Materials Science and Engineering A191 (1995) l-16

Theory, simulation, and modeling of interfaces in materials-

bridging the length-scale gap: a workshop report

Wayne E. King”, Geoffrey Campbell”, Tony Gonis”, Greg Henshall”, Don Lesuera, Ed Zywicz”,
Stephen Foilesb
aLawrence Livermore National Laboratory Livermore, CA, USA
bSandia National Laboratories, Livermore, CA, USA

Received 19 June 1994

Abstract

The workshop on interfaces in materials-bridging the length-scale gap was held on September 12-15, 1993, at the University of
California at San Diego Institute for Mechanics and Materials, La Jolla, CA. This workshop addressed length-scale issues associated
with developing a predictive capability for materials whose properties are interface controlled. The goal of this workshop was to
identify touch points bridging the various length scales important in materials modeling of systems whose properties are controlled by
interfaces. The format of this workshop broke with convention by initiating discussion at the macro scale. Each speaker identified key
physical parameters central to their model. Subsequent speakers, in order of decreasing length scale, identified where their model fitted
within the context of the larger length scales and which parameters required at the larger length scales can be predicted. The topics that
were covered include (1) modeling at the macro scale-phenomenological and finite element, (2) modeling at the micro scale-
crystalline effects, (3) modeling and simulation at the atomic scale-interatomic potentials for complex systems, (4) electronic structure
calculations-application to interfaces, and (5) critical experiments which serve to validate theoretical models.

Keywords: Interfaces; Modeling

1. Introduction required (1) to optimize performance for the desired

Improvements in material properties necessary to
meet future energy, environmental, and competitive
demands will require significant scientific and techno-
logical advancement. These “next-generation”
materials will often derive their enhanced properties
and performance characteristics by combining conven-
tional materials in a hybrid structure. In such struc-
tures, the derived property of interest, e.g. fracture
toughness or fatigue resistance, can deviate greatly from
that predicted by a simple rule of mixtures as a con-
sequence of interfaces engineered into the structure.
It will be necessary both to predict and to control the
properties, whether beneficial or detrimental, of next-
generation materials. Currently, these new materials
can require years of experimental validation before
insertion into critical applications. In addition, reliabil-
ity issues can effectively block commercialization of
advanced materials. A predictive capability is therefore
application and (2) to provide a more efficient method
to select and commercialize new materials. This pre-
dictive capability is to be differentiated from descrip-
tive capabilities that might evolve using methods such
as artificial intelligence. However, the importance of
descriptive models must not be diminished.
Unfortunately in this new class of materials, rela-
tively large, usually unacceptable, variability of macro-
scale properties compared with conventional materials
occurs either intrinsically or can be introduced during
synthesis or processing. Such variability gives rise to
inconsistent and inconclusive performance tests that
often limit applicability. This occurs because the
macroscopic performance is derived from phenomena
that are operative at a different, smaller length scale that
is often beyond the resolution of the macro-scale
property that is measured to probe the relevant per-
formance. Macro properties are a homogenization of
phenomena occurring at smaller length scales. It

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2 W.E. Kinget al. / Materials Science and Engineering A191 (1995) l-16
follows that, since macro-scale performance can only
resolve the collective performance of the constituents,
it is necessary to examine the operative length scale for
insight for development of a knowledge-based method
to reduce variability or to alter properties. Currently,
however, there exists no effective formalism to “bridge”
the gaps that separate the macro performance of
materials from the controlling phenomena. In an effort
to identify the key issues, a workshop entitled “Theory,
Simulation, and Modeling of Interfaces in Materials-
Bridging the Length-Scale Gap” was conducted during
September 12-l $1993. The workshop was organized
by the Institute for Mechanics and Materials at the
University of California at San Diego and the
Chemistry and Materials Science Department of
Lawrence Livermore National Laboratory.
It is appropriate at this point to define the range of
length scales thought to be important in controlling the
properties of materials with interfaces engineered into
their structure. These include the macro, continuum,
meso, micro, atomic, and electronic length scales. The
concept of length scales exists because of the classes of
physical theories and models that have been developed
to describe material behavior. Boundaries (either
spatial or temporal) between the length scales are
delineated by the breakdown in the assumptions impli-
cit to a particular scale. Thus we can define each scale
by the phenomena that are treated discretely and the
phenomena that are treated collectively. The two
exceptions are the end points of the length scales.
Everything at the electronic scale is treated discretely
whereas everything at the macro scale is treated
collectively. The atoms are treated discretely at the
atomic scale and the electrons are treated collectively.
At the micro scale, defects are treated discretely and
atoms are treated collectively. At the meso scale,
microstructure (such as grains) is treated discretely and
defects are treated collectively. At the continuum level,
components (here referring to parts of an assembly) are
treated discretely, and microstructures are treated
collectively. Finally, the macro scale represents a
collection of continuum treatments, i.e. the application.
Before bridges can be effectively built between or
among these length scales it is essential to answer four
questions [l]: (1) is it possible to build the bridges, (2)
do the tools exist to build the bridges, (3) on what
common “material” (measurable and calculable
quantity) will the bridges be based, and (4) where will
the bridges be built? The remarkable progress that has
been made in related fields, such as calculation of alloy
phase diagrams and simulation of microstructural and
microchemical evolution, suggests that length-scale
bridges can be constructed. In this case, the complica-
tion is the broad range of length scales that must be
spanned, i.e. in excess of 10 orders of magnitude in
space and 15 or more in time. In the following discus-
sion, the status of tools at each scale is evaluated and it
is concluded that sufficient tools are in place with
which to build the first bridges.
The outstanding issues are to identify the “material”
upon which to base the bridges and the touch points (or
near-touch points) which are most likely to give rise to
successful bridges. Analysis of the presentations of the
invited speakers has led to the proposal that the
“materials” upon which to base the bridges are energy,
space, and time. This deduction, while at first appear-
ing trivial, will likely require major reformulation or
recasting of the modeled or simulated quantities at
some length scales to facilitate bridging of the gaps. For
example, it may be necessary to express dislocation
arrays in units of energy and space when passing the
output of the micro scale to the meso or continuum. It
will also be necessary to define carefully fundamental
quantities such as interface strength, adhesion, and
toughness to fit the new paradigm.
An ongoing challenge will be to develop model
systems and model experiments that will allow valida-
tion of the bridging theories and models. These experi-
ments will probably lie on the extremes of the space
and time domains, e.g. use single, semi-infinite inter-
faces or an infinite number of very short interfaces, or
employ quasi-static experiments together with short
time scale dynamic experiments [2].
In the following discussion, we summarize what was
reported as the state of the art. We then provide an
analysis of the critical issues and close with some
observations for future work. No attempt is made to be
exhaustive in this report. The depth of the coverage of
any particular area reflects the depth of coverage at the
workshop.
2. State of the field: report from presentations
2.1. Macro scale: industrialapplication
Macro-scale modeling and simulations attempt to
describe the macroscopically observable behavior of
materials. These methods provide details about the
properties of material not accessible from smaller
length-scale descriptions. For example, dynamic codes
have been used to predict metal forming as well as the
crash behavior of automobiles. The goals of the models
are to provide an efficient method to simulate proces-
sing, resulting properties or in-service performance.
The need for models that bridge length-scale gaps
was illustrated on two different classes of structural
materials in which interfaces play a critical role: metal
matrix composites (MMCs) and cast or welded
materials. In both of these commercially important
 W. E. King et al. / Materials Science and Engineering Al 91 (1995) l-l 6
systems, modeling is the key to (a) minimizing the time
required to develop a new process, (b) assisting in the
scaling-up of commercial manufacturing processes for
high volume production and (c) processing for con-
sistent quality and reliability. The important issues
facing the automobile industry and desired end points
(input and output) for modeling work were well illus-
trated for particulate and whisker reinforced MMCs
[3]. Here the need for modeling capability that spans
several length scales was evident. In the MMCs dis-
cussed, the materials development and manufacturing
challenges are considerable. Interfaces play a critical
role: a weak interface guarantees a weak component.
Thin or non-existent interphases are desired (less than
2 run thick) and must be produced over relatively short
time scales (approximately 15 s). Thick interphases are
guaranteed failure sites. In addition, interface reaction
zones must be small and remain small throughout the
life of the component. The ability to predict the
influence of different impurity elements, flaws, and
processing histories on the characteristic of the inter-
face is critical to obtaining the full potential of these
materials and controlling costs, e.g. specifically what
impurities must be controlled and which flaws are criti-
cal?
One of the goals of future work should be to pro-
duce tailored interfaces. For this capability multiple
length-scale modeling will be needed to predict the
influence of different alloying elements on inter-facial
chemical reactions and bond strength. There are a
number of fundamental issues associated with inter-
faces in these materials. These issues, which exist at dif-
ferent length scales, influence a macro-level
characteristic, namely strength. These issues are as
follows.
(a) The influence of different alloying elements on
inter-facial reactions needs to be predicted. For
this problem equilibrium thermodynamics is not
applicable; non-equilibrium reaction products
can be produced and reaction times can be very
short owing to high surface activity. Simulations
of interface reactions must include both thermo-
dynamics and kinetics.
(b) Reinforcement surfaces are not well charac-
terized. These surfaces do not possess the bulk
chemistry or structure in most cases.
(c) The influence of local structure at the interface
(including lattice registry, dislocation type, and
defects) on interface strength needs to be pre-
dicted.
(d) The influence of impurity and alloying atoms on
interface strength should be predicted.
Supporting experimental capabilities are also
needed. Reliable techniques are needed to simulate the
effects of local composition and processing history on
3
properties. Methods are also needed to measure inter-
facial strength and the strength of small fibers. Specifi-
cally, studies should be carried out to assess
reinforcement strength as a function of local composi-
tion, processing, and service history.
For cast or welded materials, the challenge to
industry is to predict defects and the resulting micro-
structures. Current capabilities in this area were
addressed for modeling of both casting and welding [4].
The typical structural materials that are modeled
include alloys that have complex composition (such as
superalloys). In addition, the resulting microstructures
that are produced during casting are quite complex. In
addition, the resulting microstructures that are pro-
duced during casting are quite complex. Typically,
multiphase microstructures, including dendritic and
eutectic structures, are observed. Welding is a
thermal-mechanical process with complex boundary
conditions and material response. Current simulations
typically span several length scales in that they use heat
and fluid flow and mechanical behavior at the con-
tinuum level to predict the resulting influence on
microstructure. Defects such as cracking, distortion
and poor weld penetration are also predicted. The
complexities that are routinely observed and incorpor-
ated in models in these processes include an intense
local heat source, heat losses, phase changes, distor-
tion, microstructural evolution, and residual stresses.
For super-alloys, the melting range can be quite large,
spanning several hundred degrees Celsius. Currently
microstructure, as characterized by grain size and grain
growth rates, can be predicted on the basis of quanti-
ties that are derived from the simulations (thermal
gradients and cooling rates). This prediction requires
experimental data and an empirically derived under-
standing of the correlation between the thermal
gradients and cooling rates, and the resulting grain size.
As such, current models tend to be more descriptive
than predictive.
2.2. Continuum scale
Continuum-scale modeling and simulations describe
the behavior of materials by viewing components as
“continuous” or “homogenous” entities. The com-
ponents can be structural members (e.g. beams, sand-
wich panels, or plates), elements of a structural
member (e.g. the individual lamina used to make a
laminated plate), or even the constituents of a hetero-
geneous materials (e.g. reinforcement particles in an
MMC or the subregions of a complex heterogenous
silicon carbide ceramic fiber). These models attempt to
resolve the aggregate response by integrating the
geometrical configuration with the detailed continuum-
level constitutive behavior of each component. They
4 W.E. King et al. / Materials Science and Engineering Al 91 (1995) l-l 6
can predict the effective response to imposed loads and
even the energy release rate of (inter-facial) cracks.
Continuum level treatment of interfaces is greatly
simplified when the detailed mechanisms of interface
failure (controlling phenomena) are unimportant in
describing the overall material response. For example,
in fracture of certain Sic fiber reinforced (brittle)
ceramic matrix systems, load is transferred between the
fiber and the matrix during fiber pullout predominantly
by frictional means [5]. Naturally occurring curvature
of the fibers enhances the frictional work, i.e. dissipated
energy during matrix failure, since additional stresses
must be generated to slide the fiber through the matrix.
Quantitative models that treat the frictional effects by
“shear-lag” type mechanisms predict measured con-
tinuum stress-strain responses reasonably well.
Probabilistic theories of fiber failure can be combined
with the shear-lag assumptions by way of a Cur-tin
model [6]. This model accounts for the load carried by
the broken fiber pieces and requires that the nominal
shear stress associated with the shear-lag behavior (i.e.
that generated from frictional effects) and certain
Weibull distribution parameters [7] be specified. Limit-
ing the number of fractures along the fiber length to a
maximum of two yields reasonable strength values.
Inclusion of additional terms helps to replicate the
observed stress-strain response. The model also works
well in predicting fatigue life as a function of imposed
macro stress for imposed stress amplitudes greater
than the ultimate strength of the matrix. Similar
approaches can be applied to fatigue crack growth in
MMCs where the interfaces are weak and fiber
slippage must occur for a crack to grow [5]. These
models use shear-lag and crack-bridging principles
together with Paris law data to describe the matrix and
fiber failure. As before, only the shear stress generated
by friction is needed to characterize the effects of inter-
faces. Creep models represent a generalization in that
both temporal variations in mechanical and thermal
loads can be addressed.
While weak interfaces may render certain material
systems independent of inter-facial behavior (other than
friction), exceedingly strong interfaces can have the
same consequence. Consider the toughening of fiber
reinforced epoxies [S]. Here cracks advance through
the bulk material in the usual manner until the crack
front impinges against two adjacent reinforcement
fibers. Elevated loads force the crack front to bow out
around the ends pinned by the fibers. When the bowed
sections finally encompass the fiber, the crack fronts
join and advance past the fibers. This process is analo-
gous to the way dislocations advance around impene-
trable particles. Models that predict the enhancement
in toughness gained by way of crack trapping depend
solely on geometric quantities (fiber diameter and
spacing between fibers) provided that energetics of the
fiber-matrix interface preclude debonding during
trapping. (The quantity toughness can be related to the
energy dissipated per unit area of crack advancement).
Well-controlled experiments by Argon [8] show good
agreement with the toughness enhancement model
developed by Bower and Ortiz [9].
In a related situation, strong interfaces perpendicu-
lar to a crack have been found to influence the fatigue
crack growth behavior in bimaterial metal systems [ 101.
Fatigue crack growth experiments in which a crack is
driven through a lower yield strength material (ferrite)
towards a higher yield strength material (austenite)
show that, independent of the load amplitude, the
crack advancement is arrested as the crack approaches
the interface. When the configuration is reversed such
that the crack originates in the austenite, the crack
growth per cycle remains constant as the crack
approaches the interface, increases slightly as it goes
through the interface, and returns to its previous level
as the crack extends beyond the interface. Companion
finite element (FE) calculations of a statically loaded
crack at a fixed location near the interface show that
peak opening stresses directly ahead of the crack are
smaller when the crack is located in the ferrite than
when it is in the austenite. The smaller stress is accom-
panied by a correspondingly smaller crack opening dis-
placement. These observations may help to provide
insight into the experimentally observed behavior of
fatigue cracks near interfaces.
For two other bimetallic systems studied, the inter-
face and the neighboring region represent paths for easy
fracture [ 111. For example, in both the Cu-Fe and the
austenite-ferrite bimaterial systems with cracks
running parallel to the interface, the measured fracture
toughness decreases as the distance between the crack
and the bimaterial interface decreased with a threshold
distance at which the crack jumps to the interface. The
minimum observed fracture toughness occurred when
the crack propagated at the interface.
Continuum modeling and understanding of inter-
facial phenomena have also advanced in systems where
the detailed mechanisms of inter-facial failure play a
significant role in influencing the overall material
response. Examination of the fracture behavior of
“ideal” glass-epoxy composites has led to many inter-
esting observations [ 121. The critical energy release
rate for this system varies significantly with “mode
mixity”, i.e. essentially the ratio of tension and shear
tractions imposed on the crack. In general, pre-
dominantly shear loaded cracks are many times
tougher than those loaded only in tension. Experiments
using specimens with various widths yield similarly
shaped critical energy release rate vs. mode mixity
curves, but with appreciably different magnitudes.
 W.E. King et al. / Materials Science and Engineering A 191 (19%) I-I h
Comparisons with FE simulations show that the
measured crack face opening displacement is smaller
than what is calculated. One hypothesis that has been
investigated is that attractive electrostatic forces may
be present near the crack tip, effectively holding the
crack closed [ 121.
2.3. Mesoscopic scale
Meso-scale modeling and simulations describe the
aggregate behavior of materials while treating aspects
of the mircrostructure discretely. They are extremely
effective tools at addressing the variability and size
dependence of materials systems. Generally, simplify-
ing assumptions regarding the microstructural
responses are made. For example, the interfaces of
individual ceramic grains can be idealized as discrete
springs, with finite strengths, connecting adjacent
particles. By performing a series of simulations in
which loads are imposed on the exterior of a represen-
tative volume, these models can predict the variability
of specific quantities, such as fracture toughness,
ultimate strength, and modulus, as a function of
geometry and microstructural variations such as grain
size, aggregate orientation and shape, porosity, second
phase inclusions, and interfacial strength and stiffness.
In addition to yielding these discrete material quanti-
ties, these simulations provide additional insight into
the material response by showing phenomena such as
redundant fracture paths and local instabilities.
Interfacial behavior at the mesoscopic level can con-
trol the continuum behavior of many materials, includ-
ing those with weak grain boundaries [13], reaction
bonded and other porous ceramics [8], and fiber rein-
forced MMCs with a graded interphase between the
matrix and the reinforcements [ 141. This is the largest
length scale where property variability is observed in
models. When examining the continuum-level proper-
ties of these interfacially controlled materials, two
cases are observed [ 131. As the length scale used to
evaluate or determine the properties increases, i.e. the
size of the sampling element or specimen size
increases, (1) the property saturates toward a single
value, or (2) the property continues to change. The
continuum elastic modulus is an example of the former,
while the macroscopic fracture stress in brittle solids,
which has been observed to vary with the logarithm of
the volume of material tested, is an example of the later.
The problem is further complicated when variabilities
exist in the mesoscopic description. For example, in a
reaction bonded porous ceramic, the bond strength
between any adjacent grains varies depending on which
grains are sampled [S]. This variation is manifested by
variance in the continuum-level response and proper-
5
ties [8,13]. Both local variability and size dependent
properties introduce an inherent length scale that is
significant and must be accounted for properly.
The key question involved with bridging the gap
between the mesoscopic and the continuum is how to
average multiple elements, each containing interfaces,
to predict continuum properties together with their
variance or “reliability”. The goal of mesoscopic
modeling is to take information regarding micro-
structural variability, which may be gained from experi-
mental observations or potentially from modeling at a
length scale smaller than the mesoscopic, and to pro-
vide predictions of (1) continuum properties such as
elastic modulus, fracture strength, and fracture tough-
ness, (2) material reliability, i.e. the variance in these
continuum properties, and (3) geometrical information
at the mesoscopic level, such as fracture path or the
amount of damage away from the “critical” flaw that
resulted in failure [8,13]. This technique allows for a
bridge from the length scales below the mesoscopic, in
addition to a bridge up to the higher continuum length
scale. For example, output from atomistic simulations,
e.g. the stiffness and strength of a grain boundary as a
function of local boundary chemistry and structure,
could potentially be used to provide a physically based
prediction of the variability in the interface behavior at
the mesoscopic level [ 131. The mesoscopic “homogeni-
zation” is then used to produce continuum results. Pro-
vided that a load sharing or interaction relationship is
definable, then ‘reliability laws” can be calculated [ 131.
The first step in modeling at this scale is to provide a
description of the spatial arrangement of the particles
and their interfaces within a computational unit cell,
When modeling stochastic processes, it is important
that many particles and interfaces are included in the
unit cell analysis since the number of these interfaces
will affect the results, just as experimental results
depend on sample size [8,13]. The spatial arrangement
of particles and interfaces can be obtained directly by
“digitizing” experimentally observed structures [ 131,
using output from a model that predicts the arrange-
ment of interfaces [8], or simply using some idealiza-
tion of the arrangement, e.g. by specifying a unit cell
that contains a single representative reinforcement and
its surrounding matrix [14]. The next step is to repre-
sent the behavior of the interfacial region. In some
cases this can be accomplished with simple spring
models to represent the force-displacement rela-
tionship of the interface [8,13]. More complex statisti-
cal sampling techniques, which find particular use
when the interface region has a spatially varying chemi-
cal composition normal to the interface, can be used to
estimate and effectively homogenize the elastic stiff-
ness tensor as a function of position from the interface
[14]. Next, boundary conditions are imposed on the
6 W.E. Kinget al. / Materials Science and EngineeringAl
exterior of the unit cell and equilibrium is sought,
usually by minimizing the energy of the system.
When the contents of the unit cell can be completely
described with continuum relationships, classical
methods can be used to solve the problem directly. In
the specific case of an elastic unidirectional fiber com-
posite whose interphase composition is a random func-
tion of position, the results are bounds of the effective
continuum (tensorial) moduli of the composite as a
function of the length scale used to sample the inter-
phase [14].
Models of stochastic processes can produce con-
tinuum-like stress-strain curves [8,131. Such models
also provide the means for predicting the variance in a
particular continuum property by varying the spatial
arrangement of interfaces within the unit cell or by
varying the inter-facial properties [8]. These results pro-
vide a means to explore material reliability based on a
physically based mesoscopic description of material
structure. Finally, mesoscopic models that specifically
described multiple interfaces provide a spatial distribu-
tion of critical and non-critical (redundant) fracture
events. This is microstructural information that could
not be gained from a purely continuum model.
With proper accounting for the size of the computa-
tional cell and its representation of variability in the
microstructure, “unit cell” models can suggest scaling
relationships for continuum quantities that depend on
the mesoscopic length scale. The size of the unit cell is
determined by the variability of the components being
homogenized and whether the quantity being com-
puted is dependent on microstructural variability.
2.4. Microscopic scale
Micro-scale modeling and simulations describe the
behavior of materials including the effects of crystallo-
graphic defects, e.g. dislocations and grain boundaries,
and their interactions with other defects, including
second phases. Some models explicitly include the
properties and behavior of individual defects, so that
the model inputs include quantities such as the disloca-
tion Burgers’ vector and the grain boundary crystallo-
graphy. To date, such models have been used mostly as
qualitative guides to provide physical understanding.
Other models focus on the effects of large numbers of
defects in an aggregate way, so that inputs include
quantities such as forest dislocation density, grain size,
or precipitate morphology. These models often pro-
vide a quantitative description of material behavior
that can be used in continuum calculations. Thus,
unlike models at the other length scales, there is a wide
range of structural detail over which micro-scale
models have been developed. For example, consider
the simulation of grain boundary strengthening. Micro-
(1995) I-16
scale models have been developed to describe the way
in which an individual dislocation interacts with a parti-
cular grain boundary (or bimaterial interface). This
knowledge, together with models describing disloca-
tion-dislocation interactions, then can be used to
develop models describing the increased dislocation
density near grain boundaries and how the resultant
internal stresses can cause dislocation activity in an
adjacent grain. Finally, these models can provide
theoretical support for, or lead directly to, models of
grain boundary strengthening that can be used at a con-
tinuum level.
Materials with grain sizes in the nanometer range
provide a striking example of the importance and diffi-
culty in understanding the behavior of materials whose
properties are controlled by interfaces. Potentially,
these material can possess very high strenghts (as
would be predicted by the Hall-Petch relationship
[15]), making them attractive to study technologically.
The fact that their macroscopic behavior is dominated
by interfaces is easily seen by computing the percent-
age of atoms, residing within the boundaries relative to
those in the bulk. For example, in a material with a 5
run grain size, 40% of the atoms reside at the grain
boundaries [ 161. Adding to the challenge of under-
standing such materials is the extremely short distances
over which dislocations could move before encounter-
ing a boundary. Again, for a 5 run grain, a dislocation at
the center of the grain would be on the order of only 10
atom spacings from any boundary. Understanding the
deformation mechanism in such a material may require
the development of new mechanisms to properly
describe the macroscopic mechanical response.
Another challenge is to understand why the Hall-Petch
relation appears to be valid for nanocrystalline
materials, as some have observed [ 161, if the deforma-
tion mechanisms differ from conventional polycrystal-
line materials.
Examination of the interaction between dislocations
and grain boundaries or bimaterial interfaces can pro-
vide insight into phenomena at the higher length scales
[ 111. In deformation studies of Si, examination of a so-
called “2 = 9” grain boundary at the microscopic level
showed that the dislocation density near the boundary
is much larger than that far from the boundary, In other
words, near the interface the material is at a more
advanced stage of deformation than within the grain.
Potentially, this has implications for the ease of propa-
gation of cracks near the boundary compared with
propagation within the bulk. Unpredicted, but not
unpredictable, dislocation behavior was observed in
the Pd-MgO, Nb-Al,O,, and Ge-GaAs systems
where, because of image forces, misfit dislocations at
some bimaterial interfaces were found to reside at a
“stand-off” distance away from the interface within the
 W. E. King et al. / Materials Science and Engineering A 191 (1995) 1 - 16
softer material rather than within the interface itself
[Ill.
2.5. Atomic scale
Atomic-scale computer simulations attempt to
describe the atomic-level structure, energetics and
dynamics of materials. These methods provide details
about the properties of individual defects not acces-
sible from longer length-scale descriptions. For
example, while continuum elasticity can determine the
long-range strain field from a dislocation and the
energy associated with that strain field, atomic-scale
simulations can determine the atomic structure of the
dislocation core and the core energy. There are two
different goals for these calculations. In some cases, the
atomistic simulations are used as a testing ground for
ideas about the behavior or energetics of defects. An
alternative goal is to be able to make quantitative or
semiquantitative predictions about the properties of
specific systems to understand specific measurements
or as a screening tool in choosing materials.
All of these methods are based on having a “black
box”, such as interatomic interactions, which attempts
to mimic the total energy of the system in terms of
forces between individual nuclei. There are two
philosophies behind constructing these interactions
that reflect the two different goals. In the case of model
studies, model interactions, such as Lemrard-Jones
pair potentials, are used. The other approach is to
develop interactions that attempt to mimic real
materials. In the latter case, the interactions ideally
represent the Born-Oppenheimer potential surface, i.e.
the energy of both the electrons and the nuclei for a
fixed set of nuclear coordinates. It is the creation of this
potential that allows the electrons to be removed from
the problem. The development of techniques to repre-
sent this potential that are both computationally
efficient and reasonably accurate is a subject of active
research that is discussed in the next section.
There are three broad classes of calculations that
can be performed at the atomic scale. The first involves
energy minimization that determines the lowest energy
configuration of the atoms corresponding to the zero-
temperature structure. Next, molecular dynamics
simulations follow the individual motion of the atoms
as computed from Newton’s equation of motion.
Finally, Monte Carlo simulations provide a mechanism
for computing thermodynamic equilibrium properties.
All of these approaches are limited to about the same
length scale. If simple potentials are used, the number
of individual atoms that can be treated is typically tens
of thousands up to millions. This still gives length
scales of up to a few hundredths of a micron, i.e. large
enough to study individual defects and possibly defect
7
pairs, but too small to study the collective behavior of
the defects. Further, the time scale of molecular
dynamics simulations is typically limited to no more
than about a nanosecond. This is long enough to study
some dynamic processes of defects, such as the
emission of a single dislocation from a crack tip, but
excludes the direct consideration of many important
processes such as diffusion.
The most direct application of these methods to
interfaces is the computation of the atomic structure of
specific interfaces, generally grain boundaries, in con-
junction with comparison with experimental probes,
typically high resolution electron microscopy [ 171.
There have been various calculations that have
successfully computed the structure of grain bound-
aries in certain metals, in particular the Cu and Ni
columns of the periodic table as well as Al. The con-
sensus is that the ability to determine the structure of
grain boundaries in these pure metals is fairly well in
hand.
The situation for other parts of the periodic table as
well as for the crucial area of alloys, impurities, and
bimaterial interfaces is not as good. For an example,
calculations and experimental structure determinations
of the 2 = 5 (3 lO)/[OOl] symmetric tilt boundary in Nb
were presented [ 171. These showed that current
methods, such as the embedded atom method or
Finnis-Sinclair potentials, fail to predict a structure in
even qualitative agreement with experiment. This
demonstrates that these methods, which ignore the
angular dependence of the interactions, are not
adequate even though they are typical of the inter-
atomic interactions used to describe metallic systems.
This study also showed that the angular dependent
interactions that are currently being developed, in this
case the model generalized pseudopotential theory of
Moriarty, do correctly describe the structure. This
shows that some progress is being made in developing
interatomic interactions that can describe a wider
range of materials. However, it is still true that for most
industrially interesting systems, especially bimaterial
systems, there do not exist computationally efficient
interatomic interactions that can be relied on to give
quantitative predictions. The only tool available in that
case is the electronic structure methods discussed
below. The drawback to that approach is that computa-
tional considerations limit the calculations to highly
idealized boundaries. For example, it may be necessary
to force the atomic arrangement to be coherent across
the interface and so to disregard misfit dislocations.
The determination of thermal equilibrium proper-
ties of interfaces was also discussed. In particular, the
computed equilibrium segregation of Ni to a grain
boundary in a Pt-3%Ni alloy compared well with
experimental measurements from atom probe field ion
8 WE. King et al. / Materials Science and Engineering A191 (1995) l-16
microscopy [ 181. The inclusion of local atomic relaxa-
tion and atomic-level thermal vibration in such calcula-
tions was shown to be essential to the quantitative
determination of these sorts of thermal equilibrium
properties. This situation mandates the use of com-
putationally efficient interactions and so limits the
current application of these methods to the narrow
range of materials mentioned above.
In the above calculations, the goal was to make
quantitative predictions for a specific material. It is also
possible to make qualitative predictions about specific
materials or classes of materials. The motion of a
[ 1 lO]/( i 10) edge dislocation in NiAl was investigated
using molecular dynamics [ 171. The calculations
showed that, at low stresses, the dislocation core disso-
ciates into two partial dislocations that separate normal
to the slip plane and so lock the dislocation. At higher
stresses, the dislocation core was seen to convert to a
mobile configuration and the dislocation could move.
This work provides some hints to the mechanisms
involved in the brittle to ductile transition that is
observed in the so-called “hard” orientations of that
alloy. In a similar study, the atomic-scale behavior in
the vicinity of a crack tip was studied by molecular
dynamics. In part, this work showed how the effect of
hydrogen on dislocation emission from the crack tip
depended on the specific location of the hydrogen near
the tip.
In a more global context, these studies illustrated the
practical difficulties associated with studying dynamic
behavior of defects with atomic-scale simulation, i.e.
the boundary conditions impose artificial conditions on
the dynamics. The current state of the art [2,17,19] is
to include a shell of atoms in the simulations whose
positions are determined by the solution of the appro-
priate continuum problem. The atoms in the interior
are then allowed to move according to the atomic
forces. This approach has been carried through for
static energy minimization calculations [ 191. In particu-
lar, a static calculational procedure has been developed
that places an atomistic region in the middle of con-
tinuum region whose mechanical response to external
boundary conditions is computed using FE methods
[20]. For styding dynamic simulations, the methods are
less well developed. Either the calculations are per-
formed in a quasi-static manner or the outer boundary
conditions are held fixed during the course of the
simulations. In the latter case, if the dislocation moves,
the boundary conditions are then no longer appro-
priate.
Another problem arises in the case of defects with
an infinite linear dimension such as dislocations. In that
case, the system is repeated periodically along this
linear dimension to mimic roughly the infinite case.
This approach can have strong influences on the
dynamics. For example, dislocation motion proceeds
by the formation of kinks that then propagate along the
dislocation line. If the periodic length along the disloca-
tion line is short, as is frequently the case, these kinks
have an artificial interaction with their periodic images
that can influence their behavior. The consequence of
these various boundary condition problems is that,
even with accurate interactions, it is difficult to make
quantitative predictions of the dynamic response.
An important use of atomistic simulations is for the
development and validation of descriptive models of
the energetics and properties of interfaces based on
larger length-scale models such as dislocation theory or
crystallography. An important property of an interface
is its energy or work of adhesion. The knowledge of
how these values vary with the five geometric degrees
of freedom associated with a description of a grain
boundary is of great importance but is beyond the
practical limit of experimental determination. The
Read-Shockley model [21] provides a description of
the energetics of low angle grain boundaries as a func-
tion of boundary orientation. The Read-Shockley
model treats the boundary as a collection of disloca-
tions and represents the energy as the sum of the dis-
location core energies and the strain energies
associated with the boundary. These models have
traditionally been viewed as meaningful only in the low
angle limit where the dislocations are well separated.
The applicability of this model to all grain bound-
aries has been tested by studying the systematics of
grain boundary energetics for a broad range of grain
boundary orientations as computed from atomistic
simulations [22]. This examination yielded the
unexpected result that the form of the energy-
misorientation curves from the Read-Shockley model
describes the variation in the energy over the whole
range of boundary misorientations, not just low angle
boundaries as previously assumed. This Read-
Shockley model does not predict the existence of
cusps, local minima in the energy vs. misorientation
relation. However, a similar analysis of the energy of
boundaries with orientations near an energy cusp in
terms of the densities of steps at the boundary yields a
description of the energy variation in that region.
Further examination of the energetics, combined
with consideration of the pair correlation functions at
the interface, has led to another observation concern-
ing boundary energies. Low energy grain boundary
orientations occur when the boundary planes in the
two crystals are dense-packed planes [22]. This gives a
simple geometric criterion for the prediction of low
energy boundaries.
Another problem where atomistic simulations are
used as a testing ground is the understanding of the
cross-over between ductile and brittle behavior at a
 W.E. King et al. / Materials Science and EngineeringAl
crack tip. At the tip, there are two competing pro-
cesses. The first is extension of the crack by way of
further crack plane cleavage. The second process is the
emission of a dislocation from the crack tip leading to
local stress reduction and blunting of the crack tip.
Recently, Beltz and Rice [23] have proposed an
atomic-scale criterion for the dislocation emission
process in terms of what they refer to as the “unstable
stacking fault energy”. This is defined as the energy
associated with displacing the two planes by half of the
Burgers vector and is a function of interplanar spacing.
The range of validity of this model has been
examined by Thomson [24] using atomistic simula-
tions. These simulations treated a two-dimensional
hexagonal lattice where the atoms interact through
model interatomic potentials and the motion of the
atoms away from the crack is computed using lattice
Green’s functions. When the crack is subjected to
mode II loading (shear in the plane of the crack), the
atomistic simulations are in accord with the Beltz-Rice
model. However, the results of the simulation in mode I
loading (tension normal to the crack plane) do not
correspond to the model. Analysis suggests that this
disagreement is due to the breaking of bonds that
occurs during dislocation emission in mode I that are
not observed in mode II. On the basis of this observa-
tion, Thomson has suggested a modified criterion that
appears to account for the results. This example shows
the value of atomistic simulations in developing models
of behavior in terms of longer length scales.
The energetic quantities that enter these models are
being probed in experiments by Kim [25]. The strain
field in the vicinity of a dislocation on an interface is
observed by high resolution electron microscopy com-
bined with some novel data smoothing techniques. The
displacement fields, together with the elastic proper-
ties, are used to evaluate the J integral on a path around
the defect. This analysis yields the energy associated
with the relative displacements of the atomic planes at
the slip plane. This quantity can be expressed as a sum
over the interatomic potentials. Thus these results can
be used as a test of a given interatomic interaction. In
addition, the unstable stacking fault energy discussed
above can be obtained from these results. These
experiments thus provide the means of evaluating the
atomistic concepts as well as “local” continuum
properties of interfaces.
An example of where atomistic calculations were
used to provide detailed information useful at the
larger length scales involves the calculation of the
elastic constants near an interface [26]. The idea is that
there is a structure, chemical composition and internal
stress state locally near an interface that is distinct from
the region away from the interface. A methodology was
developed to predict the components of the elasticity
(1995) l-16 9
tensor in the near interface atomic planes based on an
interatomic potential model combined with local
atomic arrangements and bulk elastic constants. The
calculations predict that the local variation in elastic
properties near the interface is anisotropic and varies
in a complex manner as a function of distance normal
to the interface. These calculated interfacial elastic
constants, as opposed to bulk values, have been used to
predict the “correct” behavior of Rayleigh and Stoney
waves local to the interface. Comparison between
atomistic simulations of these near-interface lattice
phonons with continuum calculations using the “inter-
facial” elasticity tensor described previously indicate
that this “bridge” between atomic-level phenomena to
the higher length scales has met with some success.
2.6. Electronic scale
Electronic-scale modeling and simulations attempt
to describe the behavior of the electrons in a material.
These methods provide details about total energy of
the nuclear-electron system. Electronic scale calcula-
tions can currently provide information such as binding
energy across an interface [27], to elastic constants
[28], and to interatomic and multisite potentials [1,29].
The goal of this theory is to provide information of
energetics of systems and local charge densities only
using atomic numbers and the lattice structure of the
system under study.
The electronic length scale constitutes the lowest
end of the length-scale spectrum that we wish to bridge.
There are smaller length scales, of course, such as
those associated with quarks and the formation of sub-
nuclear particles. However, it is unlikely that these
scales are relevant to the study of phenomena such as
the formation of dislocations, crack propagation, and
material toughness and strength. If we were to assign a
number to characterize the lengths that are relevant at
this end of the spectrum, we might settle on the radius
of the electron sphere, associated with the volume
occupied by each electron, or the electron density. This
number, which clearly varies with the system, is of the
order of several tenths of nanometers.
It may also be useful to characterize the length scale
by the kinds of operations that one can perform in
order to analyze the energetics of the various processes
that can take place. At the electronic end of the spec-
trum, such analysis is based on the Schrodinger
equation. Assuming a certain arrangement of sta-
tionary atoms (nuclei) in space, the single-particle
Schrodinger equation allows the evaluation of the total
energy of the ground state of the associated electron
gas system, which includes the kinetic energy of the
electrons, the interaction of the electrons with the
nuclei, the mutual repulsion of the nuclei, and the
10 W.E. King et al. / Materials Science and Engineering Al 91 (I 995) l-16
mutual repulsion of the electrons. Also, since electrons
are fermions that interact by way of Coulomb forces,
and cannot be distinguished one from another, the
effects of correlation and exchange are taken into
account in evaluating the total energy of the system.
The total energy of the nuclear-electron system [30] is
the basic material that one has at one’s disposal in
attempting to build a bridge toward the banks
associated with larger length scales. These types of cal-
culations can be carried out for translationally invar-
iant materials, bulk alloys, surfaces, and interfaces in
single-element solids, compounds, and alloys [ 1,301.
Having chosen the material to be used to build the
bridge, namely the energy of the electron system, we
may now proceed to cast this energy into a form that
projects the features controlling the atomistic scale.
Almost invariably, the energetics is associated with
effective interactions between or among atoms in the
system. This is not surprising in view of the fact that the
relevant phenomena under study are associated with
the distribution and motion of atoms whose study, in
turn, requires the knowledge of the forces acting on the
atoms themselves. The language used to describe these
interactions may vary from the binding energy across
an interface [27], to elastic constants [28], to inter-
atomic and multisite potentials [1,29]. The methods
that can be used in evaluating these various manifesta-
tions of the energy at the atomistic scale depend often
on the particular aspect of the problem that one wishes
to study.
In attempting an atomistic view of adhesion, Smith et
al. [27] are able to reduce the calculation of tensile
strengths and forces to the determination of a pair of
parameters entering a universal expression for the
binding energy across an interface. Coupled with the
values of the ground state energy of the system, this
approach allows one to predict whether a given
impurity would tend to occupy an interstitial or a sub-
stitutional site at a grain boundary, and the effect of the
impurity on the strength of the boundary. For example,
one finds that, on an Mo-MoSi, boundary, 0, C, and B
impurities would tend to occupy interstitial sites, in
contrast to the substitutional impurities of S and Nb.
All impurities investigated [27] would tend to reduce
adhesive energy. At the same time, interstitial impuri-
ties (0, C, B) increase peak interfacial strength, while
substitutional impurities (S, Nb) decrease it.
This approach was further applied to the study of
metal-ceramic interfaces [27]. In these studies, Al and
Ag atoms were found to be preferentially situated on
top of the 0 atoms in an MgO-metal interface. The
results of electronic structure calculations imply the
presence of a substantial ionic component, consistent
with the hybridization of metal and MgO states, includ-
ing the filled d band in Ag. Once again the adhesive
energy follows a universal law that is consistent with a
metallic-covalent bonding mechanism. One is also able
to deduce surface energies and ideal adhesive energies,
obtaining the results that the surface energy of Al is
smaller than that of Ag, and that the adhesive energy of
MgO/Al is smaller than that of MgO/Ag. Further
analysis allows one to correlate the work of adhesion
with contact angle, where very good agreement
between theory and experiment is obtained for both
quantities. Both the work of adhesion and the contact
angle are found to be affected by the presence of misfit
dislocations, as one might have expected.
Questions of bonding strength can also be addressed
by studying the magnitude of the pair contribution to
the energy associated with atoms across an interface.
This type of contribution follows from general total
energy expansions of a system in terms of many-body
interactions, and can be evaluated in a fairly straight-
forward manner through the use of multiple-scattering
theory [ 11. In this approach, one associates a small pair
contribution with a weak bond, and a large pair con-
tribution with a strong bond. The effects of many-body
interactions and of angular forces can also be assessed.
In principle, the effects of a grain boundary on elastic
properties can also be obtained, as well as shear and
tensile stresses.
In Eberhart’s approach [28], one concentrates on
the evaluation of elastic constants which one expresses
in terms of correlated charge rearrangements. Once
again, the approach consists of evaluating appropriate
derivatives of the total energy with respect to strain.
Presumably, small (elastic) displacements of atoms in
an interface region can be studied from the knowledge
of the elastic stress tensor.
In order to study atomic motion, one needs to know
the forces acting on the atoms as they move through
the space available to them. Such forces can be derived
from potentials and methods for evaluating such poten-
tials efficiently are currently being pursued. A particu-
larly promising method is based on the calculation of
bond orbitals and the associated rapidly convergent
expressions for the site diagonal and site off-diagonal
Green functions [29]. This approach makes use of
moment expansions of the local density of states and
leads to potentials that can be used in a straightforward
way in connection with numerical simulation tech-
niques to study the motions of large numbers of atoms.
This approach has been used to study surface recon-
struction such as that of the Si( 100) surface [29].
2.7. Critical experiments
Certin experiments can be identified which provide
data directly comparable with model predictions in
order to validate a model. Other experiments provide a
 W.E. Kinget al. / Materials Science and EngineeringAl
starting point for model calculations. Electronic struc-
ture calculations need the positions and types of atoms
at an interface. Transmission electron microscopy
(TEM) plays a key role in determining the geometry of
an interface by determining the positions of atomic
columns in the high resolution mode [31] while identi-
fying and quantifying the atomic species present in the
analytic mode [32]. While quantification of energy-
dispersive X-ray and electron energy loss spectra is a
well-established technique [33] in the analytic mode,
quantification of high resolution micrographs to pro-
vide the positions, with error bars, of atomic columns is
still in its infancy [34]. The development of this tech-
nique together with more accurate image simulation
techniques is a critical component in the application of
electronic structure calculations to real interfaces and
to the arbitration of differences in atomic-scale models.
There exist a host of spectroscopic methods to
investigate the electron energy states of surfaces and
near surface material [35]. Probing the bonding states
of a buried interface, however, requires a probe and
signal that can penetrate through a significant distance
of material. Perhaps the most useful method because of
its high spatial resolution is energy loss spectroscopy of
transmitted high energy electrons in the transmission
electron microscope [36], which reveals the density of
unoccupied states through its near-edge fine structure
as modified by the presence of a core hole [37]. In a
field emission transmission electron microscope, an
electron probe which is small enough to be mostly con-
fined to the interface can probe the bonding states of
the atoms at the interface and compare them with the
bulk. Density of states calculations would reveal
whether the bonding at the interface is being properly
modeled. Quantification of segregating impurities at
the interface and their effect on the interfacial bonding
can also be determined and compared directly with the
calculated effects of impurities.
Another quantity directly calculated by electronic
structure methods is the work of adhesion. Accessible
through experiment is the force needed to separate the
interface, yielding the maximum slope in the energy vs.
separation curve. Experiments that cause the rapid
separation of an interface, such as spallation due to the
passage of a shock wave, measure this quantity without
the complications of crack propagation and associated
plasticity [38,39]. The combination of electron energy
loss spectroscopy (EELS) to confirm the expected
bonding and a measure of the work of adhesion would
provide valuable parameters for larger-scale models.
Atomistic simulations require a model of inter-
atomic interactions that is computationally rapid,
hence must be approximate. Developmental models of
the interaction require experimental validation. A good
test of the model is the determination of grain bound-
(1995) I-16 11
ary or surface structures through high resolution
microscopy, TEM or atomic force microscopy (AFM),
and comparison with calculated structures. Materials
must be chosen which test those aspects of the model
interactions that are developmental. For example, a
model accounting for angular dependent interactions
needs to be tested using a material with covalent
character [40]. Again, quantitative methods of match-
ing experimental images with simulated images based
on a model structure are required [41]. Once con-
fidence is gained in a particular model it can be applied
to circumstances that are not necessarily accessible
through experiment.
Atomistic simulations can also model impurity
segregation to interfaces. Highly accurate measures of
impurity segregation can be obtained with mass spec-
troscopic techniques, where ions are emitted or ejected
from the intersection of an interface with a surface. The
techniques include field ion microscopy (FIM) [ 181 and
focused ion beam mass spectroscopies [42]. The
accuracy of the predicted segregation isotherms can
then be evaluated.
Atomistic simulations can also calculate surface
excess elastic constants. These elastic constants will
determine, for example, the energy and dispersion of
interface phonons [26]. Access to the energies of sur-
face and interface phonons is available through EELS
[361.
Monte Carlo techniques applied to atomistic simula-
tions yield thermodynamic quantities at quasi-
equilibrium. Excess thermodynamic quantities of
interfaces, such as the free energy, are a key connection
to larger-scale phenomena. Data on these quantities
would provide validation of the simulations when
applied to new systems. There are very few techniques
[43] which measure the energies of interfaces directly.
Two well-established methods are sessile drop and
zero creep experiments. Relative energies can be deter-
mined through wetting experiments or the careful
observation of microstructural development during
heat treatments of polyphase materials.
Atomistic simulations are often applied to investi-
gate the competition between crack extension and
dislocation emission at the tip of a crack in order to
understand the ductile to brittle transitions observed in
many materials. The observation of dislocation
emission from a crack tip subjected to a well-defined
stress state is a potential link to real material behavior.
Single dislocations have been observed being emitted
from a sharp crack in Si (at temperatures above its
transition temperature) in the transmission electron
microscope [44]. This experiment done with a known
stress intensity at the crack tip would be a strong link
between atomistics and crystal plasticity. A related
issue is plasticity at a heterophase interface as a
12 W.E. Kinget al. / MateriaIsScience and Engineering A191 (1995) l-16
function of the orientation of the plastically deforming
crystal with respect to the boundary [45]. A series of
mechanical tests on bicrystals of differing orientation
explores this dependence. A systematic exploration of
the effect of the work of adhesion and interfacial
strength on the extent of crystal plasticity could lead to
constitutive relations suitable for use at the continuum
level. The effect of interface adhesion could be
explored through controlled interface doping.
Another class of interfaces is those which are purely
constrained by friction. Frictional sliding and lubri-
cated sliding are important parameters in the mechani-
cal strength and fatigue life of a class of brittle matrix,
fiber reinforced composites [46]. Tribological studies
to determine the most important parameters influenc-
ing the sliding resistance of the interface can help the
model to predict the best microstructure to achieve a
desired matrix cracking strength, ultimate tensile
strength, or fatigue resistance.
At the meso to macro scale, experiments are
designed to explore properties explicitly desirable for
the particular application. The models created are
microstructural and geometry specific to the point that
a particular experiment or class of experiments would
shed little light beyond the immediate application.
3. Analysis of critical issues
3.1. Introduction
In this section, we evaluate the outstanding issues at
each length scale. We cite limitations in current models
and simulations and identify areas that need more
work.
3.2. Macro issues
Numerous issues exist at the macroscopic level that
influence interfaces and thus the commercial utilization
of advanced materials. Many of these issues associated
with interfaces are fundamental and involve predic-
tions of local structure as well as resulting properties.
For local structure, the influence of different matrices
and local alloying elements on the interfacial reaction
needs to be predicted. This is a very complex problem
in which non-equilibrium reaction products are pro-
duced and equilibrium thermodynamics is not applic-
able. The kinetics of interface reaction is also
important including an understanding of how inter-
faces degrade with time. In MMCs the surfaces of rein-
forcement are not well characterized. In most cases
these surfaces do not possess the bulk chemistry of the
structure. Techniques need to be developed that will
characterize these interfaces. The techniques should
provide both local composition and structure. These
techniques need to be sensitive to small changes in
composition, segregants and impurities. Experiments
are also needed that will realistically simulate these
interfaces in a manufacturing environment.
For the resulting interface properties a critical issue
is the ability to predict interface strength. Experimental
techniques are needed that will characterize the local
strength of an interface. The mechanisms of critical
engineering properties such as fracture, fatigue and
wear need to be understood. Specifically the initiation
and growth of cracks at interfaces should be predict-
able from the results of calculations done at lower
length scales. The influence of these cracks or damage
on the desired property (e.g. fatigue life or fracture
toughness) needs to be adequately predictable.
3.3. Continuum issues
In describing interfacial phenomena at a continuum
level, many critical issues remain. One of the major
issues is to determine how discrete cracks interact with
interfaces. This includes the response of cracks that
approach interfaces as well as interfacial cracks them-
selves. Although smaller length-scale phenomena
clearly govern the continuum behavior, the conglomer-
ate response must be resolved. Some of the important
aspects that need to be clarified are what types of
“deformation” processes are involved and what
material properties are needed to describe these
events, e.g. interface-interphase stiffness, strength, and
toughness. Damage modeling, Lg. isolated and distri-
buted crack propagation, represents another formid-
able task to continuum modeling owing to its inherent
complexity. Damage models are necessary if the
distributed conglomerate response is to be represented
in a useful manner. While continuum techniques can
effectively explore parameter spaces, they are less
effective at simulating the effects of spatial variations in
geometry and material behavior variability. However,
one of the attractions to continuum models is that
many schemes exist to solve them including classical
mathematical and numerical methods, e.g. FE and
finite differences methods.
In continuum approaches, like mesoscopic and
microscopic formulations, extensive progress has
already been made in modeling interfacially controlled
behavior. Unfortunately, the problems are less well
defined than at the lower length scales owing to the
large numbers of variables involved and inherent statis-
tical variability of material properties and geometries.
3.4. Meso issues
Mesoscopic modeling hinges on the ability to distill
a simple and tractable model from the complex govern-
ing physics. Hence, developing useful models poses a
 W.E. King et ul. / Materiuls Science and Engineering A I91 (I 995) I-I h
formidable task. Several reasons for this are that the
precise forms of the governing relationships and the
material properties of the interfacial responses are
lacking, there is a distribution of both geometries and
local properties, and scaling relationships are not fully
understood. For example, some existing models have
approximated the interfacial force-displacement
response as that of a linear spring with a finite fracture
strength (force). While this has provided new insights,
more detailed and physically motivated interfacial
models would clearly capture additional physics,
reduce the number of ad hoc assumptions, and, it is
hoped, improve the macroscopic predictions. To date,
successful models rely on numerical methods to
predict distributions of macro stress-strain responses
and discrete quantities (e.g. fracture strength) as a
function of input variabilities. While providing insight
into the problem, the output of these models is
inherently statistical in nature and has not yet yielded
“closed-form” solutions. As the complexity in models
increases the mathematics used to solve these prob-
lems may become an additional barrier.
3.5. Micro issues
For many decades the focus of traditional mechani-
cal metallurgy has been to develop deformation and
fracture mechanisms based on micro-scale phenomena
and then to derive constitutive relationships useful at a
continuum level. Thus, the crystallography and con-
tinuum field quantities associated with micro-scale
defects, e.g. dislocations and grain boundaries, are
understood to a large degree. Despite this understand-
ing and the many successes to which it has led,
challenges remain in many areas, particularly where
interfaces play a key role in determining bulk material
behavior. Many of these challenges center on the con-
tinuing need to quantify the geometrical distributions
and collective behavior of the micro-scale defects and
their interactions with interfaces, including subgrain
and grain boundaries. Once gained, this knowledge
then must be used judiciously to derive constitutive
laws useful at the higher length scales. For inter-facially
controlled materials, significant progress has been
made in some areas, for example understanding the
nature and effects of interactions between dislocations
and high angle grain boundaries. In other cases, for
example nanocrystalline metallic materials, the
mechanisms of grain boundary strengthening are still
under investigation, and the critical defect(s) control-
ling deformation are not yet identified with certainty.
3.6. Atomistic issues
There are two broad areas of work that need to be
pursued before atomistic simulations can become a
13
widely used source of input to the larger length scales.
The first is that interatomic interactions need to be
developed that can be used reliably for a wide range of
materials. Currently, there exist approaches that work
only within limited parts of the periodic table. The
need exists to be able to treat more elements and
arbitrary combinations of elements. While progress is
being made in this direction, we are far from these
goals. The other area is understanding the systematics
of the properties of defects. Some work in this direc-
tion is in progress, as evidenced by the work presented
at this workshop. More effort in this direction is
needed because it will never be the case that the
properties of every specific defect can be calculated (or
measured for that matter). Thus the trends with respect
to all the relevant parameters, including orientation
and composition to name a couple, need to be under-
stood to go from the calculation of the properties of a
few interfaces to a prediction of typical properties and
to a prediction of the variability in properties.
3.7. Electronic issues
In order to provide a reliable determination of
parameters, such as interatomic potentials to be used in
atomistic calculations, electronic structure calculations
must be carried out in a way that takes into account
accurately the specific spatial constraints of the system
under study. For example, they must be able to treat
properly the charge distribution and the potential
inside a unit cell in a material, either ordered or dis-
ordered. They must also be able to satisfy the correct
boundary conditions associated with a defect such as a
surface or an interface.
3.8. Experimental issues
Experiment relates synergistically to theory. Results
from experiments act to validate and determine the
limits of extant theories. Simultaneously they spur the
development of new theories. Experimental efforts can
be divided into two broad categories: the structure and
chemistry of interfaces and the behavior of interfaces.
Since the behavior of interfaces depends on the struc-
ture and chemistry, the two areas are usually combined
in an experimental investigation. The role of theory is
to explain this relationship.
The structure and chemistry of interfaces is nearly
confined to two dimensions. To characterize an inter-
face normal to its plane, techniques with high spatial
resolution are required, and hence the emphasis on
TEM, FIM, and AFM. Continuing improvement in
resolution of structure and sensitivity to chemistry
increasingly broadens the capability and applicability
of these techniques. Truly atomic-scale information is
becoming available.
14 W.E. King et al. / Materials Science and Engineering Al 91 (I 995) I-16

The use of this detailed information to interpret the 4. Summary

behavior of interfaces is usually possible only in highly
controlled circumstances. Model experiments are How then does one go about building a bridge
necessary to control the overwhelming complexity across a gap in the length scale? It seems that one may
often associated with systems of practical interest. not want to attempt a direct jump from the electronic
Hence it is increasingly important to design properly scale to the observable world in an attempt to under-
the experiment in order to link the structure and stand the phenomena under consideration here
chemistry of interfaces to their behavior through (although such direct bridges are in existence in many
theory. other cases, of a different nature, such as spectro-
Two fundamental materials properties are the work scopy). Perhaps a systematic correlation of data span-
of adhesion and strength at an internal interface. The ning a given gap in the spectrum of length scales may
work of adhesion corresponds to the spatial integral of provide motivation for thought and analysis that could
the energy-separation relationship for an interface in lead to understanding. This sort of systematic correla-
absence of other energy dissipative mechanisms. The tion certainly exists in many isolated cases, and it may
strength is the point of maximum slope. In simple need only compilation and presentation in a form that
terms, the work of adhesion corresponds to the amount would be meaningful to those who walk the banks
of energy required to sever the electronic bonds at an across scale gaps. Where it does not exist, an effort
interface and to rearrange the new surfaces to form a should be made to produce such systematic compila-
stable configuration. Adhesion and interface strength tions and meaningful presentations.
are important quantities for length scale bridging
because they influence and perhaps control the activa-
tion of other dissipative mechanisms at higher length Acknowledgments
scales, such as plastic deformation, which determines
the interfacial toughness. The authors would like to express their appreciation
It should be pointed out that the definitions of to the Institute for Mechanics and Materials at the
adhesion and strength given above refer to funda- University of California at San Diego for providing
mental quantities. Often in practical application, the funding and organizational support for this workshop.
terms adhesion and strength take on different mean- The authors further extend their thanks to the invited
ings. Practical adhesion and practical interface strength speakers for their participation. This work performed
refer to the same quantity, the critical far field stress under the auspices of the Division of Materials Science
required to drive a crack. of the Office of Basic Energy Sciences, US Department
It is already possible to apply existing models to of Energy, and the Lawrence Livermore National
predict or describe interfacial adhesion. Take for Laboratory under Contract W-7405-Eng-48.
example the work of Smith et al. [27] who have
employed ab initio electronic structure calculations to
obtain so-called univeral bonding relationships. It Appendix A: Invited speakers
should also be possible to probe this relationship using
current generation atomistic simulations. Probing this A. Sachdev General Motors Research and
relationship experimentally will require very short time Development
scales to avoid other energy dissipative processes. A. Gaimei United Technologies Research
Interfacial toughness is the energy required to pro- Center
pagate a crack stably along the interface for a unit A. Argon Massachusetts Institute of
increase in crack area. This energy is dissipated Technology
through a number of mechanisms, e.g. creation of new R. McMeeking University of California-Santa
surface area (either to advance the crack or incidental Barbara
crack branching or microcracking), plastic deforma- K. S. Kim Brown University
tion, and phonon emission. The magnitude of the dissi- T. Lowe Los Alamos National Labora-
pated energy will depend on a complex interplay of the tory
operative mechanisms. Relating this interplay to the H. Kirchner University of Paris
atomic, micro-, and macrostructure of the interface, K. Liechti University of Texas
which in turn determines the adhesion and strength of J. Bassani University of Pennsylvania
the interface, is the key to understanding and P. Duxbury Michigan State University
controlling interfacial toughness. M. Ostoja-Starzewski Michigan State University
J. Weertman Northwestern Univesity
 W.E. King et al. / Materials Science and Engineering A191 (1995) l-16 15

R. Thompson National Institute of Standards 1131 P.M. Duxbury, Variability in interface properties: a key
and Technology factor in bridging the length-scale gap, Theory, Simulation,
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R. Hoaglund Washington State University Length-Scale Gap, La Jolla, CA, September 12-15,1993.
S. Suresh Brown University [I41 M. Ostoja-Starzewski and I. Jasiuk, Meso-scale continuum
D. Wolf Argonne National Laboratory models of heterogeneous materials: interphase problem in
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S. Foiles Sandia National Laboratories, tion, and Modeling of Interfaces in Materials-Bridging the
Length-Scale Gap, La Jolla, CA, September 12-15, 1993.
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