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Surface and Coatings Technology 177 178 (2004) 317324

Design criteria for wear-resistant nanostructured and glassy-metal coatings


A. Leyland*, A. Matthews
Department of Engineering Materials, The University of Sheffield, Sheffield S1 3JD, UK

Abstract
There is increasing scientific and commercial interest in the development of nanostructured coatings, particularly those based
on low-miscibility ceramicceramic or ceramicmetal crystallineyamorphous nanocomposite phase mixtures deposited by
plasma-assisted PVD or CVD. In laboratory mechanical testing, extreme values of hardness (which may be in excess of 70 GPa)
are often found for such films, similar to those claimed for intrinsically hard materials such as c-BN and diamond. High hardness
is, however, often accompanied by an associated high elastic modulus, which although desirable in principle for cutting tool
materials andyor coatings, may in practice limit coating durability, on low-strength, low-modulus substrates (e.g. low-alloy steels
and the light alloys) and in many wear applications other than metal cutting. In this paper, we discuss the benefits of using the
ratio of hardness to elastic modulus (HyE) as an indicator of coating durability since this parameter essentially describes the
elastic strain to failure capability (and resilience) of a candidate material. Furthermore, we consider the likely need for tribological
coatings to accommodate some degree of substrate deformation; in this respect film toughness, i.e. engineering toughness in the
sense of an ability to absorb deformation energy (both elastic and plastic) needs to be considered. The concept of predominantly
metallic films with a nanograined andyor glassy microstructure (containing little or no high-modulus ceramic constituents) is
introduced, through which we point to the importance of retaining sufficient coating hardness, whilst reducing coating elastic
moduli to more closely match those of candidate substrate materials. With regard to the implications of HyE for practical
tribological coating applications, we propose that closer matching of the coatingysubstrate interfacial elastic properties and thus
an improved ability for the coating to accommodate substrate strain, where necessary, is often a more important factor in wear
resistance than is extremely high hardness.
2003 Elsevier B.V. All rights reserved.
Keywords: Nanostructured coatings; Glassy-metal coatings; Wear resistance; Resilience; Toughness; HyE

1. Introduction
As the authors have discussed previously w1x, classical
theories of wear tend often to emphasise hardness in
defining the wear resistance of a surface; this generally
implies a need to use ceramic bulk materials (or indeed
coatings) in tribological applications, whereby both
hardness and elastic modulus tend to be high. However,
it is also known that a high ratio of hardness to elastic
modulus (HyE) is indicative of good wear resistance in
a disparate range of materials w2x: ceramic, metallic and
polymeric (for example: c-BN, tool steel, nylon, respectively), which are equally effective in resisting attrition
for their particular intended application. Despite the lack
of conclusive evidence for a need to enhance the
elasticity, or resilience, of materials in order to improve
*Corresponding author.
Tel.: q44-0-114-222-5466; fax: q44-0-114-222-5943.
E-mail address: a.leyland@sheffield.ac.uk (A. Leyland).

their wear resistance (i.e. to reduce E, rather than


increase H), such an approach seems logical when
considering the behaviour of tribological coatings. The
wear characteristics of a coated surface are rarely fully
independent of the underlying substrate. Since many
candidate substrate materials are metallic (and are,
therefore, generally lacking in stiffness compared to
most engineering ceramics), the elastic behaviour of the
coatingysubstrate combination is often intrinsically mismatched. There is an inherent tendency for (low-modulus) substrate elastic deflections under load to place the
(high-modulus) ceramic coating in tension, to the likely
detriment of coating durability; such conditions are
exacerbated, should the substrate also begin to yield.
Thus, vapour-deposited ceramic films are probably unable to perform to their full potential in many prospective applications.
Nevertheless, the advent of commercially-viable
plasma-assisted PVD and CVD based surface treatment

0257-8972/04/$ - see front matter 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2003.09.011

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A. Leyland, A. Matthews / Surface and Coatings Technology 177 178 (2004) 317324

processes to produce ceramic coatings has to a considerable extent driven the emergence of Surface Engineering as a technological field in its own right. The benefits
of thin (i.e. -10 mm) and inert, high-hardness, highstiffness ceramic films in improving the performance
and productivity obtained from cutting tools (particularly) and from other machine tools used in materials
processing is indisputable. However, many of the traditional surface treatment processing routes for tribology applications, such as electroplating and thermal
spraying, are characterised by the widespread use of
predominantly metallic coating materials which although
chosen to be generally quite hard are also (relative to
many ceramic coatings) resilient and tough. By the
latter, we mean that as well as exhibiting a quite long
elastic strain-to-failure, they also demonstrate an ability
to accommodate plastic strain (either in themselves or
of the substrate), where necessary: a characteristic which
is absent in most engineering ceramics. We believe that
the traditional metallic film approach remains valid for
many prospective tribological applications of plasmaassisted PVD and CVD coatingsparticularly for lowmodulus substrate materials (of which many are widely
used) and for conditions of abrasion, impact and erosion,
where engineering toughness (i.e. accommodation of
plastic strain) andyor resilience are of more practical
relevance than are extremely high hardness or stiffness.
2. Practical considerations for vapour deposition of
nanostructured coatings
An updated, contemporary metallic film approach is
proposed by the authors, in which the advantages of
vapour deposition techniques (particularly of low-temperature plasma-assisted PVD methods, in the 200400
8C range) are harnessed to provide superior structure,
adhesion and high hardness for a metallic filmtogether
with improved toughness andyor resilience, compared
to ceramic films. The inherent ability of such techniques
to provide very high effective quench rates in the
depositing film, generating unusual levels of supersaturation of both interstitial and low-miscibility substitutional alloying elements, is an important factor in
promoting nanocrystalline or glassy phase formation in
vapour-deposited coatings. Furthermore, it is widely
known that thin ceramic films, despite their chemical
inertness, do not usually provide adequate corrosion
resistance since they tend to suffer from through-coating
defects and porosity, through which corrosive attack of
the coatingysubstrate interface can proceed, leading to
coating spallation. Such effects are exacerbated when
(as is often the case) a thin metallic interlayer is
deposited between coating and substrate (the latter of
which is already highly activated by the sputter precleaning process), to improve interfacial adhesion and
accommodate strain mismatch; for example, the titanium

interlayer deposited between a steel substrate and a PVD


TiN coating is known to be susceptible to galvanic
attack w3x. Metallic films can generally be vapour
deposited with less residual compressive stress than their
ceramic counterparts, allowing thicker (i.e. several tens
of mms) films to be deployed with reduced risk of
spallation; also, the maximum rate at which a dense
metallic film of the required stoichiometry can (for a
chosen substrate temperature) be deposited, is many
times higher than for ceramic compounds. With current
commercial vapour deposition technology, growth rates
of only a few mmyh are realistically attainable for
ceramic films at the 200400 8C deposition temperatures
suitable for many metallic substrate materials. However,
there is a realistic prospect of depositing metallic films
at rates of 10 mmyh or higher at these temperatures
(with consequent low-porosity and enhanced abrasiony
erosion resistance), equivalent in thickness and performance to (or better than), say, traditional electroplated
hard chromium or electroless nickelphosphorus metallic coatings. There are also strong arguments in the
literature that nanostructuredyamorphous metals might,
for example, provide more uniform and predictable
sacrificial corrosion protection due primarily to their
small and uniformly distributed features w4x; such arguments might reasonably be expected to translate directly
to the behaviour of nanostructured metallic films. We
address some of the above issues in the following
sections of this paper, indicating where possible what
the likely design and materials selection criteria might
be to achieve a desired combination of mechanical,
tribological and other (e.g. corrosion-resistant) properties in a nanostructured film.
3. Design and materials considerations for metallicnanocomposite and glassy-metal films
3.1. Background to metal nanocomposite films (and
associated design considerations)
Recent developments in plasma-assisted PVDyCVD
thin film technology, particularly in the production of
nanostructured films, have revealed that it is possible to
adjust the hardness and elastic modulus of a tribological
coating with some degree of independence, introducing
exciting possibilities to produce wear-resistant surfaces
with combinations of properties which were previously
unobtainable. Scientific interest in, particularly, sputter
PVD (but also plasma-assisted CVD) processes to produce so-called nanocomposite coatings has so far been
directed primarily towards the development of superhard coatings (where H typically exceeds 40 GPa) for
dry sliding wear resistance and high thermal stability.
This is based on the premise of creating a composite of
ceramic nanocrystallites embedded in an amorphous
ceramic w5,6x (i.e. ceramicceramic nanocomposite) or

A. Leyland, A. Matthews / Surface and Coatings Technology 177 178 (2004) 317324

low-miscibility metallic w7,8x (i.e. ceramicmetal nanocomposite) grain-boundary phase. As we suggested


above, many such films tend also to exhibit a high
elastic modulus, which may be beneficial for coated
tooling, but perhaps not in other applications. This led
us initially to propose that metalmetal nanocomposite
coatings might be a more rewarding subject for investigation w1x, since they promise considerable scope to
provide (and adjust) a low coating elastic modulus in a
range similar to that of many candidate substrate materials whilst, with appropriate materials and processing
route selection, allowing ceramic values of hardness
(i.e. of the order of 1520 GPa or higher) to be
achieved. This approach stemmed mainly from our
earlier work on metallic coatings of, for example, Cr
w9x, W w10x, TiAl w11x or stainless steel w12,13x, each
doped with nitrogen, carbon andyor boron (i.e. films
containing a supersaturation of interstitially located elements), where we found frequently that the coating
which performed best in wear applications was not
necessarily that which was hardest but, more often, that
which exhibited a high HyE ratio.
Taking for instance the example of nitrogen-doped
chromium w9x, we found that a moderately hard (i.e.
1215 GPa) metallic film with approximately 1215
at.% N in supersaturated solid solution (the equilibrium solubility of nitrogen in chromium is predicted to
reach a maximum of approx. 4.3 at.% between 1650
and 1700 8C and is negligible below 1000 8C w14x)
gave results superior to those of significantly harder (i.e.
2025 GPa) ceramic nitride films, when subjected to
severe impact wear. Experiments were performed using
a ball-on-plate configuration, whereby a 10-mm diameter ball of either chromium steel or WCCo was
repeatedly driven against a coated plate at a load of
several hundred Newtonssufficient to cause considerable plastic deformation of the underlying substrate
material. For both ball materials, the impact crater wear
volume after 50 000 cycles was high for low-nitrogen
(i.e. low hardness) chromium films, but similarly low
for both the high-nitrogen chromium and ceramic nitride
films; i.e. increasing the hardness beyond 15 GPa had
little further effect in reducing the impact crater volume.
However, the overall performance of the high-nitrogen
metallic films was superior, in that (despite the substantial substrate plastic deformation) there was little or no
cracking or debonding of the tough, lower-modulus
metallic films whereas the brittle, higher-modulus ceramic films exhibited extensive circumferential cracking
around the crater rim, with extensive fracture and
debonding in the central zone of the crater itself.
Analogous observations can be made regarding the
superior abrasion and erosion behaviour of TiyTiN
multilayer (e.g. w15x) or CrNyelectroless nickel duplex
(e.g. w16x) coatings, where the relatively ductile metal
constituents in the film allow plastic strain to be accom-

319

modated (and thicker films to be deposited), to the


benefit of both wear and corrosion behaviour.
Returning to nitrogen-doped chromium metallic films
for a moment: in the light of the above (and of the
arguments for the likely benefits of a nanocomposite
metal film w1x), one next logical step might be to modify
a nitrogen-doped chromium film by the introduction of
a secondary, immiscible metal constituent (preferably
with a fairly low elastic modulus). This would either be
captured substitutionally in the chromium (to the likely
frustration of dislocation movement, and thus early
yielding, when loaded) or, with suitable choice of
coating deposition parameters (andyor post-coat annealing treatment), form a thin intergranular phase and
promote a nanograined composite structure, with similarly increased resistance to plastic deformation (not
least through HallPetch effectsalthough other anomalous effects may also occur w1x). In either case, the
likely overall effect would be expected to present itself
as a further substantial increase in yield strength and,
by implication, hardness, whilst the modulus remained
similar or with appropriate alloying material selection,
became substantially reduced. Thus, a substantial
increase in HyE ratio would result to the benefit of
coating resilience (if not of toughness); providing prospects to tailor both composition and structure to, in
principle, engineer coating toughness, resilience and
modulus to match closely the mechanical properties of
almost any (but particularly any metallic) substrate
material that might be chosen. Our preliminary work in
this area was directed towards addition of copper to the
Cr(N) metallic film system, since copper exhibits almost
complete immiscibility with chromium under most conditions, has roughly half the elastic modulus of chromium (130 GPa cf. 280 GPa) and, from a practical
perspective, is relatively inexpensive and widely available in a suitable high purity form. Our preliminary
work on this coating system, with additions of both
nitrogen and boron, has recently been published, with a
number of encouraging results obtained w17,18x. Nevertheless, there are many other candidate coating systems
which might be considered for the synthesis of wearresistant metallic films based on the above mentioned
requirementsand other materials-related design considerations, as outlined in the following section.
In attempting to design effective metalmetal nanocomposite coatings, one consideration which needs to
be made is that of choosing an appropriate alloy composition (and grain size issues related to this). As the
authors discussed previously w1x, one claimed advantage
of a nanograined structure is anomalously high hardness
in the (typically) 10100 nm grain size range. In
addition to the HallPetch relationship between
(increasing) hardness or yield-strength and (decreasing)
grain size, where the stress required to propagate dislocations from one grain to another increases as their size

320

A. Leyland, A. Matthews / Surface and Coatings Technology 177 178 (2004) 317324

reduces, there is theoretically a dimension range of


several tens to one or two hundreds of nanometres
(depending on the chosen element or alloy) below which
a Frank-Read dislocation loop source (widely believed
to be the main mechanism for dislocation multiplication
and, therefore, grain boundary pile-up, which largely
drives the deformation process from grain to grain)
cannot operate. Thus, high hardness (but also reduced
ductility) may result from a nanograined structure.
However, it has been observed that as the grain size
approaches the order of a typical grain boundary dimension (i.e. as the grain diameter reduces below 510
nm), grain rotation within the grain boundary matrix
can occur, leading to an inverse HallPetch softening
effect. Furthermore, in an idealised metallic nanocomposite, one might envisage a majority of hard nitride
former transition metal grains (e.g. chromium, interstitially supersaturated with nitrogen) surrounded by a
minority (e.g. -20 at.%) disordered grain boundary
phase of a low-modulus, immiscible metal phase (e.g.
copper), as being the type of structure likely to provide
a desirable combination of hardness, resilience and
ductility. The amount (for example) of copper which
would need to be added to chromium to achieve such a
structure (assuming, hypothetically for the moment, that
a processing route could be found to deposit a coating
with these properties) would be interdependent with the
chromium grain size produced. Table 1 explores such a
scenario, by examining the amount of copper theoretically required to produce a continuous grain boundary
layer (of anywhere between 1 and 15 atoms thick), for
different sizes of Cr nanograin in the range of interest.
Although many (questionable) assumptions have to be
made in such a treatment, it is nevertheless illuminating
to examine the different possibilities which emerge. For
example, if it were possible to choose conditions whereby a coating with relatively large (G100 nm) Cr

nanograins was produced, the amount of Cu required to


generate a typical grain boundary layer of, say, 510
atom widths would be little more than 35 at.% (Table
1). However, at grain sizes F10 nm, up to 50 at.% Cu
might be needed to generate a continuous grain boundary phase, based on the same criterion. Such a high
content of (soft and ductile) grain boundary material
might not be expected to be beneficial for coating
mechanical and tribological properties. Particularly, at
such small grain sizes, the grain radius is approaching
the dimension of the grain boundary width, such that
small fluctuations in grain boundary phase content could
encourage grain rotation, making it difficult to accurately
control coating behaviour from batch to batch in a real
deposition process. Conversely, quite wide fluctuations
in grain boundary phase content could probably be
better accommodated at larger grain sizes, since the
grain width will always remain an order of magnitude
higher than the grain boundary dimension, preventing
grain rotation. In practice, one might ideally choose an
intermediate grain size (i.e. 2540 nm) and composition
(i.e. 1015 at.% Cu). Certainly, this range of grain sizes
and a 90y10 to 85y15 ratio between nanocrystalline and
amorphous (grain boundary) phases appears to work
well in TiAlBN nanocrystalline-ceramicyamorphousceramic, pseudo-binary nc-TiAlNya-BN nanocomposite
coatings for cutting tool applications w19,20x. It remains
to be seen what, if any, is the optimum for metalmetal
nanocomposite films. Other authors have had considerable success with ceramicceramic nanocrystalliney
amorphous films (e.g. nc-TiNya-SiNx w5,6x) at similar
phase ratios, but with very small grain sizes (-5 nm).
The key to good performance in this case appears to be
the avoidance of a fully percolated structure (i.e.
nanograins completely separated from each other by the
matrix) w21x, since interpenetrating networks of crystalline and amorphous regions avoid the grain boundary
rotation issues referred to above. This argument is
supported by Table 1; it is obvious that (although the
elementsyphases involved are very different), a sub-5
nm TiN grain size, combined with an amorphous SiNx
content of -15%, is unlikely to generate structures
where complete coverage of the nanocrystallites by the
intergranular phase can occur. Spontaneous unmixing of
inherently immiscible binary metal alloys at the limit of
metastability (so-called spinodal decomposition) has
historically been shown often to create such interpenetrating networks, with the uphill diffusion processes
and timescales involved tending naturally to produce a
periodic spacing of ;510 nm (see w22x for references).
One of the main challenges in developing metallic
nanocomposite coatings will be to determine which
possible structural features outlined above can give the
most appropriate tribological behaviour in individual
applications; it seems unlikely that one particular
approach will provide a universal solution.

A. Leyland, A. Matthews / Surface and Coatings Technology 177 178 (2004) 317324

321

Table 2
Candidate low-miscibility nitride-forming and non-nitride-forming elements which might be considered for alloying to produce metallic nanocomposite or glassy metal films
Element

Crystallographic
structure

Elastic modulus
E (GPa)

Atomic radius
(pm)

Tm
8C (K)

Ti
Zr
Hf
V
Nb
Ta
Cr
Mo
W
Al
Si

cph
cph
cph
bcc
bcc
bcc
bcc
bcc
bcc
bcc
cubic

115
68
78
128
105
186
280
330
410
70
47

140
160
155
135
145
145
140
145
135
125
112

1675
1852
2150
1895
2470
2996
1890
2610
3415
660
1410

(1948)
(2125)
(2423)
(2168)
(2743)
(3269)
(2163)
(2883)
(3688)
(933)
(1683)

376
435
535
450
641
817
448
688
956
38
288

Mg
Ca
Sc
Ni
Cu
Y
Ag
In
Sn
La
Au
Pb

cph
cubic
cph
fcc
fcc
cph
fcc
fct
bct
cph
fcc
fcc

44
20
74
200
124
64
76
11
40
37
78
16

150
180
160
135
135
180
160
155
145
195
135
180

651
845
1539
1455
1083
1497
961
157
232
920
1063
328

(924)
(1118)
(1812)
(1728)
(1356)
(1770)
(1234)
(430)
(505)
(1193)
(1336)
(601)

35
100
331
303
179
317
138
y130
y105
125
172
y73

3.2. Materials selection for nanostructured films (and


prospective benefits in glassy film formation)
The chromiumcoppernitrogen system appeared to
the authors to be an obvious materials choice for further
investigation of the potential benefits of metallic-nanocomposite films over and above the (to some extent
proven) benefits of, for example, PVD nitrogen-doped
hard chromium metal films. However, it was also immediately apparent that a number of other candidate systems should exist, with the potential to develop a diverse
spectrum of unusual and extreme mechanicalytribological properties, which might not be attainable through
many of the conventional materials processing (or
vapour deposition) approaches currently favoured for
scientific investigation. Firstly, consider the nitrideforming elements which are generally selected for the
production of refractory ceramic nitride, carbide, boride
or oxide materials used in tribology: namely, the Group
IVbVIb elements (TiyZryHf; VyNbyTa; CryMoyW)
and the group IIIayIVa elements Al and Si. Whether
they are bulk materials or coatings, these are the 11
elements which, in various combinations tend exclusively to be used with B, C, N andyor O to produce wearresistant engineering ceramics. Excepting Al, the
remaining 10 elements all have melting temperatures
(Tm) of ;1700 K or above (up to approx. 3700 K, in
the case of W) and are, therefore, inherently quite
refractory (see Table 2). Let us now also consider

TyTms1y3
8C (K)
(649)
(708)
(808)
(723)
(914)
(1090)
(721)
(961)
(1229)
(311)
(561)
(308)
(373)
(604)
(576)
(452)
(590)
(411)
(143)
(168)
(398)
(445)
(200)

(somewhat arbitrarily) a homologous temperature (Ty


Tm) of 1y3, as a point at which, one might argue,
diffusion mechanisms could start to significantly alter
the microstructure of a bulk material over a fairly short
time-frame (i.e. of the order of a few hours to a few
tens of hours); one might infer from this that the 10
elemental materials in question would tend to exhibit
some inherent thermal stability up to a few 100 8C or
more and could, therefore be considered quite suitable
as candidate tribological materials in their own right,
assuming (for instance) that a nanocrystalline microstructure could be generated to maximise their hardness
and load-bearing capability. For the purposes of creating
such a small grain size, the addition of a second, lowmiscibility element has been shown to be very effective
particularly in vapour deposition of metallic thin films
(e.g. AlY w23x, CrCu w17x). There are a surprisingly
high number of (metallic) elements which, when introduced to create a binary alloy with the candidate
elements identified above, exhibit a wide miscibility gap
in the solid state. Examples of elements for which there
is evidence of such behaviour when mixed with some
or all of the IIIa, IVa, IVb, Vb and VIb nitride-forming
elements identified are, in order of atomic number: Mg,
Ca, Sc, Ni, Cu, Y, Ag, In, Sn, La, Au, Pbalthough
this list is by no means exhaustive. Of these 12, only
five (Sc, Ni, Y and perhaps also Cu and Au) might be
considered to exhibit sufficient refractory tendencies
(i.e. Tm)1000 8C), that they could be expected to

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A. Leyland, A. Matthews / Surface and Coatings Technology 177 178 (2004) 317324

demonstrate some inherent thermal stability above ambient. Such considerations may be relevant in selecting
material combinations for applications such as, for
example, dry (or marginally lubricated) sliding components, where local flash temperatures may reach several
100 8C. However, low-melting point metals such as In,
Sn and Pb (with little inherent thermal stability) also
exhibit very low elastic moduli (11 GPa, 40 GPa and
16 GPa, respectively), which may be attractive in
adjusting the overall modulus of a tribological film to
meet a specific substrate requirement (e.g. protective
coatings for magnesium alloys, where the substrate
elastic modulus is only about 45 GPa). Conversely,
some of the more refractory transition metal elements
(e.g. Zr, Hf) and their low-miscibility rare earth counterparts (Sc, Y) have surprisingly low elastic moduli in
the 6080 GPa range, making them potentially very
suitable for coating aluminium alloys with similar elastic
properties. Furthermore, refractory combinations such as
TaNi (Tms2996 8C and 1455 8C, Es186 GPa and
200 GPa, respectively) might be considered for protection of steel substrates with similar moduli. By way of
comparison, the elastic moduli of most refractory ceramics are in the 400700 GPa range: i.e. an order of
magnitude higher than for a typical aluminium or magnesium light alloy. Intuitively, one would not expect a
coating of such a ceramic to provide any long-term wear
protection to these kinds of substrate material whereas,
as proposed above, considerable promise is shown by
the concept of a (relatively) hard metallic coating of
very similar elastic properties to the chosen substrate.
As one further point on this topic, the candidate nitrideforming elements above (and the PVD coating process)
lend themselves to the production of functionally graded
films, whereby the substrateycoating interface can be
elastically matched, but the nitrogen (or indeed carbon,
boron or oxygen) content in the coating can be adjusted
with deposition time to generate an increasing highmodulus (and tribochemically stable) ceramic phase
content near the surface of the filmshould the intended
application necessitate such a requirement.
Having considered simple binary metal alloy systems
(disregarding for a moment the introduction of a third,
interstitial element to such systems), we now turn our
attention to the implications for coating properties of
combining three or more metallic elements. In the
alloying of different (metallic) elements, Hume-Rothery
w24x proposed a 14% rule, whereby it can be considered that atoms of two elements whose atomic radii
differ by more than 14% will most likely be quite
restricted in their mutual solubility, with considerable
lattice strain occurring (and implied lattice friction
increases) if one element is substituted for the other in
a crystalline structure; one expected result of such an
effect would be substantially increased yield strength
(and hardness). Thus, very large (e.g. with diameters of

0.18 nm or above) or small (e.g. with diameters of 0.12


nm or below) substitutional atoms would tend not to be
highly miscible with an average (0.15"0.01-nm diameter) metal atom. Even notionally very similar atoms
such as, for example, the group IVb metals Ti (;0.14
nm) and Zr (;0.16 nm) can be quite different in size
and one might expect substantial lattice strain to occur
when they are mixed. Superimposed with this effect,
many of the elements identified, respectively, in the
upper and lower portions of Table 2, exhibit very
different crystallographic structure, due in part to their
contrasting valence electron configurations. Thus many
of these elements, despite being of similar atomic size,
show electronic incompatibilities, which often restrict
their mutual solubility (again, the bcc-Cryfcc-Cu system
provides a typical example of this). When attempts are
made to mix several elements with different atom sizes
and preferred crystallographic structures, it is often the
case that the driving force for crystallisation on solidification from the melt or (in the case of PVDyCVD)
vapour is suppressed to the point that the creation of an
amorphous structure is equally (or more) favourable
energetically. In other words, the formation of a regular,
crystalline lattice is frustrated by the existence of many
incompatible atom sizes and electron configurations to
the point that long range order is thermodynamically
difficult to establish even at very mild quench rates of
the order of ;1 Kys. Such a phenomenon was predicted
over 50 years ago by Turnbull w25x, who first described
the concept of a reduced glass transition temperature
(i.e. Tg yTm) which, when rising from approximately 1y
2 to 2y3, would (due to the alloying effects mentioned
above) cause homogeneous nucleation from an (undercooled) alloy melt to become extremely slow. Subsequent work by Duwez et al. w26x, Turnbull and Chen
w27,28x and more recently by others such as Davies
w29x, Tanner w30x, Johnson and Peker w31,32x, and
particularly by Inoue and co-workers w3335x, has led
to the development of a range of bulk metallic glass
forming alloys, which can be characterised broadly into
ferrous and non-ferrous systems w33x. Many of these
systems (particularly the ferrous) are of interest for
soft magnetic applications where, for example, the lack
of grain boundaries can be of considerable benefit, but
several authors have commented on the high yield
strengths and low moduli obtainable (i.e. providing high
HyE ratios, although this is not explicitly said), suggesting suitability for certain mechanical and tribological
applications. So far, however, very few attempts have
been made to exploit the bulk mechanical or surface
tribological properties of these materials w36,37x. A
particular issue with bulk metallic glasses is the tendency
towards brittle behaviour (particularly in tension). In
reality, this observation appears to relate more to shear
band localisation, which leads to unstable yield behaviour and early fracture; a lack of grain boundaries (and

A. Leyland, A. Matthews / Surface and Coatings Technology 177 178 (2004) 317324

thus also work hardening mechanisms) is believed to be


the main cause of such behaviour w36x. Some current
work in this area is being directed towards procedures
to introduce crystalline phases (e.g. by partial devitrification w33x or production of amorphous matrixy
crystalline-fibre composite materials w36x) to delocalise
shear band formation. However, it is claimed that impact
tests generally indicate a fairly high fracture toughness
for metallic glasses (although somewhat lower than for
most polycrystalline metals) w36x; furthermore, many
metallic glasses can be successfully cold-rolled to very
thin sections without annealing (e.g. w32x), and might
be said to exhibit superplastic deformation behaviour in
this respect. In fact, numerous other physical benefits
have also been observed for metallic glasses (again due
largely to the absence of grain boundaries), such as
better corrosion resistance w38x with more uniform sacrificial behaviour and reduced pitting claimed, and
improved fatigue behaviour. The potential benefits of
glassy phase formation in vapour-deposited thin films
are enormous, but are as yet under researched, with only
a few authors (e.g. Frantz, Billard and Sanchette w39
41x) having explored the topic in any systematic way.
The ability to post-coat amorphise a nanocrystalline
film through plasma-diffusion treatment w12,13x or conversely, post-coat anneal a glassy film to partially
devitrify and create controlled nanocomposite structures
w33x are two examples of topics in the vapour-deposited
thin film field which appear to merit further investigation. Furthermore, low-temperature (i.e. F350 8C) plasma-assisted PVD techniques in particular raise the
exciting prospect of investigating new metallic glass
compositions which may currently be difficult to synthesise via conventional bulk casting methods, but might
yield novel physical behaviourwhether that be
mechanical, tribological, chemical, magnetic, or other
functional properties.
4. Summary and conclusions
Alloys of low-miscibility metals exhibit untapped
potential for producing nanostructured and glassy-metal
vapour-deposited coatings with unusual combinations of
properties, which may be extremely useful for a variety
of tribological (and other) applications. In particular,
combinations of high hardness and low modulus together
with ductility and toughness (in an engineering context) are likely to provide a viable route to the effective
wear protection of low-strength steels and light alloys,
where few solutions presently exist.
Binary alloys of a nitride-forming transition metal
with another low-modulus, low-miscibility transition
metal elementthe former being doped to supersaturation with an interstitial element (i.e. B, C, N or O) to
increase yield strengthappear to provide one promising route to achieving the desired properties. However,

323

alloys of ternary, quaternary or higher mixtures of


elements with different atomic radii andyor valence
electron configurations provide scope to form a glassy
metal film over an extremely wide range of
compositions.
Many such films can (like metallic nanocomposite
coatings) provide hardness values in excess of 20 GPa
and can in some cases approach superhardness (i.e.
approx. 40 GPa), whilst retaining the (low) elastic
moduli of the constituent metallic phases. Thus, vapourdeposited coatings with high HyE ratios and (perhaps
more importantly) similar elastic properties to their
intended substrate material can be created at high rate
()10 mmyh), which perform particularly well in abrasion, erosion and impact wear, but also show benefits
in (for example) sliding wear and corrosion.
There are a number of coating materials and processing aspects that require further consideration in designing effective nanocomposite films. Criteria such as the
alloying elements incorporated, relative quantities of
each constituent, the influence of deposition parameters
on grain sizes produced, post-coat thermal treatments
(particularly in the case of glassy films): all such factors
are likely to interact with each other to strongly influence
the resulting mechanical and tribological properties of
the film.
Acknowledgments
The support of the UK Engineering and Physical
Sciences Research Council (EPSRC) in this work, under
project GRyN03495, is acknowledged with thanks.
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