SCIENCE’S COMPASS ● REVIEW

Graded Materials for Resistance to Contact

Deformation and Damage
S. Suresh
in graded materials primarily focused on con-
The mechanical response of materials with spatial gradients in composition and trolling thermal stresses in structures exposed
structure is of considerable interest in disciplines as diverse as tribology, geology, to very high temperatures (⬃2000 K) in com-
optoelectronics, biomechanics, fracture mechanics, and nanotechnology. The damage ponents used in aerospace applications and
and failure resistance of surfaces to normal and sliding contact or impact can be solid-oxide fuel cells, and in energy conver-
changed substantially through such gradients. This review assesses the current un- sion systems using thermoelectric or thermi-
derstanding of the resistance of graded materials to contact deformation and damage, onic materials (15). The use of graded layers
and outlines future research directions and possible applications for graded materials. and interfaces in materials exposed to high
temperatures for long periods of time, how-
ever, is complicated because of diffusion.
Research has therefore increasingly focused

T
he composition, structure, and me- traced back to the blades of Japanese steel on lower temperature applications of graded
chanical properties of a material may swords using a graded transition from a softer materials on the basis of their resistance to
vary, continuously or in discrete steps, and tougher core to a hardened edge (5). contact damage. This research direction was
with depth beneath a free surface. Gradations Carburizing and nitriding treatments are com- also motivated by advances in techniques for
in microstructure and/or porosity are com- monly given to steel surfaces to impart hard- controlled indentation and by a growing need
monly seen in biological structures such as ness, and fatigue and wear resistance in trans- to develop damage-resistant surfaces and
bamboo, plant stems, and bone, where the mission gear teeth. However, theoretical un- coatings—for example, in magnetic storage
strongest elements are located in regions that derstanding of such phenomena has not re- media, nano- and microelectromechanical
experience the highest stresses (1, 2). Gradual ceived much attention. systems, barrier coatings for structural com-
changes in the elastic properties of sands, Graded transitions in composition, either ponents, dental implants, articulating surfaces
soils, and rocks beneath Earth’s surface in- continuous or in fine, discrete steps, across an in hip and knee prostheses, and penetration-
fluence the settlement and stability of struc- interface between two dissimilar materials resistant materials for armor plates and bul-
tural foundations, plate tectonics, and the (such as a metal and a ceramic), can be used to let-proof vests (16).
ease of drilling into the ground (3, 4). In redistribute thermal stresses (6, 7), thereby lim-
engineered materials, gradations in composi- iting the stresses at critical locations and thus Contact Resistance of Graded Surfaces
tion occur unintentionally, for example, as a suppressing the onset of permanent ( plastic) The indentation of a surface with a sharp or
consequence of lattice and grain boundary deformation, damage, or cracking (8, 9). Grad- blunt probe (indenter) provides basic and
diffusion, oxidation, and clustering of atomic ed transitions can also reduce stress concentra- quantitative information that typifies the re-
species or reinforcement particles. In many tions at the intersection between an interface sistance of the surface to normal contact. If
cases, such gradations may not even be de- and a free surface (10, 11). Similarly, the local the spatial variation of the mechanical prop-
sirable. Learning from nature, materials sci- driving force for crack growth across an inter- erty with depth beneath the indented surface
entists increasingly aim to engineer graded face can be increased or reduced by altering the is well defined and known a priori, analysis
materials that are more damage-resistant than gradients in elastic and plastic properties across of the indentation load versus indenter pene-
their conventional homogeneous counter- the interface (12, 13). Smooth transitions in tration depth into the surface can also provide
parts. This is particularly important at surfac- composition across an interface also improve valuable information about the contact-dam-
es or at interfaces between dissimilar materi- interfacial bonding between dissimilar materi- age resistance of the surface.
als, where contact failure commonly occurs. als (2), thereby facilitating the deposition of Theories of normal elastic contact. Over
With established methods currently available much thicker surface coatings (typically more the past several decades, the geomechanics
to synthesize and process materials, grada- than 1 mm thick) than is feasible with sharp community has studied the evolution of
tions in composition, structure, and properties interfaces. In some applications, such as diesel- stresses and displacements, under a point
could be engineered over a wide range of engine piston heads, thicker coatings impart load, in elastically graded substrates (3, 4,
length scales ranging from nanometers to better protection against thermal degradation. 17–22). In these studies, the Young’s modu-
meters. Thin films with graded composition play an lus, E, was varied as a function of depth
important role in heteroepitaxial multilayers beneath the indented surface, z, according to
Motivation for the Use of Graded used in semiconductor devices. The graded the power-law function E ⫽ E0z k, where E0 is
Materials films are deposited between a substrate and a the reference Young’s modulus at the surface
It has long been recognized that gradients in quantum well to control the density and kinetics and 0 ⱕ k ⬍ 1 (k ⫽ 0 for a homogeneous
surface composition can improve the me- of threading dislocations. They protect the material). Such variations in elastic modulus
chanical performance of a material [e.g., (1, quantum wells and light-emitting diodes with are typically seen in sandy soils and consol-
2)]. Early examples of the use of synthetic specific optoelectronic properties from the del- idated clay deposits. These studies did not
materials with graded properties can be eterious effects of these dislocations, which are provide general solutions of the variation of
introduced at interfaces as a result of lattice indentation load (P) with the depth of pene-
Department of Materials Science and Engineering,
mismatch and thermal expansion mismatch tration (h) of the indenter into the surface for
Massachusetts Institute of Technology, 77 Massachu- strains during layer deposition (14). common indenter geometries (such as a
setts Avenue, Cambridge, MA 02139 – 4307, USA. In the late 1980s and early 1990s, interest sphere, cone, cylinder, or a pyramid) or with

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 SCIENCE’S COMPASS
the contact radius, a, of the indenter with the mal residual stresses, thereby complicating phases), with a power-law increase in modu-
substrate, which are needed for direct exper- interpretations of such experiments. This lus beneath the sliding surface, showed that a
imental validation of such theories. problem can be circumvented by synthesizing graded material with a 40 vol. % soft glass
A general theory for frictionless normal a “clean” model system in which the constit- phase at the surface could sustain as high a
indentation of elastically graded materials by uent phases have the same coefficient of ther- load as the homogeneous alumina without
point loads and axisymmetric indenters was mal expansion (CTE) and Poisson ratio (␯), developing any “herringbone” cracks (26).
recently developed (23) for two general vari- but markedly different Young’s moduli. These circular cracks develop around the
ations in Young’s modulus with respect to Such a graded elastic system has been contact perimeter under the influence of the
depth: the power-law variation, E ⫽ E0z k, produced by infiltrating an oxynitride glass maximum principal tensile stress (27, 28).
and an exponential variation, E ⫽ E0e␣z into a fine-grained ␣-Si3N4 matrix (24). The The graded composite could sustain a normal
(where 1/␣ signifies a length scale associated ␣-Si3N4 matrix, consisting of 93.7% of the load more than twice that carried by the
with the gradient in modulus beneath the bulk Si3N4, contained elongated grains, 0.5 monolithic glass before herringbone cracks
surface when ␣ ⫽ 0), for any specific value ␮m in diameter and 2 ␮m in length, in a glass developed in the glass. Despite its low
of Poisson ratio, ␯ (the ratio of the negative of matrix. The infiltrated oxynitride glass, here- strength and low toughness at the contact
the lateral strain to the axial strain in a uni- after referred to as SiAlYON, had a chemical
axial tension test), which was taken to be composition close to that of the glass matrix
spatially invariant. Explicit analytical expres- in the bulk Si3N4. Infiltration of SiAlYON at
sions were derived to relate the indentation 1500°C for 2 hours produced a continuously
load, P, to the penetration depth, h, or the graded elastic composite, with ⬃30 volume
contact radius, a, for different indenter geom- % glass at the surface gradually decreasing to
etries. Computer simulations of the simulta- 0% about 0.5 mm beneath the surface (Fig.
neous variation of the Poisson ratio, ␯, with 2A). The elastic modulus of ␣-Si3N4 is 320
depth revealed that the effect of varying ␯ GPa and that of SiAlYON glass is ⬃110
was substantially smaller than that of varying GPa; ␯ ⬇ 0.22 for both materials. The CTE of
E. ␣-Si3N4 is essentially the same as that of the
Predictions of resistance to normal elastic infiltrated glass, and therefore no long-range
contact. Consider an elastically graded mate- internal stresses develop in the graded com-
rial with constant ␯ that is subjected to inden- posite. However, because the modulus ␣-
tation by a rigid sphere of radius R (Fig. 1A). Si3N4 is three times that of glass, a change in
Let the Young’s modulus increase or de- glass composition from 30% at the surface to
crease exponentially, or remain constant as a 0% 0.5 mm beneath the surface resulted in a
function z (Fig. 1B). A homogeneous elastic corresponding smooth variation of elastic
material exhibits an indentation response for modulus from about 225 GPa at the surface to
which P scales with h1.5 (Fig. 1C). If E about 315 GPa over the same depth (Fig. 2B).
increases beneath the indented surface, the In a cross section perpendicular to the
indentation response is stiffer; the stiffness of indented free surface of the homogeneous
the response reaches a vertical asymptote as ␣-Si3N4 ceramic (Fig. 2C), classic Hertzian
the limit of the exponential increase in elastic cone cracks are seen after spherical indenta-
modulus is reached. If ␣ ⬍ 0, the elastically tion to a maximum load of 3 kN with a
softer material beneath the indented surface WC-Co indenter with a radius of 4.76 mm.
promotes a compliant response compared These cracks form at the contact perimeter
with a homogeneous solid; the indentation where the maximum tensile stresses develop.
load-carrying capacity vanishes in the asymp- Homogeneous SiAlYON glass, and a nitride/
totic limit as E decreases exponentially be- glass composite of uniform composition
neath the surface. equal to the surface composition of the grad-
Theory (23) also predicts that when the ed material, develop similar cone cracks un-
modulus increases (or decreases) monotoni- der spherical indentation. Despite the lower
cally with depth, peak values of local tensile strength and lower toughness of the glass at
stresses, which result in the nucleation of the surface, the graded nitride-glass compos-
damage at the surface, are spread further into ite could sustain an indentation load as high
the interior (or moved closer to the surface) as that in homogeneous ␣-Si3N4 without Fig. 1. Indentation response of an elastically
compared with a homogeneous material. This forming any cone cracks (Fig. 2D), solely as graded surface. (A) Details of the contact re-
is because the underlying material has a high- a consequence of the reduction in maximum gion underneath the spherical indenter subject-
er (or lower) E than the surface and can thus tensile stress at the contact surface due to ed to a load P. (B) Schematic illustration of an
sustain a greater (or lower) stress. grading. Similar beneficial effects of modu- exponential increase (␣ ⬎ 0) or decrease (␣ ⬍
0) in Young’s modulus as a function of depth z
Experimental evidence. Experimental ver- lus gradations have been demonstrated in a beneath the indented surface; E ⫽ E0e ␣z, where
ification of the effect of a continuous elastic fine-grained aluminum oxide infiltrated with E0 is Young’s modulus at the surface and ␣ ⫽ 0
gradation on indentation cracking resistance aluminosilicate glass (25). represents an elastically homogeneous materi-
requires a composite microstructure with at Resistance of graded materials to sliding- al. (C) Schematic illustration of the variation of
least two different constituent phases of dif- contact damage. Experiments of frictional normalized indentation load as a function of
ferent elastic moduli, whose relative concen- sliding of spheres on elastically graded sur- normalized depth of penetration for the homo-
geneous and graded surfaces. For the graded
trations are gradually changed beneath the faces also point to the beneficial effects of surfaces, the variation of P with the penetration
surface. Synthesis of such a system at elevat- modulus gradients. Frictional sliding by a depth h is a complex function of the surface
ed temperatures and subsequent cooling to steel sphere on an alumina-glass graded com- and indenter properties, the indenter radius,
room temperature would introduce large ther- posite (with CTE-matched alumina and glass and the gradient in elastic modulus ␣ (23).

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response is a function of the gradient in into contact-damage suppression and wear tion highlights some possible applications, and
strength, m, indenter shape and tip geometry, resistance remains to be established through examines key challenges.
and strength (Fig. 4C). If ␴y decreases with systematic experiments. Such studies should With recent advances in instrumented
depth, the material rapidly loses its capability also assess the complex interactions among micro- and nano-indentation (36 ), depth-
to sustain the indentation load, and the in- contact loads, contact geometry, property sensing indentation is rapidly becoming a
denter sinks into the substrate. If ␴y increases gradients, the mechanics of contact fracture research tool to characterize the elastic,
beneath the indented surface, the indentation and fatigue at surfaces, and the evolution of plastic, and fracture characteristics of a
stiffness is higher compared with that of a wear damage in different environments. variety of engineering materials and surfac-
plastically homogeneous material. Issues of length scale. Analyses of homo- es at length scales approaching atomic and
A comprehensive theoretical framework geneous, isotropic materials by contact me- molecular dimensions. Such interest is also
for the interpretation of blunt and sharp in- chanics require consideration of different spurred by the rapid miniaturization of fea-
dentation of plastically graded metals with length scales. For continuum analyses to be tures and components in microelectronic
different strain-hardening characteristics is valid, mechanical length scales, such as the devices, magnetic storage media, and nano-
presently unavailable. The extent to which contact radius a or the depth of penetration h and microelectromechanical structures. Ex-
changes in the P-h response arising from (which are influenced by the shape and size amples include electromechanical and bio-
plasticity gradients at the surface translate of the indenter), should be large compared logical sensors and actuators, and miniature
with the characteristic structural size scale power devices such as microturbines, mo-
such as grain size. In graded systems (for tors, and pumps (37, 38).
example, Fig. 2), the zone of influence of the In many of these applications, graded sur-
contact loads beneath the indented surface faces provide appealing prospects for control-
should be sufficiently large to capture signif- ling surface damage and failure during re-
icant variations in elastic and plastic proper- peated contact. Progress in materials synthe-
ties. In geological systems, this size scale sis—for example, by molecular beam epi-
could be hundreds of meters (as in the case of taxy, vapor deposition, three-dimensional
drilling to lay the foundation for a tall struc- printing, bulk and surface micromachining,
ture), whereas for nanostructured coatings it and lithography—now afford the flexibility
could be as small as a few nanometers. The to fabricate gradients at surfaces with dimen-
yield strength of metallic films scales with sions approaching a few atomic layers to
the square root of the dislocation density, and macroscopic size scales (1, 2, 37, 38). How-
therefore gradients in dislocation density over ever, systematic studies of the effects of com-
small distances beneath a surface could also positional gradation on the indentation re-
induce plasticity gradients which, in turn, sponse and contact-damage resistance and
could strongly influence nanoindentation re- failure of crystalline and amorphous solids
sponse. Although strain-gradient plasticity and surface coatings have thus far not been
theories seek to address such length-scale conducted. The mechanisms of damage evo-
issues by accounting for higher order effects lution in these situations also have not been
(32, 33), systematic experiments at different examined by characterization techniques
length scales, which would provide estimates such as atomic force or electron microscopy.
of the regions of validity of such theories, are Further interest in the resistance of graded
currently unavailable. materials to contact loading stems from their
Continuum descriptions of elastic indenta- possible use as penetration-resistant surfaces.
tion response are known to be valid to indenta- Hertzian cone cracks (Fig. 2C) are
tion penetration depths as small as a few nano- known to be deleterious to contact resis-
meters (34). However, experiments show (34, tance and tribological performance at sur-
35) that even homogeneous thin films of crys- faces. The suppression of such cracks
talline metals exhibit discrete jumps in inden- through modulus gradients provides one
Fig. 4. Conical sharp indentation of a plasti- tation response as a consequence of defect nu- avenue for enhancing the contact-damage
cally graded surface. (A) Details of contact cleation and motion. In general, gradients in resistance without introducing tensile resid-
around the conical indenter. The included tip elastic and plastic properties in the vicinity of ual stresses in the bulk. Alternative meth-
angle of the conical indenter is 2␥. (B) Stress-
stress response, ␴, versus ε at three different
the surface should be tailored in such a way that ods, such as tempering, layering, phase-
points (1, 2, 3) below the indented surface. the field of indentation produced around the transformation, coating, ion-exchange, dif-
(C) The yield strength of this rigid plastic contact region samples the entire length scale ferential densification, grinding, and sur-
material, ␴y, either increases or decreases over which property gradients occur, so that the face heat treatment, promote compressive
linearly with depth below the surface z (as full effect of compositional gradation can be residual stresses at contact surfaces but also
indicated by the red or green straight line, realized. lead to the concomitant generation of ten-
respectively). The yield strength value is ␴y,0
at the surface, and the slope of the ␴y versus
sile residual stresses in the bulk of the
Outstanding Scientific Issues and material (24, 25), which can promote crack-
z plot is m. For a plastically homogeneous
surface indented by a conical indenter, P Challenges ing. On the other hand, the introduction of
scales with h 2. However, for the graded sur- The use of graded materials in contact-critical heterogeneities, such as second-phase parti-
face, theory (31) indicates that P ⫽ C1h 2 ⫹ applications has important implications for a cles, to introduce compressive residual stress-
C2h 3, where C1 ⫽ 11.88␴y,0(tan ␥)2, and C2 ⫽ multitude of disciplines. Studies of the effects es at surfaces and thereby suppress contact
Bm␴y,0(tan ␥)3, where B ⫽ 13.86 for m ⬎ 0
and B ⫽ 16 for m ⬍ 0. A positive (negative)
of compositional, structural, and property gra- cracks has the deleterious effect of imparting
value of m leads to a stiffer (more compliant) dients on the resistance of surfaces to normal, nonlinearity to the deformation response of
indentation response than that for a homo- sliding, rolling, or fretting contact and wear the material which, in turn, can lead to an
geneous material for which m ⫽ 0. have only recently begun to emerge. This sec- inferior tribological response and fatigue life.

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It is important to note that the use of a Such gradients in pore concentration could 12. A. S. Kim, S. Suresh, C. F. Shih, Intl. J. Solids Struct. 34,
low-strength and low-toughness layer at a 3415 (1997).
also be used to facilitate the growth of bone
13. A. S. Kim, J. Besson, A. Pineau, Intl. J. Solids Struct. 36,
contact surface could lead to an increased and tissue in many biomedical applications. 1845 (1999).
susceptibility to wear damage and material In polymeric materials (such as ultrahigh mo- 14. E. A. Fitzgerald et al., J. Vacuum Sci. Tech. B 10, 1807
loss, despite the benefits of suppressing in- lecular weight polyethylene, which is used, (1992).
15. T. Hirai, in Materials Science and Technology—A
dentation cracks during normal loading and for example, in knee prosthesis), gradients in Comprehensive Treatment, R. J. Brook, Ed. (VCH,
frictional sliding. Several different strategies elastic properties can be induced by the in- Weinheim, Germany, 1996), vol. 17B, Part 2, pp.
can be implemented to overcome these limi- troduction of spatial variations in degree of 293–341.
16. W. Kaysser, Ed., Proceedings of the Fifth International
tations. First, methods other than infiltration crystallinity and/or molecular weight. Conference on Functionally Graded Materials,
can be used to develop stepwise gradients in In summary, recent theoretical and experi- Dresden, Germany, October 1998 (Trans Tech Publi-
elastic moduli at the surface where the mod- mental work has established that controlled gra- cations, Zurich, Switzerland, 1999).
17. V. I. Mossakovskii, Prikl. Mat. Mekh. 22, 123 (1958).
ulus increases from a hard surface layer (such dients in mechanical properties offer unprece- 18. R. E. Gibson, Geotechnique 17, 58 (1967).
as Si3N4) to a graded layer (with Si3N4 and dented opportunities for the design of surfaces 19. N. A. Rostovtsev, K. Khranevskaia, Geotechnique 35,
SiC phases). Such graded materials have with resistance to contact deformation and 1053 (1971).
been synthesized by sintering to enhance re- damage that cannot be realized in conventional 20. R. E. Gibson, G. C. Sills, Q. J. Mech. Appl. Math. 28,
233 (1975).
sistance to both contact damage and wear homogeneous materials. With currently avail- 21. X. Calladine, J. A. Greenwood, Q. J. Mech. Appl. Math.
(24). Second, a thin (less than 1 ␮m thick) able materials synthesis and processing capabil- 31, 507 (1978).
surface layer of a hard, wear-resistant coat- ities, engineered gradations in properties, over 22. J. R. Booker, N. P. Balaam, E. H. Davis, Int. J. Num.
Anal. Methods Geomech. 9, 353, (1985).
ing, such as a layer of diamond-like carbon, nanometer to macroscopic length scales, offer 23. A. E. Giannakopoulos, S. Suresh, Int. J. Solids Struct.
could be deposited on the graded surface. appealing prospects for the design of damage-, 34, 2357 (1997).
Because such coatings could be deposited fracture-, and wear-resistant surfaces in appli- 24. D. Pender et al., Acta Mater., in press.
25. J. Jitcharoen et al., J. Am. Ceram. Soc. 81, 2301
with a Young’s modulus range of 45 to 250 cations as diverse as magnetic storage media, (1998).
GP and with significant improvements in microelectronics, bioimplants for humans, load- 26. S. Suresh et al., Acta Mater. 47, 3915 (1999).
wear resistance, elastic moduli gradations bearing engineering structures, protective coat- 27. B. R. Lawn, Fracture of Brittle Solids (Cambridge Univ.
could be introduced near the contact surface ings, and nano- and microelectromechanical Press, Cambridge, ed. 2, 1993).
28. K. L. Johnson, Contact Mechanics (Cambridge Univ.
while maintaining a wear-resistant layer at systems. Press, Cambridge, 1985).
the top layer of contact. If the elastic field of 29. O. Joergensen, A. E. Giannakopoulos, S. Suresh, Int. J.
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niques et Universitaires Romandes, Lausanne, 1995). ratory for Experimental and Computational Microme-
Wear-resistant, nanocrystalline surface Several articles in this volume describe examples of chanics, Massachusetts Institute of Technology, Cam-
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can be tailored beneath contact surfaces to 9. A. E. Giannakopoulos, S. Suresh. M. Finot, M. Olsson, 40. The preparation of this manuscript was supported by
Acta Metall. Mater. 43, 1335 (1995). the United States Air Force, Office of Scientific Re-
improve resistance to contact damage as, for
10. F. Erdogan, A. C. Kaya, P. F. Joseph, J. Appl. Mech. 58, search (grant F49620-00-1-0104). I am grateful to N.
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