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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).
0257-8972/04/$ - see front matter 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2003.09.011
318
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
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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
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)
322
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
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A. Leyland, A. Matthews / Surface and Coatings Technology 177 178 (2004) 317324