MKM6144

ADVANCED MATERIAL
FACULTY OF MECHANICAL ENGINEERING
UNIVERSITI MALAYSIA PAHANG

Introduction
Subject
Course Code
Credits
Semester
Team Teaching

: ADVANCED MATERIAL
: MKM6144
: 4 Credits
: 2 2015/2016
: Dr. YULI PANCA ASMARA
Dr. TEDI KURNIAWAN
Dr. DANDI BACHTIAR
Dr. JANUAR PARLAUNGAN SIREGAR

High - Temperature
Metal Gas Reactions

 Corrosion of Metals and Alloys

Review of thermodynamic principles
Review of diffusion principles: point defects in
metals and oxides
Principles of oxidation and corrosion
Parabolic and transition from parabolic
External vs. internal oxidation (Selective
oxidation)
Oxide adherence
Environmental influences in real systems
(Evaporation,H2O content, dual atmosphere,
pressure, breakaway
corrosion, corrosion in multi component
gases)

Scaling, Dry Corrosion

At temp. increase Metal
oxidation increase gas turbines,
rocket engines, furnaces and hightemp. petrochemical process.

Mechanisms and
Kinetics
Pilling-Bedworth Ratio
Oxidation resistance should be
related to the volumn ratio of
oxide and metal

R = Wd / Dw
W

molecular wt. of the

oxide
w

= atomic wt. of the metal

D,d = the specific densities of

the oxide and metal

 Volumn ratio < 1 insufficient

oxide to cover the metal and is
unprotective.
Volumn ratio >1 large
compressive stresses poor
oxidation resistance cracking
and spalling.
The ideal ratio = close to 1
This ratio does not accurately
predict oxidation resistance .

To be protective an oxide must

posses a coefficient of expansion
nearly equal to that of the metal
substrate, good adherence, a high
melting pt.,
a low vapor
pressure, good high-temp. plasticity
to resist fracture, low electrical
conductivity or low diffusion coeff.

For metal ions or oxygen, and a

volume ratio close to 1 to avoid
compressive stresses or lack of
complete surface coverage. Thus,
oxidation resistance of a metal or
alloys depends on a numbers of
complex factors.

Electrochemical and Morphological

Aspects of Oxidation

Oxidation by gaseous oxygen is an

electrochemical process.
M
M+2 + 2e
(at the metal scale interface)
1/2O2 + 2e
O-2
(at the scale-gas interface)
M + 1/2O2
MO (Overall)

 Metal ions are formed at the metalscale interface and oxygen is reduce
to oxygen ions at the scale-gas
interface.

 Oxide layer serves simultaneously

as
1. an ionic conductor (electrolyte)
2. an electronic conductor.
3. an electrode at which oxygen is
reduced.
4. a diffusion barrier through
which ions and electrons must
migrate.

* The electronic conductivities of

oxides are usually one or more
orders of magnitude greater than
their ionic conductivities, so that
the movement of either cations or
oxygen ions controls the reaction
rate.

The oxidation rate is most effectively

retarded in practice by reducing
the flux of ions diffusing through
the scale.

 Many metal-oxygen phase

diagrams indicate several stable
binary oxides. For ex., iron may
from the compounds FeO, Fe3O4
and Fe2O3; copper may form Cu2O
and CuO; etc.
Fe above 5600C.
Fe/FeO/Fe3O4/Fe2O3/O2

The most oxygen-rich compound

at the scale-gas interface

is found

1. Scales formed on the common

base metals Fe, Ni, Cu, Co and
others grow principally at the scalegas interface by outward cation
diffusion.

However because of vacancy

condensation at the metal-scale
interface some of the oxide in the
middle of the scale dissociates
sending cations outward and oxygen
molecules inward through these
voids.

2. More tradition base metals as Ta,

Nb, Hf, Ti and Zr form oxides in
which oxygen-ion diffusion would
predominate over cation diffusion,
so that simple diffusion control
would result in scale formation at
the metal-scale interface

 the oxide formed at the

metal-scale interface (with a
large increase in volumn) is
porous on a microscopic
scales and is cracked on a
macroscopic scale
these scales are said to be
nonprotective.

 Morphological occurrences often

cause the oxidation mechanism to
deviate from the simple ideal
electrochemical model.

In addition, the significant dissolution

of oxygen atoms in some metals, the
high volatility of some oxides and
metals , the low melting points of some
oxides, and grain boundaries in the
scale and in the metal often complicate
the oxidation mechanisms of pure
metals.

Oxide Defect Structure

In general, all oxides are

nonstoichiometric compounds
Metal-excess oxide
ZnO
2 extra zinc ions
4 excess electron

Zinc oxide is termed an n-type semiconductor

since it contains an excess of negatively charged
electronic current carriers (electrons).

 Other n-type CdO, TiO2, Ta2O5,

Al2O3, SiO2, Cb2O5 and PbO2
Metal-difficient oxide
Electron hole (or
absence of an
electron)

Electronic conduction occurs by

the diffusion of these positively
charged electron holes this oxide
is termed a p-type semiconductor.
Ionic transport occurs by the
diffusion of the nickel vacancies.
Other oxides of this type are FeO,

Summarizing, the oxidation of

some metals is controlled by the
diffusion of ionic defects through the
scale. In principle, a diffusioncontrolled oxidation may be retarded
by decreasing the concentration of
ionic defects in the scale.

Oxidation Kinetics

Fig 11-6 Oxidation rate laws.

W = kL t
kL = linear rate const.
porous or cracked scale is formed
Na, K R

<

Ta, Cb R

2.5

W2 = kpt + C
Ideal ionic diffusion-controlled
oxidation of pure metals
paraboric oxidation rate law.
kp = parabolic rate const.
C = const.
Non-steady-state diffusioncontrolled reactions.
oxide layer thickness increase.

The ionic diffusion flux is inversely

proportional to the thickness of the
diffusion barrier, and the change in
scale thickness or weight is likewise
proportional to the ionic diffusion
flux.

W = ke log (Ct + A)
Where ke, C and A are const.
1/w = C ki log t
Where ki and C are const.
Logarithmic oxidation behavior is
generally observed with thin oxide
layers (e.g., less than 1000
angstroms) at low temp.

 Aluminum, Copper, Iron.

The exact mechanism is not
completely understood.
Under specific conditions.
W3 = kct

kc and C are const.

 Oxidation of Zirconium
combination of diffusion-limited
scale formation and oxygen
dissolution into the metal.
* linear oxidation rate is the least
desirable.
Aluminum oxidizes in air at

Effect of Alloying
The concentration of ionic defects
(interstitial cations and excess
electrons, or metal ion vacancies
and electron holes) may be
influenced by the presence of
foreign ions in the lattice (the

1. n-Type Oxides
(Metal Excess-eq. ZnO)

a) Introduction of lower vacancy

metallic ions into the lattice increase
the concentration of interstitial
metallic ions and decreases the
number of excess electrons. A
diffusion-controlled oxidation rate

1. n-Type Oxides
(Metal Excess-eq. ZnO)

b) Introduction of metallic ions

possessing higher valency decreases
the concentration of interstitial
metallic ions and increases the
number of excess electrons. A
diffusion-controlled oxidation rate

2) p-Type Oxides
(Metal Deficient-eg. NiO)

a) The incorporation of lower

vacancy cations decreases
theconcentration of cation vacancies
and increases the number of electron
holes. A diffusion controlled oxidation
rate would be decreased.

2) p-Type Oxides
(Metal Deficient-eg. NiO)

b) The addition of higher valency

cations increases vacancy
concentration and decreases
electron hole concentration. A
diffusion-controlled oxidation rate

Table 11-2 Oxidation of zinc and zinc alloys

3900C, 1 atm O2

Material

Parabolic oxidation
constant Kp, g2/cm2hr

Zn

8x10-10

Zn + 1.0 atomic %Al

1x10-11

Zn + 0.4 atomic %Li

2x10-7

Table 11-3 Oxidation of nickel and nickel alloys

Nickel and chromium-nikel alloys at 10000C in pure
oxygen

Wt. %Cr

Parabolic oxidation
constant Kp, g2/cm2hr

3.8x10-10

0.3

15x10-10

1.0

28x10-10

3.0

36x10-10

10.0

5.0x10-10

NiCr2O4

Table 11-3 Oxidation of nickel and nickel alloys

Effect of lithium oxide vapor on the oxidation of nickel
at 10000C in oxygen

Atmosphere

O2
O2

Parabolic oxidation
constant Kp, g2/cm2hr
2.5x10-10

Li2O

5.8x10-11

Catastrophic Oxidation
Metal-oxygen systems which react
at continuously increasing rates.
linear oxidation kinetics
rapid, exothermic reaction at their
surfaces.

If the rate of heat transfer to the

metal and surroundings is less than
the heat produced by the reaction,
surface temp. increases chainreaction characteristic-temp. and
reaction rate increases.

Ex. Columbium (Niobium), ignition

of the metal occurs. Mo, tungsten,
osmium and vanadium volatile
oxides may oxidize catastrophically.

The formation of low-melting

eutectic oxide mixtures produces a
liquid beneath the scale, which is
less protective. Catastrophic
oxidation can also occur if vanadium
oxide or lead oxide compounds are
present in the gas phase.

Internal Oxidation
In certain alloy systems, one or
more dilute components which
may form more stable oxides than
the base metal may oxidize
preferentially below the external
surface of the metal, or below the
metal scale interface.
Dilute copper-and silver-base
alloys containing Al. Zn, Cd, Be,

Other Metal-Gas
Reactions
Decarburization and Hydrogen
attack
At elevated temp. hydrogen can
influence the mechanical
properties of metal in a variety of
ways.

 reduction of tensile strength and

an increase in ductility and creep
rate
Reverse process, carburization, can
also occur in hydrogen-hydrocarbon
gas. (petroleum refining operations)
decreases its ductility and remove
certain solid-solution elements
through carbide precipitation.

Hydrogen and Hydrocarbon

Gases
C(Fe) + 2H2

CH4

The equilibrium between carbon

steel and hydrogen methane gas
mixtures can be obtained from
thermodynamic data.

Because atomic hydrogen diffused

readily in steel, cracking may result
from the formation of CH4 in internal
voids in the metal. Chromium and Mo
additions to a steel improves its
resistance to cracking and
decarburization in hydrogen
atmospheres.

Hydrogen and water

Vapor
C(Fe) + H O = H
+ CO
2

Carbides and carbon react with

water vapor to form hydrogen
carbonmonoxide.
Fe

H 2O

FeO

H2

Thus. In hydrogen-water vapor

environments both decarburization
and oxidation are possible.

Equilibriums in the Fe-O-H

system.

Fig. 11-14 Equilibrium diagram of the Fe-H2-H2O

Carbon Monoxide-Carbon Dioxide

Mixtures.

Fe

C(Fe)

CO2

CO2

2CO

FeO

CO

Hydrogen Sulfide and Sulfur-containing

Gases.

H2S - a frequent component of

hightemperature gases.
- act as an oxidizing agent in
the
formation of sulfide scales
on
metal substances at high
temp.

In general, nickel and rich alloys

are usually rapidly attacked in the
presence of hydrogen sulfide and
other sulfur-bearing gases. Attack is
frequently catastrophic with rapid
intergranular penetration by a liquid
sulfide product and subsequent

Iron-base alloys are often used to

contain hydrogen sulfide
environment because of their low
cost and good chemical resistance.

Diffusion in Solids
ISSUES TO ADDRESS...
How does diffusion occur?
Why is it an important part of processing?
How can the rate of diffusion be predicted for
some simple cases?
How does diffusion depend on structure
and temperature?
68

Diffusion
Diffusion -

Mass transport by atomic motion

Mechanisms
Gases & Liquids random (Brownian) motion
Solids vacancy diffusion or interstitial diffusion

69

Diffusion
Interdiffusion: In an alloy, atoms tend to migrate
from regions of high conc. to regions of low conc.
Initially

After some time

Adapted from
Figs. 5.1 and
5.2, Callister
7e.

70

Diffusion
Self-diffusion: In an elemental solid, atoms
also migrate.
Label some atoms

C
A
D
B

After some time

C
D

A
B

71

Diffusion Mechanisms
Vacancy Diffusion:
atoms exchange with vacancies
applies to substitutional impurities atoms
rate depends on:
--number of vacancies
--activation energy to exchange.

increasing elapsed time

72

Diffusion Simulation
Simulation of
interdiffusion
across an interface:
Rate of substitutional
diffusion depends on:
--vacancy concentration
--frequency of jumping.

(Courtesy P.M. Anderson)

73

Diffusion Mechanisms
Interstitial diffusion smaller atoms can
diffuse between atoms.

Adapted from Fig. 5.3 (b), Callister 7e.

More rapid than vacancy diffusion

74

Processing Using Diffusion

Case Hardening:

Adapted from
chapter-opening
photograph,
Chapter 5, Callister
7e. (Courtesy of
Surface Division,
Midland-Ross.)

--Diffuse carbon atoms

into the host iron atoms
at the surface.
--Example of interstitial
diffusion is a case
hardened gear.

Result: The presence of C

atoms makes iron (steel) harder.

75

Processing Using Diffusion

Doping silicon with phosphorus for n-type semiconductors:

0.5 mm
Process:
1. Deposit P rich
layers on surface.
magnified image of a computer chip

silicon
2. Heat it.
3. Result: Doped
semiconductor
regions.

silicon

light regions: Si atoms

light regions: Al atoms

Adapted from chapter-opening photograph,
Chapter 18, Callister 7e.
76

Diffusion

How do we quantify the amount or rate of diffusion?

moles (or mass) diffusing

mol
kg
J Flux

or
2
surface area time
cm s m2s

Measured empirically

Make thin film (membrane) of known surface area

Impose concentration gradient
Measure how fast atoms or molecules diffuse through the membrane

M
l dM

At A dt

M=
mass
diffused

J slope
time
77

Steady-State
Diffusion
Rate of diffusion independent of time
dC
dx

Flux proportional to concentration gradient =

C1 C1

Ficks first law of diffusion

C2
x1

C2

dC
J D
dx

x2

dC C C2 C1
if linear

dx
x
x2 x1

D diffusion coefficient

78

Example: Chemical Protective Clothing

(CPC)
Methylene chloride is a common ingredient of paint
removers. Besides being an irritant, it also may be
absorbed through skin. When using this paint
remover, 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?
Data:
diffusion coefficient in butyl rubber:
D = 110 x10-8 cm2/sC = 0.44 g/cm3
1
surface concentrations: C = 0.02 g/cm3
2

79

Example (cont).
Solution assuming linear conc. gradient
glove
C1

2
tb
6D

paint
remover

skin

Data:

C2
x1 x2

J (110 x 10

-8

dC
C2 C1
J -D
D
dx
x2 x1
D = 110 x 10-8 cm2/s
C1 = 0.44 g/cm3
C2 = 0.02 g/cm3
x2 x1 = 0.04 cm

(0.02 g/cm 3 0.44 g/cm 3 )

g
cm /s)
1.16 x 10-5
(0.04 cm)
cm2s
2

80

Diffusion and Temperature

Diffusion coefficient increases with increasing T.
Qd

D Do exp
RT
D

= diffusion coefficient [m2/s]

Do = pre-exponential [m2/s]
Qd = activation energy [J/mol or eV/atom]
R

= gas constant [8.314 J/mol-K]

= absolute temperature [K]

81

Diffusion and Temperature

300

600

1000

10-8

1500

D has exponential dependence on T

D (m2/s)
10

T(C)

D interstitial
C in -Fe
C in -Fe

-14

10-20

>> D substitutional

0.5

1.0

1.5

Al in Al
Fe in -Fe
Fe in -Fe

1000 K/T

Adapted from Fig. 5.7, Callister 7e. (Date for Fig. 5.7 taken from E.A.
Brandes and G.B. Brook (Ed.) Smithells Metals Reference Book, 7th ed.,
Butterworth-Heinemann, Oxford, 1992.)

82

Example: At 300C the diffusion coefficient and activation

energy for Cu in Si are
D(300C) = 7.8 x 10-11 m2/s
Qd = 41.5 kJ/mol
What is the diffusion coefficient at 350C?
transform
data

Temp = T

Qd
ln D2 ln D0
R

ln D

1/T

T2

and

D
Q
ln D2 ln D1 ln 2 d
D1
R

Qd
ln D1 ln D0
R
1
1

T2 T1
83

T1

Example (cont.)

Qd
D2 D1 exp
R

1
1

T2 T1

T1 = 273 + 300 = 573 K

T2 = 273 + 350 = 623 K
D2 (7.8 x 10

11

41,500 J/mol
1
1
m /s) exp

8.314 J/mol - K 623 K 573 K
2

D2 = 15.7 x 10-11 m2/s

84

Example: Chemical Protective Clothing

(CPC)

Methylene chloride is a common ingredient of paint removers.

Besides being an irritant, it also may be absorbed through skin.
When using this paint remover, protective gloves should be
worn.
If butyl rubber gloves (0.04 cm thick) are used, what is the
breakthrough time (tb), i.e., how long could the gloves be used
before methylene chloride reaches the hand?
Data (from Table 22.5)
diffusion coefficient in butyl rubber:
D = 110 x10-8 cm2/s

85

Example (cont).
Solution assuming linear conc. gradient
glove

2
tb
6D

C1
paint
remover

skin
C2

Equation 22.24

x 2 x1 0.04 cm

x1 x2

D = 110 x 10-8 cm2/s

tb

(0.04 cm) 2
( 6)(110 x 10

-8

cm /s)

240 s 4 min

Time required for breakthrough ca. 4 min

86

Non-steady State
Diffusion

The concentration of diffucing species is a function of both time and position C = C(x,t)
In this case Ficks Second Law is used

Ficks Second Law

C
2C
D 2
t
x

87

Non-steady State
Copper diffuses into a bar of aluminum.
Diffusion
Surface conc.,
C s of Cu atoms

bar
pre-existing conc., Co of copper atoms

Cs
Adapted from
Fig. 5.5, Callister
7e.

B.C.

at t = 0, C = Co for 0 x

at t > 0, C = CS for x = 0 (const. surf. conc.)

C = Co for x =
88

Solution:
C x , t Co
1 erf
Cs Co

C(x,t) = Conc. at point x at

time t
erf (z) = error function

y 2

dy

2 Dt

CS

C(x,t)
Co

erf(z) values are given in

Table 5.1
89

Summary
Diffusion FASTER for...

Diffusion SLOWER for...

open crystal structures

close-packed structures

materials w/secondary
bonding

materials w/covalent
bonding

smaller diffusing atoms

larger diffusing atoms

lower density materials

higher density materials

90

 Thanks