Interfaces: Grain boundaries and interphase interfaces

Structure and energy of grain boundaries

Low-angle and high-angle grain boundaries
Special low-energy high-angle grain boundaries
Interphase interfaces
Coherent, semicoherent and incoherent interphase boundaries
Shape of precipitates: Effects of misfit strain and interfacial energy
Loss of coherency

References:
Porter and Easterling, Ch. 3.3.1-3.3.3, 3.4
Allen and Thomas, Ch. 5.3
Jim Howe, Interfaces in Materials

University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Grain boundaries
Single-phase polycrystalline material consist many crystals or grains that have different
crystallographic orientation. There exist atomic mismatch within the regions where grains meet.
These regions are grain boundaries.
Structure and energy of a grain boundary is defined by the misorientation of the two grains and
the orientation of the boundary plane. 5 independent variables (degrees of freedom) are needed
to define the rotation axis, rotation angle and the plane of the boundary. Rigid-body translation of
two grains with respect to each other add 3 more variables.

2 special cases can be distinguished:

pure tilt boundary - axis of rotation is pure twist boundary - axis of rotation is
parallel to the plane of the boundary perpendicular to the plane of the boundary

axis of tilt boundary

twist axis

axis of tilt symmetry plane

University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Low-angle grain boundaries
Low-angle grain boundaries (misorientation 15) can be represented by an array of dislocations
In particular, low-angle tilt boundaries can be represented by an array of edge dislocations

b b b
D sin D
2 2 2 sin( / 2)

D - dislocation spacing
for small
- misorientation angle

recall our discussion of dislocation walls

h
low-angle symmetrical tilt boundary in a
simple cubic lattice

x
University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Low-angle grain boundaries

In asymmetric tilt boundary, the second set of

dislocations appears so that the boundary plane
moves off the plane of reflectional symmetry

b b|
D D|
cos sin

- is the angle of inclination of the boundary plane with

respect to the symmetric orientation

low-angle asymmetric tilt boundary in a simple

cubic lattice

University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Low-angle grain boundaries
Low-angle grain boundaries (misorientation 15) can be represented by an array of dislocations
Low-angle twist boundary is a cross-grid of two sets of screw dislocations

atoms between the dislocations fit almost perfectly

to the adjoining crystals, with the distorted regions
localized along the dislocation cores

low-angle twist boundary in a simple cubic lattice

atoms in crystal below boundary are shown by circles,
atoms above boundary are shown by dots

University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Energy of low-angle grain boundaries
for small , the distance between dislocations is large and the
energy of the grain boundary, GB, is proportional to the
dislocation density:
1 xx
GB ~ ~
D

as increases, the strain fields of dislocations

increasingly cancel out and GB tend to saturate

when approaches ~15, core regions of the

dislocations start to overlap and the description of
GB in terms of dislocation wall is no longer useful

GB 10-15

random high-
angle GB

low-
angle
TEM image of a small angle
tilt boundary in Si
University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Energy of grain boundaries
1 SV SV GB

energy of random high angle GB: GB examples: [mJ/m 2 ]
3
(open disordered structure) Pt 2340 660
Ag 1140 375
Au 1410 378
Cu 1670 625

there are specific combinations of GB

misorientations and boundary planes
that correspond to low energies
energy of symmetrical <110> tilt boundary in Al

special high-angle grain boundaries

from Porter and Easterling

University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Special high-angle grain boundaries
special boundary with good atomic fit low grain boundary energy

twin boundary In general, GB energy is a function of at least

5 parameters needed to describe the boundary

For a given misorientation, the energy of GB

will depend on the orientation of the GB plane

Twin boundary - special case of low angle,

high symmetry grain boundary. Most
commonly, twinning corresponds to mirror
symmetry around twinning plane.

coherent twin
boundary

incoherent twin boundary (much higher energy)

good atomic fit at coherent twin boundary low energy comparable to that of a stacking fault
University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Special high-angle grain boundaries: Faceting
strong dependence of the GB energy on the orientation of the boundary plane optimization of
grain boundary - faceting, i.e., decomposition of the grain boundary plane into planes with low
energies (or large areas on low-energy planes + small areas of connecting high-energy planes)

faceting: even though the total GB

area increases, the energy decreases

Faceting readily occurs and can reduce energy of the boundary -

somewhat similar to
misorientation of grains is more important than the orientation of
dislocations adopting low-
energy configurations in boundary planes.
Peierls energy landscape
The size facets can be large (observed in optical microscope) for
coherent twins and is smaller for other low-energy GBs - look
curved in a microscope.
metal carbide precipitation on GBs (1),
incoherent twin boundaries (2) & coherent
twin boundaries (3) in Fe-20Cr-25Ni (wt.%)
stainless steel
Sourmail & Bhadeshia,
Metall. Mater. Trans. A 36A, 23, 2005
University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Special high-angle grain boundaries: Coincidence site lattice
Lets consider rotation of two overlapping crystals with respect to each other about a certain
rotation axis. At certain misorientations one can get perfect overlap of the lattice sites in the two
crystals. The overlapping lattice sites create a new lattice called coincidence site lattice (CSL)

53.1 rotation of a cubic lattice about [100] cases 1/5 of the lattice sites to coincide
The (100) twist and (210) tilt GB shown above are high-density planes of CSL correspond to
low-energy GBs
University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Special high-angle grain boundaries: Coincidence site lattice
CSL is characterized by that is defined as
= volume ratio of the unit cell of the CSL to that of the original crystal lattice
= reciprocal density of coinciding sites

1: perfect crystal of small deviations from

perfect crystal (low-angle GB)
3: twin boundary - largest number of
coinciding lattice points ( is always odd)

GB that contains a high density of lattice points

in CSL is expected to have low energy because
of good atomic fit

high density of CSL lattice points requires both

special misorientation and the boundary plane
pure tilt or twist boundaries are good candidates

tilt boundary twist boundary

5, 36.9 <100> in cubic lattice
(GD plane paper) (GD plane || paper)

University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Energy of high-angle grain boundaries
atomistic modeling experiment
low boundaries tend to have
lower energies than average

the correlation with is not simple

- there is no monotonous energy
decrease with increasing

deviations from the ideal CSL

orientation may be accommodated
by local atomic relaxation or the
inclusion of dislocations into the
boundary

<100> (a, b) and <110> (c,d) symmetric tilt boundaries

University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Energy of high-angle grain boundaries
other models attempting to describe energies of GB include
structural (polyhedral) unit model proposed by Sutton and Vitek
Philos. Trans. R. Soc. London, Ser. A 309, 37, 1983

for a given tilt axis there are short-period grain-boundary

structures consisting of a single type of structural unit
GBs at intermediate misorientation angles can be
constructed by combining this units
the minority units are considered to be dislocation cores

disclination and disclination-structural unit models

Li, Surf. Sci. 31,12, 1972
Gertsman et al., Phil. Mag. A 59, 1113, 1989

grain boundary regions can be disordered/amorphous, in

particular in polymers and ceramic materials

chemical composition of grain boundary regions can be different

from the bulk of the grains

no universal theory exists to describe high-angle GBs

University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Interphase boundaries
interphase boundary separates two different phases which may have different composition,
crystal structure and/or lattice parameter limited (if any) options for perfect matching of
planes and directions in the two crystals
depending on atomic structure, 3 types of interphase boundaries can incoherent
be distinguished: coherent, semicoherent, and incoherent

coherent (commensurate) interface: two crystals match perfectly at

the interface plane (small lattice mismatch can be accommodated by
elastic strain in the adjacent crystals)
semicoherent
semicoherent (discommensurate) interface: lattice mismatch is
accommodated by periodic array of misfit dislocations
incoherent (incommensurate) interface: disordered atomic structure
of the interface

a a1
coherent
lattice misfit at the interface: 2
a1
even in the case of perfect atomic matching, there is always a chemical
contribution to the interface energy

University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Coherent interphase boundaries
strain-free coherent (commensurate) interfaces:
two crystals match perfectly at the interface plane
interfacial plane has the same atomic configuration in both phases

The indices of the planes comprising the boundary do not have to be the
same in each phase but orientation relationship between the two phases
should be satisfied. This relationship is specified in terms of a pair of
parallel planes and directions, i.e., {hkl}//{hkl} and <uvw>//<uvw>
same crystal structure
Example: interface between and phases in Cu-Si

(111) plane of phase

matches almost perfectly
(0001) plane in phase

hcp phase
fcc phase different crystal structure
orientation relationship:
111 //0001 and 1 10

// 1120

University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Strained coherent interphase boundaries
Small differences in lattice parameter can be accommodated by elastic strain and coherent
interface can be maintained. If the upper crystal is uniformly strained in tension and the lower
half uniformly compressed, the crystals match perfectly.

a2 a1

a2 a1
0
a1

Smith and Shiflet, Mater. Sci. Eng. 86, 67, 1987

This coherency strain reduces the interfacial energy at the expense of increasing energy of the
two phases adjoining the interface coherent interfaces are favored when
(1) interface is strong,
(2) misfit is small (few percent),
(3) the size of one of the crystals is small (thin overlayer or small precipitate)

While the structure of the interface is perfect, the interfacial energy is due to the bonding between
atoms from different phase (has only chemical contribution): 1 200 mJ/m 2
coh chem

University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Semicoherent interphase boundaries
When the energy due to the coherency strain becomes too large, formation of a semicoherent
interface can become energetically favorable uniform elastic strains are replaced with
localized strain due to an array of dislocations that do not create long-range strain fields

a2 a1

a1 d

and/or d are too

large to maintain
coherent interface

a2 b
dislocation spacing in 1D: D

a1 a2 b1
b - Burgers vector of misfit dislocations D1
2 1

In two dimensions, a network involving more than one Burgers b2

D2
vector may be required to accommodate the misfit 2

University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Semicoherent interphase boundaries
Example: lattice-mismatched Ag film - Cu-substrate interface
1
aCu 3.63 A a Ag aCu b [1 1 0 ]

2
1

0.13
a Ag 4.09 A aCu 1
b 2 [11 0 ]

2
b a
D1 D2 6.3a 5.44a b
2
coherency strain is partially relieved by misfit dislocations, Wu, Thomas, Lin, Zhigilei,
Appl. Phys. A 104, 781-792, 2011.
with residual compressive strain present in the film
Energies of semicoherent interfaces have both chemical and structural
(distortions due to the misfit dislocations) contributions: semicoh chem str 200 500 mJ/m 2

str can be estimated similarly to low-angle GBs, by dividing the energy per unit length of the
dislocations, Gb2/2, by the dislocation spacing, b/ str Gb/2. For G = 50 GPa, b = 3 ,
and = 0.01, str = 500.30.01/2 = 75 mJ/m2
similarly to low-angle GB, str ~ (proportional to density of dislocations) for large D but
following a logarithmic dependence and saturate as D decreases

the limit to dislocation-based structures is at ~ 0.25 D = 4b cores start to overlap

University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Incoherent interphase boundaries
very different (incompatible) structure of the two phases or large lattice mismatch ( 0.25)
prevents good matching across the interface incoherent interface with disordered structure,
similar to random large-angle GB

large interfacial energy largely dominated by the structural contribution:

incoh chem str 500 1000 mJ/m 2

table in Howe, Interfaces in Materials

University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Shape of precipitates: Dependence on interfacial energy
lets consider a strain-free precipitate of phase in an phase matrix

the interface around a precipitate is, in general, not the same over the
entire surface - precipitates possess a mixture of interface types along
their surface
minimum free energy of this system corresponds to the orientation
Ai i min of the equilibrium shape
relationship and shape optimized to give the lowest tot N
remember our discussion
i 1
of crystallites and Wulff
coherent precipitates construction
small precipitates can form low-energy coherent
interfaces on all sides if and phases have the
same crystal structure and similar lattice parameter
Examples:
precipitation of fcc Co in Cu matrix, fcc Ag in Al matrix
fully-coherent precipitates are called Guinier-Preston zones

3D reconstruction of GP zones in Al-2.7

at.% Ag alloy (TEM and atom probe tips)
Marquis, Bartelt, Leonard,
Microsc. Microanal. 12, 1724 CD, 2006
University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Shape of precipitates: Dependence on interfacial energy
partially coherent precipitates

when and phases have different crystal structures, orientation relationship leading to low-
energy coherent or semi-coherent interface may be found only for one habitat plane
other planes will be incoherent and will have higher interfacial energies

the equilibrium shape of the precipitate can then be determined

coh i
similarly to the equilibrium shape of crystallites (-plot and Wulff
construction) large coherent facets terminated by incoherent edges

Examples:
hcp Ti in bcc Ti (slowly cooled two-phase Ti alloys)
tetragonal phase precipitates in Al-Cu
hcp precipitates in Al-Ag

orientation relationship:
111 //0001 and 1 10

// 112 0

Moore and Howe,

Acta Materialia 48, 4083, 2000 precipitate in
University of Virginia, MSE 6020: Defects and Microstructure in Materials, LeonidAl4.2 at.% Ag alloy
Zhigilei
 Shape of precipitates: Dependence on interfacial energy
partially coherent precipitates - Widmansttten pattern
cubic symmetry of the matrix many possible orientations for the precipitate plates

Al4 at.% Ag alloy

Widmansttten pattern in iron meteorites: precipitation and growth of Ni-poor kamacite (bcc)
plates in the taenite (fcc) crystals proceeds by diffusion of Ni at 450-700C, and take place
during very slow cooling that takes several million years the presence of large-scale
Widmansttten patterns proves extraterrestrial origin of the material

University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Shape of precipitates: Dependence on interfacial energy
incoherent precipitates

very different crystal structures or random orientation absence of coherent or semi-coherent

interfaces -plot and Wulff construction predict roughly spherical shapes of precipitates
some cusps on -plot may appear for certain crystallographic planes of the precipitate faceting
that does not reflect the existence of coherent and semi-coherent interfaces

Examples of incoherent precipitates in Al: CuAl2, Al6Mn, Al3Fe

precipitation on GB

heterogeneous nucleation at GB can give rise to precipitates that are incoherent on one side, and
semi-coherent on the other side
Cu-In alloy
shapes of precipitates are defined by minimization of the
interfacial energy and balance of interfacial tensions at
junctions of the interfaces and GB

precipitate and GB triple point of - Cu-In alloy

interfaces A and B are incoherent, C is semicoherent
University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Shape of precipitates: Effect of misfit strain
coherent precipitates
The effects of elastic interactions between the matrix and the precipitate can be as important as
for the interfacial energy. The two effects can compete: this is one reason for changes during
growth, such as the loss of coherency.

A
coherency strain should be accounted N
Gs min
for in minimization of the free energy: i 1
i i

elastic strain energy

a a

a

the elastic energy associated with the dilatational strains is of order 2 V, where V is the volume
of precipitate
for isotropic matrix and precipitate, the elastic energy is independent of shape: Gs = 4G2V

effect of difference in elastic properties:

Precipitate stiffer than matrix: minimum elastic energy occurs for a sphere
Precipitate more compliant than matrix: minimum elastic energy occurs for a disc
Anisotropic matrix: most cubic metals are more compliant along <100> and harder along <111>
elastic energy
University considerations
of Virginia, MSE 6020: favor discs
Defects and parallel to {100}
Microstructure in Materials, Leonid Zhigilei
 Shape of precipitates: Strain energy vs. interfacial energy
competition between elastic energy and interfacial energy can result is a sequence of
precipitation reactions appearance of successively more stable precipitates, each of which
has a larger nucleation barrier

Example: in Al alloys with 5% Cu (maximum solid solubility of Cu in Al at Te

The sequence is 0 1 + GP-zones 2 + 3 + 4 +

n - fcc aluminum; nth subscript denotes each equilibrium
GP zones - mono-atomic layers of Cu on (001)Al
- thin discs, fully coherent with matrix
- disc-shaped, semi-coherent on (001) bct
- incoherent interface, ~spherical, complex body-centered tetragonal (bct)

The precipitate with the smallest nucleation barrier (generally) appears first. Small nucleation
barriers are associated with coherent interfaces (small interfacial energy) and similar lattices
(small elastic energies from misfit).

University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei
 Loss of coherency
competition of volumetric elastic strain energy and interfacial energy precipitate may start as
fully coherent but nucleate interfacial dislocations once it reaches a critical size

Assuming that elastic strain energy is significant for the fully coherent precipitate but not for
incoherent or semicoherent ones, the free energies of crystals with coherent and non-coherent
precipitates can be written as
4
Gcoherent Gelastic Ginterface 4G 2 r 3 chem 4r 2
Gcoherent 3
G
Gnoncoherent Gelastic Ginterface 0 chem str 4r 2

Gnoncoherent
3 st
Gcoherent Gnoncoherent rcr
4G 2
1
for semicoherent interfaces with large D: st ~ rcr ~
rcr r

at r > rcr, dislocations can be nucleated the character of the

interface will change coherency will be lost

University of Virginia, MSE 6020: Defects and Microstructure in Materials, Leonid Zhigilei