Wear, 165 (1993) 85-95 85

Review of multicomponent and multilayer coatings for tribological

applications

C. Subramanian* and K. N. Strafford

Surface Engineering Research Group, Deparhent of Metallurgy, Gartrell School of Mining, Metal@ and Applied Geology
The University of South Australia, Z%e LeveCF, SA 5095 (Awtralia)

(Received July 6, 1992; revised and accepted October 15, 1992)

Abstract

Improvement in performance of engineering components is achieved through the proper choice of materials,
design, or both. Materials perform more efficiently even under severe working conditions when they are surface-
engineered, ie. coated and/or surface treated. Physical and chemical vapour deposition techniques have found
increasingly wider use in such applications in recent years. The so-called first generation coatings (e.g. TiN) are
widely used in industrial applications, whereas adoption and implementation of second generation coatings (e.g.
Ti (CN), (TiAl) N) are currently under serious consideration. The third generation of coatings - multicomponent
and multilayer coating variants - are at the research stage. In this paper, the development of multicomponent
and multilayer coatings for tribological applications are reviewed and the rationale behind the improved performance
- established and anticipated - of such coatings is discussed.

1. Introduction Combinations of various substrate and coating ma-

terials have been studied. Depending upon the appli-
The ever-increasing demands of design and produc- cation, a substratexoating combination or a system is
tion engineers have led to the search for new materials selected. Because of vastly differing properties of sub-
with significantly improved properties. In recent years strate and coating materials, only a few combinations
many new materials have been synthesized, character- have been successful in achieving the required level of
ized and put into use. Among these materials, composites system integrity. The important material parameters to
and surface-engineered materials deserve special men- be considered in achieving better performance are elastic
tion. Surface-engineered materials generally have their moduli (stress discontinuity), thermal expansion coef-
surfaces modified, e.g. by infusion of C and/or N, or ficients, crystal structures and chemical compatibility
coated with some other material(s) so that their re- of the coating and substrate materials [6]. This becomes
sistance to wear, corrosion or fatigue is improved. clearer if the requirements of the surface coating, the
The last 30 years have seen many advances in the interface and the substrate, as illustrated in Fig. 1 [ll,
surface engineering field - firstly with the commer- 121, are considered.
cialization of the chemical vapour deposition (CVD)
process, and secondly through the evolution of physical
vapour deposition (PVD) techniques with both sput- Surfsca - interactionwith workpiece
J (adhesWabrashfa wear) or
tering and evaporative sources. These developments environment(conwlon/oxidatkm)
have been reviewed elsewhere [l-9].
The principal driving force behind these developments + hardness (fatigue)strength,
internalstrees, fracture toughness
was the economic benefits achieved by applying these
technologies in metal cutting, metal forming and other
adherewe
fields of manufacture. A large improvement in the life c interaction(reaction)substrate/layer
thermal expansion misfit
of a cutting tool or a drilling tool (often more than
10 times) after coating with a hard material (eg. TiN),
for a fraction of the cost of the tool, has been reported
WI*
*Author to whom correspondence should be addressed. Fig. 1. Fundamentals of a coating system [ll].

0043-1648/93/$6.00 0 1993 - Elsevier Sequoia. All rights reserved

86 C. Subramam’an, K. N. &afford i ~~~t~orn~ne~t and multilayer coatings

Once the substrate-coating selection is complete, the tribological and corrosion behaviour. Table 1 lists various
next problem is to determine the particular processing borides, carbides, nitrides and oxides which can be
route. This includes factors such as coating thickness, employed in mitigating corrosion and wear 1131.Table
~atin~substrate ~mpatibili~ (and thus bond coat or 2 shows various compounds used as coatings. They are
graded-interface requirements) and other parameters. mainly based on transitional metals and elements of
Generally, one or more intermediate layers are applied Groups IV and VI in the Periodic Table. Like metals
between the actual coating and the substrate to improve forming alloys, these mononitrides and monocarbides
the compatibility between them, i.e. to match mainly can form binary nitrides and binary carbides (ternary
the chemical bonding and thermal expansion coeffi- phase systems) by adding another suitable metallic
cients. This naturally points to the need for a multilayer element to them. For example, in TiN, the lattice of
coating system for better and especially optimum per- Ti can be partly substituted by V or Al. A complete
formance. list of such ternary (e.g. binary nitride =TiAlN) and
In this paper, multicom~nent and multilayer coating quaternary systems are shown in Table 3 (data taken
systems are reviewed with an emphasis on stoichiometry, from refs. 14-26). It is clear from Tables 2 and 3 that
thickness, number of layers, methods of preparation not all the compounds listed in Table 1 are used as
and property improvements. Some directions for future coatings. These hard compounds can be classified
research are also indicated. based on the bonding type - metallic, covalent or
ionic. (Fig. 3 [14, 151). The properties of each group
of materials are qualitativeiy compared in Fig. 4.
2. Te~inolo~ It is obvious that no one group has all the prop-
erties to the highest level (Fig. 4). For example, if
A wide variety of terms have been used to describe hardness is to be maximized, brittleness cannot
composite coatings in the literature, e.g. multicompo- completely be avoided. Naturally a combination of
nent, hybrid, multiphase (polyphase), heterogeneous, different materials is desirable to achieve optimum per-
multilayer, microlaminate, gradient and composite coat-
formance.
ings. Here it is proposed to follow the definitions of
One of the ways to ~prove/optim~e properties of
the terms as described below.
a hard material is to substitute the metal lattice of the
By adjusting the composition of the coating material,
compound phase with another compatible metal, e.g.
either multicomponent (binary, ternary, etc., solid so-
in TiN the lattice of Ti is partly substituted by Al, V,
lutions) or multiphase/~m~site (solid solutions and/
Zr or Hf. Another method is to vary the relative
or intermetallic compounds) coatings can be obtained.
concentrations of the non-metallic elements. By doing
Depending upon the size and distribution of secondary
so, the valence electron concentration (VEC) of the
phases in the primary matrix, a coating can either be
phase changes and thus its mechanical and physical
called ~~lti~h~se or composite. The term “composite”
properties change too. As an example, Fig. 5 shows
is used when one phase is dispersed in a matrix which
how microhardness values of certain carbides, mixed
is ~ntinuous; the term “multiphase” (or “polyphase”)
carbides and carbonitrides vary [14]. When the VEC
is used when both are equally present and none of
value is around 8.4, maximum hardness occurs for most
them is continuous.
By using these coatings, it is possible then to lay of the compounds. Similar diagrams for other properties
them on the substrate to create multilayer or gradient such as toughness, chemical stability and wear resistance
coatings. “Gradient coating” refers to a system whose should be obtained as a function of VEC, so that the
composition gradually varies from one layer to another, ability topredict the performance of coatings from basic
i.e. no sharp transition exists. However, the term “gra- principles can be enhanced.
dient layers” has also been used to represent a multilayer Even in a single nitride, depending on the concen-
coating which has sharp transitions in composition tration of nitrogen, the properties of the nitride vary.
between layers [ll]. Microlaminate composites are mul- For example, in TiXNl_, the value of x determines
tilayer coatings which consist of alternate layers of two mechanical and physical properties [6]. When it comes
different materials [ 131.Figure 2 schematically illustrates to ternary and quaternary systems of hard compounds,
these variations in the coatings. the situation becomes more complex. Phase diagrams
of such systems are then useful in this context. From
the~odynamic data, phase diagrams can be predicted
3. Multico~ponent coatings and experimentally verified. Phase diagram data can
also be used to predict the phases formed under non-
Initially mononitride and monocarbide were produced equilibrium conditions (such as in vapour deposition)
as coating materials on various substrates to improve to some extent 1143. One such example is shown in
 C. Subranumian, K N. Strafford / Mdticomponent and multilayer coatings

Alloyed (or ‘Multicomponent’) MUitiph~~ Composite Multilayer Gradient

M,M,X, M,X,Xs etc TiC/TiN Tic/Al,o, TiCfliN/AI,O 3 TiN/TiCN/TiC
TiAlN TiCN
Fig. 2. Schematic illustration of the structure of different types of coatings.

TABLE 1. Carbides, nitrides, oxides and borides employed to TABLE 3. Ternary and quatemary hard compounds used as
resist corrosion and wear [13] tribological coatings (data from various sources)

Carbides Nitrides Oxides Borides Ti

Corrosion-resistant ceramics Zr Hf V Nb Ta Cr MO W Al Si AIV AIZr

Sic Si& Sialon A&O3 TiB,
HfC I-UN SiOr MOB B
ZrC ZrN TiOr WI3 C l l

TiN ZrOr MB2

N l eeeee l l l

Sn02 TaB2 0 l

MgAlzOb ZrB, CN l l l l

MgO Hfs2 ON l

Cr203 oc l

OCN
Tribological ceramics
Tic TiN A12o3 TiB2
HfC HfN Si02 MOB
Hard Materials
ZrC Si& Ti02 WB
Sic BN zfl2 N’-JB~

W ZrN Tar05 TaB2 metallic covalent ionic

B2C TaN Cr203 ZrB,

w2c AlN Hf02 HfB2
borides oxides
VN VB
of Ai, Zr, Ti, Be
Cr7C3 v203
carbides carbides
Cr3G NbN
Cr23G nitrides of the nitrides
TaC transition metals of Ai, Bi B,
diamond
vc
NbC
WC e.g. e.g.
;I ,k;Cc’ TiN, B,C, SIC, BN
I

TABLE 2. Various compounds used as coating materials for Fig. 3. Classification of various hard materials [14, 151.
tribological applications (data from various sources)
4. Multilayer coatings
IV B VB VIB III A IV A
- -
As mentioned earlier, the adhesion between coating
Ti Zr I-If V Nb Ta Cr MO W B Al Si
and substrate should be high for a successful application
B .o 0 of a coating system. To improve adhesion and other
C l eeeeee l l l mechanical and physical properties, one or more in-
N l eeeeeee l e l termediate layers are applied. Multilayer coatings may
0 l e l l
be produced by a range of techniques which include
CN l
ON l
PVD, CVD and their derivatives. It should be mentioned
OC l here that the multilayer coatings produced by painting,
OCN l plasma thermal spray, electroplating, electroless plating
and any other method [27-311 are not discussed in this
paper. Also, multilayer coatings of microelectronic de-
vices [28-301 will not be dealt with here, albeit re-
Fig. 6 for Tic-TiB2, where solid solution or amorphous cognising the involvement of PVD in their production.
structure exists, depending on the substrate temper- It should, however, be mentioned that the rutionde
ature. behind multilayer coatings can be applied to any type
88 C. Subramanian, K. N. Strafford I Multicomponent and multilayer coatings

Propelties and behaviour of various roups of hard materials

(M = Metallic: C = Covalent; I = IonicB

I I I I I I I I I I

1 \“‘g”l 1C 1 1 1 M 1 1 1 1 1 M 1 M 1M 1
I\ Ii I I I I I I I 1

I I I I I I
Fig. 4. Properties and behaviour of various groups of hard materials.

35oOm

.-a-.-

3oK-

I
2500 -
E
e

3
)NbC

20@- )TlN
.’
)HfN

1 TaC

valence electron concentration (VEC) -.----+

Fig. 5. Microhardness of carbides, mixed carbides or carbonitrides as a function of the valence electron concentration [14].

of coating system. Discussion is therefore confined in sequential magnetron sputtering system [32, 331. The
this section to the production, properties and per- production of PVD coatings is generally faster than
formance of hard tribological coatings in multilayer CVD due to a higher deposition rate.
formats. Historically, CVD coatings were first developed and
Hard multilayer coatings are produced either by PVD marketed in 1968 by Krupp in (West) Germany under
or by CVD methods. It is well known that CVD coatings the brand name Widia. This was followed by Sweden’s
are traditionally produced at much higher temperatures Sandvik, another big name in the cutting tool industry.
than those used for PVD coatings. Therefore, in CVD Hara et al. [34] at Sumitomo Electric (Japan) have
coatings the interfaces between the layers (or the coat- developed a proprietary coating using CVD methods.
ing/substrate interface in a single layer coating system) It has a triple layer format - the outer layer being
are often not as sharp as those found in PVD coatings aluminium oxide for hardness and chemical stability.
owing to the occurrence of diffusion at high temper- The inner layer is a titanium-based compound (Tic or
atures. Diffusion is sometimes advantageous as it im- TiN) for good bonding to the cemented carbide substrate
proves the adhesion, provided that the interface phase but significantly there is also an intermediate layer
is not brittle. Other differences between CVD and PVD whose composition is not givei. Hara et al. [34] have
coatings are the number and the thickness of layers. reported that multilayer coating systems perform better
PVD processes, especially the magnetron sputtering than single or double layer coatings in metal-cutting
techniques, have flexibility in controlling the thickness operations at higher speeds. Kennametal Inc. (USA)
of each layer. For example, Holleck and his co-workers have successfully designed and developed a multilayer
have produced up to 1000 layers of TiCRiB* of total coating system with alternative layers of TiCN, A&O,
thickness 5 pm (i.e. each layer is 5 nm thick) using a and TiN [35]. A typical microstructure is shown in Fig.
 C. Subramanian, K N. Strafford I Multicomponent and multilayer coatings 89

has been shown to perform better than its single layer

counterparts (and is also based on CVD techniques)
is reported by Schinthneister et al. [37]. They have
concluded that the wear and thermal cracking resistance
of the multilayer (TiC/I’iCN/riN) coating system is
superior to that of a single TiN coating under the
P 3100 machining conditions used (speed = 200 m min-‘; feed
.E
f 2900
rate =0.41 mm rev-‘; depth of cut =2 mm; work
material=C60 Steel). Coleman [38] has recently com-
B 2700 piled data for various machining operations such as
E 2500 turning, boring and milling of a range of materials, viz.
steels, grey cast iron, modular cast iron, alumin-
2300
Tic + TiB2
ium-silicon alloy and titanium alloys, using multilayer-
coated cutting tools. He also discusses the limitations
f of such sophisticated tools in terms of cutting speed,
feed rate, depth of cut and other machining parameters
Equilibrium
(for example, the machining of certain commercial high
phases temperature alloys such as ‘Inconel’, ‘Hastelloy’ and
‘Rene’). As these super alloys are very strong and tough,
fee Ti(CxBy) - turning them requires a specially sharp cutting edge.
solid solution As CVD multilayers are more effectively applied on
a honed, radiused edge, coatings on sharp edges may
amorphous not withstand the load under such operating conditions.
solid solution
Introduction of plasmas into conventional PVD or
20 40 60 80 T,C CVD processes offers many advantages as reviewed
T’a,
mol % Tic recently [39, 401. The application of plasmas, or ion
assistance with CVD processes, could incorporate the
Fig. 6. Section TiB,-TiC in Ti-B-C systems - phase obtained
by vapour quenching (schematic PVD phase fields [HI).
advantages of ‘pure’ CVD and ‘pure’ PVD with the
associated advantages of good throwing power and
controlled microstructure respectively. One of the main
TIN , TC,N advantages of plasma-assisted CVD (PACVD) processes
/
is that the reaction occurs at temperatures lower than
for ‘pure’ CVD. Further, the substrate is bombarded
with energetic particles prior to and during film growth
and thus microstructural refinement is possible, leading
to enhanced physical properties. As PACVD can be
performed at relatively low temperatures, certain ma-
terials (e.g. tool steels), which cannot be coated in
conventional CVD processes, can now be easily treated
without any adverse effect on the properties of the
substrate. Plasma-assisted PVD (PAPVD) covers a
broad range of PVD processes in which plasmas or
glow discharges are involved to deposit coatings. PAPVD
processes have been reviewed recently by Fancey and
Matthews [40]. The main advantages of PAPVD include
Fig. 7. Schematic of a multilayer coating architecture of Ken-
improved coating adhesion due to sputter-cleaned sub-
nametal’s KC990 grade cutting tool [38].
strates, uniform coating thickness, controlled micro-
structure and thus improved properties. Also some of
7. Sandvik Coromant (Sweden) have also marketed a the materials, which cannot be coated by ‘pure’ PVD,
multilayer ceramic coating for cutting tool inserts, which can easily be treated with PAPVD. These plasma-
is generally based on the TiCEiN/Al,O, (outerlayer) assisted processes offer many advantages, especially in
format [36]. the production of hard multilayer coatings, as mentioned
Many traditional CVD coating treatments used in- later in this section.
dustrially for carbide tool inserts employ three coating Moore ef al. [41] have investigated a multilayer coating
layers. Another three-layered cutting tool coating which system which consists of layers of TiN, Al,O,, Tic and
90 C. Subramanian, K. N. Strafford f Multicomponent and multilayer coatings

TaC on a WC-Co substrate prepared in a commercial applications using magnetron sputtering techniques [ll,
hot-walled CVD reactor. They have used a novel ap- 14, 15, 441.
proach of taper sectioning to study the interface phe- As mentioned earlier, Holleck and his co-workers
nomena, such as diffusion, using various surface an- have broadly studied multilayer coatings along with
alytical tools, viz. scanning electron microscope (SEM), multicomponents, multiple phase (composite), meta-
scanning Auger microscope (SAM) and small spot X- stable and gradient coatings. A similarly broad approach
ray photoelectron spectroscopy (XPS). Other coatings is reported by Freller and Haessler [45], who have
produced by CVD method are reported by Renji et al. compared various ion-plating processes and discussed
[42] and Habig [43]. Renji et al. [42] have studied wear the suitability of such processing techniques in depos-
mechanisms of multilayer coating systems consisting of iting multicomponent, gradient and multilayer coatings.
Tic, TiCN and TiN (thickness of each layer is 0.5-l An example of coating constitution and deposition
pm and total thickness is 5.5 pm). They suggest that possibilities for various types of coating produced by
wear of these coatings occurs by a ‘multilayer wear various methods is shown in Fig. 9 [15].
mechanism’ where removal of material takes place layer Magnetron sputtering with a rotating target holder
by layer. Such a mechanism is schematically shown in has been successfully used by Knotek and Leyendecker
Fig. 8. As there are more interfaces in the multilayer [46] to produce a 30 layer coating of TiN and Al,O,
coating, it is hypothesized that cracks are deflected by (thickness of each layer is 0.03-0.5 pm and total thick-
the interfaces. In other words, the multilayer coating ness is about 5 pm) on a cemented carbide substrate.
materials are tougher than single layers. This will be In some cases, TiN has been substituted for by Tic.
discussed in more detail later. Keem [47] has reported improved performance from
Habig [43] has investigated Tic, TiC/TiN, TiC/A1,03 drill bits coated with HfC/HfN multilayer coatings,
and TiCmiN/Al,O, multilayer coatings produced using produced by a planar magnetron sputtering unit, when
CVD and PVD methods. Some of the coatings in compared with TiN single layer coatings. Keem has
multilayer format were produced by a combinations of also modelled the effects of rotational speed of the
CVD and PVD methods. These duplex processing drill bits within the coating chamber; the dwell time
techniques are advantageous: the high temperature of the tools in the deposition field of each cathode
diffusion reaction during the CVD process improves determines the thickness of each layer and this influences
adhesion between the substrate and the first coating the machining performance.
layer, whilst the subsequent PVD coating layers provide Nippon Steel (Japan) claim to have developed the
a fine grained microstructure with better wear resistance world’s first continuous, multilayer, dry coating system
and toughness. Therefore a coating of TiN (PVD) on
TiC (CVD) outperformed all other coatings studied by
Habig [43]. Lsyrr Mstsrlsl
Concrpt
PVD using either electron beam evaporation or mag-
netron sputtering has been successfully applied to pro-
duce multilayer coatings on various substrates [ll, 14, Solid Solution Coatings
15, 44-511. Holleck and his co-workers have made a
systematic study of the production, properties and per-
Gradient Coatings
formance of multilayer coating systems for tribological

Multilayers
.: *. .
c
,. . . ;.-.. ;,.
.:.. .: .._.. .., .
z:., .‘. . ..‘. Metastable
/,, I/,/////‘I ///‘,///////‘/
Layer Materials

Multiphase Layer materials

= Plasma Spmyl
5 Low Pressure 8 cuum) Plasma Spraying

PVD ;${;~~~t”$=w;~.~.,
PACVD
= Maanetron Swttsrina
ES = IonPlating ’ -
IS I Arc Evaporation (‘Ion Bond’ Method)
(a) (b)
Fig. 8. Comparison of wear mechanisms of coatings with: (a) Fig. 9. Suitability of various coating techniques for advanced
single layer; (b) multilayer [42]. multilayer system [15].
 C. Subramanian, K N. Strafford / Multicomponent and multilayer coatings 91

to coat stainless steel strip using a process line consisting TiB2 or TiN [50, 591. However, the application of
of ion plating, sputtering and plasma assisted CVD chromium before TiN coating has been reported to
[48]. It also allows the production of metallic and have adverse effects of adhesion [60]. Interfacialmetallic
composite coatings. layers such as nickel and titanium have been observed
Other workers who have discussed multilayered coat- to increase the resistance of TiB, and TiC coatings to
ings include Turennout and Reiter [52], Yamamoto erosion [50].
[53], Schmoeckel et al. [54], Kempis [55], Dreyer and
Kolaska [56] and Konig et al. [57]. The coating systems
studied are various combinations of TiN, TiCN, A&O3 5. Discussion
and other compounds. Various multilayer coating sys-
tems are listed in Table 4. According to Leyland et al. [61], first generationcoat-
Some of the multilayer coating systems contain me- ings, such as TiN, are already in widespread use, whereas
tallic interlayers to improve adhesion, toughness and/ second generation coatings such as Ti(C,N), Ti(B,N),
or corrosion resistance. For example, chromium or (TiAl)N and (Ti,N)C are now being seriously considered
titanium (0.1-0.2 pm) is applied to stainless steel sub- for certain ‘niche’ wear applications. Leyland et al. also
strates before TiN is coated [49, 581. In another case, envisage a potential growth marked for thirdgeneration
nickel or electroless nickel is the first layer (close to coatings, Gz. multicomponent and multilayer systems.
the substrate) followed by titanium and then by Tic, In the preceding sections, many examples of studies

TABLE 4. A list of investigations on multilayer hard coating system

Reference Composition No. of layers Thickness (pm) Comments

Each Total

14 TiC/TiB*
TiNniB, 10 0.5 5 PVD
23 TiC/TiCNfI’iN 3 3.5, 1.5, 2 I Commercial
TtC/AIZO, 2 =lO
TiC/AI,OJI’iN 3 -10 Coatings
TIC + Al24 2 8, 3 11 CVD
TiAlOC/“TiN 2 3-5 CVD
32, 33 TiCfIiBr 1000 0.004 4 Magnetron sputtering
35, 38 TiCN/AI,O,/TiN 7 6, 3, 1 18 CVD
36 TiCNfliN 2 2, 6 8 CVD
TiN/TiC/TiN 3 - 3
TiC/Al,OB 2 - 10 CVD
TiCN/A120JI’iN 3 - 9 CVD
TiCDiN 2 - 8 CVD
TiC/A&OJIiN 3 - 8 CVD
37 TiCTiN 2 5, 6 11 CVD
41 TaC/TtC/A120JTiN 4 - - CVD
42 TiC/TiCN/TiN 7 0.5, 1 5.5 CVD
43 TiC/TiN 2-3 l-3 10 CVD
TiC/Al,O, 2-3 1-3 10 CVD
TiC/TiN/AlrO, 2-3 l-3 10 CVD
TiCIWiN 2-3 l-3 10 PVD
TiCTiN 2-3 l-3 10 CVIWVD
44 TiN/TiB, 1ck1000 0.001 5 PVD
TiC/TiB, la-loo0 0.002 5 PVD
TiCniN lo-loo0 0.003-0.004 5 PVD
45 TiC/A120, 30 0.03, 0.5 5 PVD
TiN/AIrO,
47 HfC/HfN 9 - - PVD
51 TiN/TiCN/i-C 3 5, 0.5, 10 lo-15 I-C (ion-assisted
deposition of carbon)
92 C. Subramanian, K. N. Strafford i Multicomponent and multilayer coatings

devoted to the development of third generation coatings

have been identified which can be applied in tribological
situations, especially for metalcutting and metalforming
tools. In fact, some of the multicomponent and mul-
tilayer coatings have already found commercial use, for
example TiCN [62] produced by PVD methods, and
TiN/TiC/TiN and TiC/Al,O,/TiN [36] produced by ‘high
temperature’ CVD methods. However, the temperature
limitations of traditional CVD techniques reduce the
range of substrate materials to which these coatings
can be applied. Hence the increasing interest in pro-
ducing plasma-assisted PVD and plasma-assisted CVD
multilayered coatings of sufficient mechanical integrity PROPERTIES PERFORMANCE
at low temperature. In some cases, what is known as / \/ \

‘duplex surface engineering’ [61, 631 has been used;

that is two or more different methods to produce a
set of coating layers - multilayers. For example, PVD
Fig. 10. Inter-relationship between various fundamental param-
and CVD can be combined to produce a multilayer eters of a coating system.
coating system [43], and other such possible duplex
treatments are listed in Table 5 [63]. These two or
more types of treatment could result in layers of ma-
terials which have different properties, possibly leading Some workers have found good correlation between
to a multilayer system as such. grain size (as low as 20 nm) of thin films and their
Surface-related properties, such as friction, wear, hardness values [66-681. As mentioned earlier, hardness
corrosion, fatigue and biocompatibility, can be improved values of multilayer coating systems have been reported
or modified by suitable surface treatment and/or coat- to be higher than those for comparable single layer
ings. Figure 10 shows the inter-relationship between coatings (see for example refs. 32 and 33). Coating
processing, properties and performance with structure hardness is not only dependent on grain size but also
as the main parameter. It is clear from Fig. 10 that on other parameters such as texture, porosity, residual
the properties of a component which is coated or surface- stress, etc., which are influenced by processing param-
treated, and ultimately its performance, are dependent eters [6].
on the structure of the coating, which, in turn, is In a multilayer situation, the flow stress of the coating
influenced by the processing parameters. More details material depends on the thickness of each layer, sharp-
of these parameters can be found in publications pre- ness of interface boundaries, flow stress of individual
viously identified. layers, etc. This becomes evident if the theory of strength-
ening mechanisms of spinodal decomposition (where
5.1. Hardness modulated structures of varying composition occur) is
It is well known that the flow stress (hardness) of extended to modulated structures of multilayers [69,
a material depends on its grain size - the Hall-Petch 701. Recently, Krzanowski has shown analytically that
relationship [64, 651: the degree of strengthening is strongly dependent on
the interface profile, becoming higher when the interface
becomes thinner and sharper [71]. Theoretical studies
where H = hardness, Ho = intrinsic hardness for a single with regard to multilayer strengthening up to five layers
crystal, d = grain size, K = a material constant. have been presented by Kamat et al. [72]. However,
the formidable task of theoretically analysing a mul-
TABLE 5. Various duplex treatments [63] tilayer system with “n” layers remains to be tackled
[711*
Thermal spraying+ laser processing A semi-analytical, semi-numerical method, using fast
Plasma spraying + laser processing Fourier transform algorithms, has been developed by
Ion beam mixing+ ion-assisted coating
Overlay coating + hot isostatic pressing
Leroy et al. [73] to calculate the thermoelastic stress
Carburizing+ thermochemical treatment fields which could lead to thermomechanical cracking
Laser hardening + thermochemical treatment when the multilayer coating system slides under load.
Carburizing + CVD treatment Leroy et al. [73] have shown the importance of elastic
Nitriding + PVD treatment and mechanical properties of coating and substrate
Nitriding + ion implantation
materials.
5.2. Adhesion choice of testing parameters may change these results
The most widely accepted measurement technique considerably.
for hard thin coating adhesion is that of the scratch The design of a coating system should begin from the
test, where a diamond stylus is traversed across the user end - understanding the application conditions,
coating surface with increasing normal load and the particularly, stress, velocity, and temperature levels.
acoustic emission and tangential (fictional) force are Then, using “alloy design” principles, a coating system
continuously recorded. When a critical load (L,) is should be designed and tested in a situation as close
reached the coating is removed. The value of L, can as possible to the real application. These three important
be found from the acoustic signal, tangential force and/ aspects are illustrated in Fig. 10. Generally, the hardness
or microscopic observations of the scratch. This method and adhesion of coatings is measured and evaluated
has been reviewed in ref. 74. Although this method by a simple test (such as scratch testing) or performance-
does not give an absolute value for the adhesive strength tested in a real application situation, such as single
of a hard coating, it does qualitatively discriminate point turning, or drilling. These tests tend to be carried
“good’ and “bad” coatings. The value of L, depends out under arbitrary conditions, which yield a result
not only on the adhesive strength of the coating to its “expected” by the researcher broadly in accordance
substrate but also on the thickness of the coating [75, with the set-out rationale. Laboratory or ‘in field’ per-
761, the friction coefficient between the coating and formance tests should however be conducted for various
the stylus [77, 781, elastic properties of the substrate coating deposition parameters, such that the full po-
161, 791, etc. The critical load for multilayer coatings tential of a coating system can be realized.
is generally reported to be high, as shown in Table 6.
As mentioned before, processing parameters, such as
bias voltage and workpiece current density, have sig- 6. Conclusions and future research directions
nificant influence on the values of L, 1441.
A review of multicomponent and multilayer coatings
indicates that improved performance in tribological
5.3. Perjormance applications can be achieved using thirdgenerationcoat-
Performance testing of a coating under a given set ings. Such coatings containing multilayers of thickness
of conditions is the ‘ultimate test’. It should be em- in the nanometre range render improved toughness,
phasized that a coating which performs well in a par- hardness and wear resistance.
ticular situation may not perform to expectation in In the literature three distinct generations of coatings
other situations. Similarly, a coating which is ranked have been identified, representing a logical development
high in laboratory tests may not live up to expectation broadly to more sophisticated types in terms of com-
in actual applications. As seen earlier, multilayer and position and structure. Strafford et al. [80] have discussed
multicomponent (third generation) hard coatings have the problems and rationale in designing, ab initio,
been reported to show improved performance over coatings systems with improved resistance to wear and
monolayer and mon~om~nent coatings (first gener- corrosion. They have identified, in particular, the com-
axon) [e.g. 32, 42, 43, 451. For example, Fig. 11 shows patibili~ problems - the ~ndamentally differing re-
relative performance of a multicomponent coating [17, quirements - of, for example, a coated toollworkpiece
741 whereas Fig. 12 exhibits the better performance of environment on the one hand, and those requirements
multilayer coatings [32]. It is important to note that of the coating/substrate interface on the other.

TABLE 6. Values of critical load for selected single and multiiayer coating systems

Coating Thickness Deposition technique Critical Refs.

(pm) load (N)

TiCYIIBz Magnetron sputtering > 1OON 44

TiN 7 Random arc 55f5 25
7 Steered arc 85rt5 25
TiHfN 5 Steered arc 85+5 25
0.94 0.06
TiNbN 5.4 Steered arc 9015 25
0.92 0.08
TiC Magnetron sputtering 10 33
TiB, Magnetron sputtering 20 33
TiCniB Magnetron sputtering 38 33
94 C. Subramanian, K. N. &afford I M&component and multilayer coatings

Number of drilled holes till failure or more likely a multilayer coating system - thus
400 $ 0-W Nx constituting the so-called third generation type of coating.
The open literature concerning such coatings indicates
that success may be achieved through the use of such
&Ill: GGhrina 6 mm 0 a multilayer constitution. However it is by no means
Mpterial: x210Crw12
strength: 770 N/mm’
established that optimization - fitness-for-purpose -
MI: 242 has yet been achieved. Much intensive research needs
to be conducted, ranging from appraisal of potential
coating materials properties - physical, mechanical
and chemical - for incorporation into the design audit,
followed by systematic performance analysis of various
components coated in multilayer format. Attention to
quality assurance here is seen as a critical element
WI.
It is believed that much will be learnt initially on a
‘compare and contrast’basis - where a standard method
of analysis and diagnosis of, e.g., tool wear/failure in
a particular working situation, e.g. drilling or single
Reversible
cutung tip: SNUN 12O4O2 point turning, will be adopted for uncoated components
s?awfC#JyuSlC 1054)
Cut&&
Speed: 24Omlmin. and components coated with a “well known” coating
Feed: 0.22 mm/rev.
Depth of cut: 1.5lllm
such as TiN (to act as controls), such performance to
DUr&bll: bmin. be directly compared with corresponding behaviour of
multilayer coating systems.

b
Fig. 11. (a) Drilling tests with various coatings; (b) crater and
flank wear of reversible cutting tools [17, 741. References

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