. Using error function table, calculate how long it would take at 1,000⁰C
to reach a carbon content of 0.6 wt % [i.e., (𝑐 − 𝑐0 )/ 𝑐𝑠 − 𝑐0 = 0.5] at a distance of 1mm from the surface.
(D in iron at 1000 C = 2.98 x 10 -11 m2/s)
erf(z)
0.5205
0.5
0.4755
0.45 ? 0.5 z
𝑐 𝑥,𝑡 −𝑐𝑜 𝑥
𝑐𝑠 −𝑐𝑜
= 1 − erf 2 𝐷𝑡
High Li-diffusivity for fast (dis)charging 19
In electric vehicle, high Li-diffusivity is required for fast (dis)charging.
Measurement of Li-diffusivity 20
Adv. Energy Mater.2021, 11, 2100204
- Using the electrochemical technique, such as the galvanostatic intermittent
titration technique (GITT), Li-diffusivity can be measured during (dis)charging.
- If you want to learn about the details of the technique >> J. Electrochem. Soc.
160, A1842–A1846 (2013)
Dbulk VS Dgrain boundary 21
- Dbulk < Dgrain boundary. Is it true for all systems?
Dbulk VS Dgrain boundary 22
[Link].2018, 140, 362−368
- Previously, researchers compared Li-diffusivity in bulk and grain boundary of
polycrystalline solid electrolyte Li3OCl using computational method.
Dbulk VS Dgrain boundary 23
[Link].2018, 140, 362−368
- It is revealed that GB has larger Ea than bulk in representative systems.
Dbulk VS Dgrain boundary 24
𝐸𝑎 𝐺𝐵 > 𝐸𝑎 𝐵𝑢𝑙𝑘 𝐸𝑎 𝐺𝐵 <≈ 𝐸𝑎 𝐵𝑢𝑙𝑘
[Link].2018, 140, 362−368
25
Summary
(ch.2~ch.5)
Bonding
26
Ionic bonding is a result of coulombic attraction between oppositely charged ions.
F = Fc+FR (Fc is positive and FR is negative)
Covalent bonding shares valence electrons between two adjacent atoms.
7 crystal systems 27
14 Bravais lattices 28
Motif + lattice = crystal structure 29
Lattice positions 30
Lattice directions 31
Angle between two directions in cubic system 32
Lattice planes 33
1. Choosing the origin
2. Identifying intercepts
3. Reciprocal intercepts
4. Simplify to smallest integers
5. Using (hkl) notation
Planar density(FCC) 34
4
2 𝑎𝑡𝑜𝑚𝑠 2𝑎𝑡𝑜𝑚𝑠 2 𝑎𝑡𝑜𝑚𝑠 𝑎𝑡𝑜𝑚𝑠
= 2𝑎𝑡𝑜𝑚𝑠 3
𝑎2 2𝑎2 𝑎2 =
3 2 𝑎2
2 𝑎
Planar density(BCC) 35
𝑎 2𝑎
2𝑎 2𝑎
𝑎 𝑎 3
𝑎
2
2𝑎
1
1 𝑎𝑡𝑜𝑚𝑠 2𝑎𝑡𝑜𝑚𝑠 2 𝑎𝑡𝑜𝑚𝑠 𝑎𝑡𝑜𝑚𝑠
1𝑎𝑡𝑜𝑚𝑠 3
= =
𝑎2 2𝑎2 𝑎2 3 2 𝑎2
2 𝑎
Atomic packing factor 36
In crystallography, atomic packing factor (APF), packing efficiency, or packing fraction is the fraction of volume in a crystal
structure that is occupied by constituent particles.
APF: 0.68 APF: 0.74 APF: 0.74
X-ray Diffraction (Bragg’s Law)
37
Incident X-ray Scattered X−ray
• The X-rays can be thought of
diffracting off of crystallographic
planes. Constructive Interference Destructive Interference
• When x-rays constructive interfere,
diffraction peak appears.
X-ray Diffraction (Bragg’s Law)
38
Incident X-ray Scattered X−ray 2𝜋
𝑆𝑖𝑛 (𝑥 + 𝑛𝜆)
𝜆
• If 𝜙 = 𝑛𝜆, where n is an integer, then the two
waves will always constructively interfere.
• Notice from the schematic, if
𝟐𝒅𝑺𝒊𝒏𝜽 = 𝒏𝝀
𝑭𝑮 the waves will constructively interfere. This is
𝑺𝒊𝒏𝜽 =
𝒅 known as Bragg’s Law.
2𝜋 2𝜋
𝑆𝑖𝑛 𝑥 , 𝑆𝑖𝑛 (𝑥 + 𝜙)
𝜆 𝜆
Distance between the Planes using Miller indices and condition for diffraction
39
𝒂
𝒅𝒉𝒌𝒍 =
𝒉𝟐 + 𝒌𝟐 + 𝒍𝟐
• This equation is only true for cubic system.
𝑎
2𝑑ℎ𝑘𝑙 𝑠𝑖𝑛𝜃 = 𝜆 𝑑ℎ𝑘𝑙 =
ℎ1 2 + 𝑘1 2 + 𝑙1 2
2𝑎𝑆𝑖𝑛𝜃 2
( ) = ℎ2 + 𝑘 2 + 𝑙2
𝜆
This should be an integer
X-ray Diffraction
40
h k l (𝒉𝒌𝒍) ℎ2 + 𝑘 2 + 𝑙 2 Simple Cubic BCC FCC
1 0 0 (100) 1 1
1 1 0 (110) 2 2 2
1 1 1 (111) 3 3 3
2 0 0 (200) 4 4 4 4
2 1 0 (210) 5 5
2 1 1 (211) 6 6 6
2 2 0 (220) 8 8 8 8
3 0 0 (300) or (221) 9 9
3 1 0 (310) 10 10 10
3 1 1 (311) 11 11 11
2 2 2 (222) 12 12 12 12
3 2 0 (320) 13 13
3 2 1 (321) 14 14 14
4 0 0 (400) 16 16 16 16
Chemical imperfection(solid solution): Hume-Rothery rule
41
For complete miscibility to occur in metallic solid solution, the two metals must be quite similar,
defined by Hume-Rothery rule.
i) less than about 15% difference in atomic radii: (Rlarge-Rsmall)/Rsmall
ii) the same crystal structure (e.g. FCC, BCC, HCP etc)
iii) similar electronegativities
iv) the same valence (e.g. +1, +2, -1, -2)
If one or more of the Hume-Rothery rule are violated, only partial solubility is possible.
Defect
42
Point defect(0D)
Linear defect(1D)
Edge dislocations Screw dislocations
Defect
43
Defect
Plane defects(2D)
grain boundaries Stacking faults Twin boundaries
Fick’s law
44
Concentration Gradient: cm-4
Fick’s First Law
𝜕𝑐
𝐽𝑥 = −𝐷 Described the flux of atoms in the presence of concentration gradient
𝜕𝑥
Diffusion Coefficient: cm2/s
Flux of atoms moving in the x-direction
(number of particles per unit area per unit
time: cm-2s-1)
Fick’s Second Law
𝜕𝑐 𝜕 2𝑐
=𝐷 2
𝜕𝑡 𝜕𝑥
The concentration gradient or the flux can change with time and position. This transient nature is expressed by
Fick’s second law.
Arrhenius equation
45
The process rate rises exponentially with temperature, and is described by Arrhenius Equation.
𝑟𝑎𝑡𝑒 = 𝐶𝑒 −𝑄/𝑅𝑇
C: pre-exponential constant independent of temperature
Q: activation energy per mole
R: Universal gas constant
T: absolute temperature in Kelvins
𝑄1
ln 𝑟𝑎𝑡𝑒 = − + 𝑙𝑛𝐶
𝑅𝑇
y slope x y-intercept
46
Thank you