MET 311E

PHYSICAL METALLURGY COURSE

2010-11 FALL SEMESTER

LECTURE 6

“Interfaces”
Interfaces

November 05, 2010

Assist Prof
Assist. Prof. Dr
Dr. Burak ÖZKAL
• Virtually all of the metals with which one comes
into daily contact are polycrystalline.Metallurgists
polycrystalline Metallurgists
refer to the small crystalline regions as Grains,
and the average Grain size in most metal objects
ranges from 0 0.015
015 to 0
0.24
24 mm
mm.
• Grains are frequently not perfect single crystals
but are divided into smaller subgrains that are
nearlyl perfect
f t single
i l crystals.
t l
• The grain boundaries and subgrain boundaries are
interfaces between crystals of different
orientation.
• Since the physical properties of metals are
dependent on the physical properties of these
interfaces, the study of the nature of metal
interfaces is very important in physical
metallurgy.
t ll
 CLASSIFICATION, GEOMETRY, AND ENERGY OF INTERFACES
• In order to describe the ggeometryy of g
grain boundaries we begin
g by y
considering two dimensional lattices. Figure below shows two
lattices that are oriented at some angle to each other; that angle is
indicated as θ
• When these two lattices are brought together a grain boundary is
formed between them. There are two different ways in which the
boundary might form, depending on the angle between the boundary
and a plane in one of the lattices. To completely define the boundary
one must specify:
• 1. The orientation of one lattice with respect to the other, θ
• 2. The orientation of the boundary with respect to a lattice, Φ

• Since the boundary can be specified with two angles it could be

called a two-degree-of-freedom boundary.
 Contemporary Model based
Early Model by Beilby
on Experiments
Grain Boundary Models: a) a thin layer of atoms that has an amorphous structure and
acts almost as a liquid boundary layer separating the crystals. b) Recent experimental
studies indicate that grain boundaries are more closely represented by this model.Nearly
perfect crystals extend up to each other and touch at irregular points. The boundary
contains atoms that belong to both crystals, D, and atoms belonging to neither
crystal A; it contains compression zones
crystal, zones, B,
B and tensile zones,
zones C.C In general,
general the width
of the grain boundary is thought to be quite narrow, only a few angstroms.
• The ggeneral ggrain boundaryy has five degrees
g of freedom;
three degrees specify the orientation of one grain relative
to the other and two degrees specify the orientation of
the boundaryy relative to one of the g
grains.
• The interfaces that form in crystals because of
orientation mismatches between different regions of the
crystal are termed grain boundaries.
boundaries
• We are also interested in other interfaces that are not
grain boundaries such as free surfaces, stacking faults,
and antiphase domain boundaries
boundaries.
SMALL-ANGLE
SMALL ANGLE BOUNDARIES
• If the orientation mismatch
between two crystals is quite small
the boundary between the crystals
is called a small
small-angle
angle boundary
boundary.
Very simple small-angle
boundaries can be described by
dislocation arrangements.
• Tilt Boundary
y

Strain field along a tilt

boundary
• Twist Boundary

Small Angle Twist Boundary

Twist Boundary is the simplest screw dislocation grain boundary

whereas Tilt Boundary is the simplest edge dislocation grain boundary.
 Grain boundaries are often classified by a
scheme which is given roughly as follows:

• Small-angle
Small angle boundaries θ =0° - 3° to 10°
• Medium-angle boundaries θ =3° to 10° ---> 15°
• Large-angle boundaries θ =15° --->
 Grain Boundary Energy

Small Angle Grain Boundary

Energy Formula
It does not give the correct
values after 5
5-6
6 degrees
degrees...

- The energies of large-angle grain boundaries are approximately constant at

around 500-600 ergs/cm2.
- In polycrystalline metals over 90% of all the grain boundaries are high-angle
boundaries because the probability that all three orientation angles are low is very
small. Consequently, the grain boundary energy in polycrystalline metals may be
taken as constant at around 500-600 ergs/cm2.
 COHERENT BOUNDARIES
• This is the name for a special type of boundary having to do with the
degree of fit of the lattices across the boundary.

• There is a one-to-one
one to one matching of the lattice planes across the
boundary. This generally produces lattice strains around the
boundary where the lattice planes must be "bent" to give this one-to-
one matching.
• In an incoherent boundary there is no regularity of lattice-plane
lattice plane
matching across the boundary.
• High-angle boundaries are incoherent boundaries.
• We can also use the definitions of p
partially
y coherent or semicoherent
boundary terms.
 Partially Coherent Grain Boundary

A perfect lattice matching occurs every six spacings of the β lattice. Notice also
that every six spacings one obtains a β plane situated directly between the two lower α
planes.
planes
In real crystals the boundaries relax under the forces between atoms into the
dashed positions, and this leaves an edge dislocation at the point where the β plane is
located symmetrically between two α planes
 Twin Boundaries
• Twin
T i bboundaries
d i are perhaps h th
the simplest
i l t off allll grain
i bboundaries.
d i
One may classify twin boundaries as either coherent or partially
coherent. Notice that the twin boundaryis a symmetry plane, a mirror
plane Complete coherency at the boundary is obtained without any
plane.
straining of the lattices because a perfect registry of the lattices is
naturally obtained at these special boundaries. If the twin boundary
plane rotates off the symmetry plane as shown in obtains a partially
coherent twin boundary (usually called a non-coherent twin)

Coherent Twin
Boundary
Partially Coherent
Twin Boundary
 Energy of Interfaces
The interface energy is a
measure of the energy per
area of the interface region
minus the energy per area
of that region without an
interface; that is the energy
is defined relative to a
perfect lattice.

It is frequently useful to consider the interface energy to be partitioned into

two forms, strain energy and chemical energy. Figure shows a hypothetical
energy
e e gy versus-distance
e sus d s a ce cucurve
e for
o aan a
atom
o within a ccrystal
ys a lattice,
a ce, where
ee
positions S are the lattice sites. When an atom is displaced from its lattice site
by some force (stress), a strain energy is produced as shown as B. The
chemical energy is shown on Figure as A. This energy may be thought of as
arising from the unstrained chemical bonds
bonds, and its magnitude depends on
the number and strength of these bonds.
DIFFERENT WETTING STAGES SURFACE CHARACTERISTICS

θ*= r cosθ WENZEL

r: roughness

cosθ *= −11 +φ (cosθ + 1) CASSIE,

CASSIE
BAXTER
φ: contact parts
[Wettability at high Temperatures,
N. Eustathopoulos, M.G. Nicholas, B. Drevet, Pergamon 1999] [J. Bico, C. Marzolin, D. Quere, Europhys. Lett, 47 (2), (1999)]
R
Rough
h surfaces
f
Wenzel: Liquid
completely fills the
grooves off the
th solid
lid

Cassie and Baxter:

Liquid “sits” on the
surface roughness
 (a) (b)

SEM images of carbon nanotube forests (a) As-grown forest prepared by PECVD
with nanotube diameter of 50 nm and a height of 2 ím
ím, (b) PTFE
PTFE-coated
coated forest after
HFCVD treatment.
SEM images of an essentially spherical water droplet
suspended on the PTFE-coated forest.
Boundary
B d Mi
Migration
ti During
D i growth th off bubbles.
b bbl B
Bubbles
bbl presentt an
excellent model for grain boundaries.
For aliquid drop on a solid surface tension balance

No wetting condition

Complete wetting
 Applications
• There are a number of cases where the
above ideas have direct practical
significance and three of them will be
discussed here.
1. Sintering There are many applications
in sintering. As an example consider
carbide tool bits.
bits In this case a
powdered carbide such as tungsten
carbide, WC, is bonded together with a
metal such as Co. To produce good
bonding one wants the bonding metal
to wet the carbides and microstructures
such as seen in Figureare desired.
Hence, one must be able to produce a
very low dihedral angle between the
carbide and the bonding metal.
• 2. Hot shortness in steel. Sulfur combines with Fe to
form FeS, which melts at 988°C. When the steel is hot
rolled this compound melts. Since it has a low value of δ
in steel it wets the grain boundaries and the steel
becomes brittle causing the failure known as hot
shortness.
• It takes only a very small quantity of liquid to cover the
grain boundaries and, consequently, only a small
amount of sulfur impurity is required to cause this
difficulty Hot shortness is overcome by the addition of
difficulty.
Mn to steel which causes MnS to form preferentially, and
this compound melts at 1610°C.
• 3. Soldering.
g A successful solder must wet the
surface of the metals to be-soldered. Hence, the
dihedral angle of a drop of liquid solder on the
metal must approach zero
zero. As pointed out
above this condition requires the surface
tensions to satisfyy

• Consequently we require a low value for the

surface tension between the liquid solder and
the base metal. A successful flux will promote
this condition
condition.
 HIGH TEMPERATURE WETTABILITY

LOTUS - Effect

High temperature – LOTUS - Effect

 The Lotus-effect :
Superhydrophobicity

ƒ Microstructural
epidermal cells

N t t l
ƒNanostructural
wax-crystals
20 µm

W. Barthlott, C.
Neinhuis; 1997
 The Lotus-effect :
Self-cleaning

1 µm 50 µm

Both contamination and water have a

small contact area with the leaves
The Lotus-effect
Self-cleaning

Water rolls off the

g the
surface taking
contamination along
 Shape of Grains
• There are two known restrictions that limits the shapes of
grains
• ((1)) Grains must fill space,
p , that is there can be no voids ((2))
thermodynamic potential γA must be a minimum.
• “Grains with just a few sides (small grains) will have curved
b
boundaries
d i and d th
the curvature
t will
ill b
be concave iinward;
d andd
grains with many sides (large grains) will have boundaries
curved concave outward”

Relation of grain boundary curvature and number of grain sides

 Grain Boundary Segregation

Cu -1 % Sn Two single crystal “bicrystal”,

If you measure the composition across the grain boundary

with a very fine probe, it is possible to observe Sn atoms
segregated into the grain boundary. This phenomenon is
called “grain-boundary
grain boundary segregation”,
segregation , and usually results in an
excess solute concentration. But sometimes a solute
depletion at the boundary may occur.
To understand why grain boundary segregation
occurs
occu s we e co
consider
s de tthe
eeeffect
ect o
of tthe
eSSn ato
atom in tthe
e
Cu lattice when it dissolves.

The larger Sn atoms bend the Cu lattice planes

and these atoms produce a considerable strain
energy to its surroundings. Since the grain
boundary will have regions that are quite open we
expect the Sn to locate there and to produce a
very low strain energy.
 Motion of Grain Boundaries

• Driving Forces
• 1. Stored Energy
• 2. Elastic Strain
• 3. Interface Curvature
 Grain Boundary Mobility
• 1.
1 Impurity Atoms
• 2. Presence of Second Phase Particles
• 3.Temperature
• 4. Orientation of Grains across
Boundary
 Grain Growth

Tungsten filament example

How we avoid from grain growth ?

Please read following topics through p. 198 - 212 (Verhoven)
 Next week, no lecture....we are visiting
1 h IInternational
15th i lMMetallurgy
ll &M
Materials
i l
Congress

Interesting Invited Talks Related to

Physical Metallurgy
1)) “Studyy of Precipitation
p in Next Generation HSLA Steels”,, Peter
Hodgson Nov. 12 Friday Hall Marmara 11:15 (Please review High
Strength Low Alloy Steel Knowledge before going to congress)

2) “Heat Treatment: State of the Art, Future Trends”, George E. Totten,

Nov. 13 Saturday Hall Karadeniz 13:30
PHY MET 311E GRADING
1st Lecture September 24 Quizzes (min 4) = 30 %
2nd Lecture October 01
3rd Lecture October 08 MidTerm = 25 %
4th Lecture October 15
5th Lecture October 22 Term Paper = 0%*
October 29 (NH) (
(number
b off students
t d t > 25)
6th Lecture November 05
7th Lecture November 12 Final 45 %
November 19 (NH)
8th Lecture November 26 --------------------------------
December 03 (MID TERM EXAM) Total 100 %
9th Lecture December 10
10th Lecture December 17 ATTENDANCE
11th Lecture December 24
12th Lecture December 31 At least 70 % attendance is
expected to enter Final.
Course web page
http://web.itu.edu.tr/ozk
al
Research Assistant : Ahmet Umut
SÖYLER 43

soylera@itu.edu.tr