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TITANIU" NITRIDE PYD

COATING TECHNOLOGY

Surface engineering
designer's guide
Dr ALLAN
MATTHEWS:
Lecturer, Department
of Engineering
Design and
Manufacture,
University of Hull.

A. Matthews
The latest techniques to become widely available
commercially to design engineers and others who
specify surface coatings are those for ionization
assisted physical vapour deposition; titanium nitride
being the main coating material at this time. The
background to this new technology is outlined and
information is provided about the main commercial
processes. An indication is given of potential problems
which can arise, leading to performance variability.

The availability of processes to deposit hard ceramic


titanium nitride coatings on to hardened high speed
steels and hot working die steels without causing
softening has been one of the most significant
breakthroughs
in surface engineering in the past 20
years. The processes in the main replicate the
precoated surface finish, and items can thus be finish
machined before coating. Already many cutting and
forming tools are being PVD (physical vapour
deposition) coated with titanium nitride; it is likely,
though, that the range of applications will expand
considerably
as the potential
of these coatings
becomes more widely recognized, and indeed as other
ceramic coatings emerge. In general, the coatings
have hardnesses of over 2000 kg mm - 2; twice as
hard, for example, as electroplated hard chrome or a
thermochemically
treated alloy steel. Furthermore,
the coatings have good friction and corrosion
properties, as well as high temperature stability.
One problem which seems to have slowed down
industry's
adoption
of the processes
has been
confusion
over the relative characteristics
and
capabilities of the various techniques available. This
guide begins with an overview
of the main
commercial methods, with the aim of removing this
confusion. It should be said that at this time all the
processes are able to report successes; equally, it is
probably fair to say that they. have also encountered
some problems as they move through the initial
development
stages. We shall therefore include a
description of some of the potential problems which
can arise in these processes, concluding with some
applications information.
PROCESS DETAILS
All the processes relevant to the present guide are
PVD
techniques,
which
obtain
the titanium
constituent
in the coating
by vaporizing
soli9
titanium. The CVD (chemical vapour deposition)
process, on the other hand, is fundamentally different
in that the titanium is obtained in the form of a

Details of applications reported by users are included.


It is intended that with the aid of this guide engineers,
designers, and other potential users will have a clearer
picture of the technology involved and its strengths and
weaknesses.
SE/11

1985 The Institute of Metals


for Surface Engineering.

and the Wolfson Institute

gaseous reagent, such as titanium


tetrachloride.
Various other process features are different in the
CVD process, the main one being that deposition
temperatures are typically about 1000C, compared
to less than
for the PVD processes. CVD also
operates under rougher vacuum conditions.
The available PVD processes can be divided into
two groups. One group thermally evaporates the
titanium, most usually with some form of electron
beam gun. Within this group we shall include arc
evaporation, in which the titanium is volatilized by
striking an arc discharge on its surface. The other
group uses an atomic bombardment
(sputtering)
process to atomize the solid source material.

sooac

Evaporative processes
The common
feature
of all the commercial
techniques, and the breakthrough
which has allowed
their recent introduction,
is that they incorporate
ionization
of the depositing
species - imparting
greater
energy
and enabling
lower deposition
temperatures
to be used. These processes
are
therefore sometimes known as plasma (or ionization)
assisted techniques - signifying the presence of a
discharge
plasma
within
the
system.
Early
researchers in the field coined the title 'ion plating' 1
but this term is now less widely used. As process
developments
occurred
in both sputtering
and
evaporation,
researchers
have
invented
new
ionization enhancing techniques and terminologies.
Professor
Bunshah
of UCLA
has contributed
significantly to the contemporary
move towards
ionization
assistance
in ceramic deposition.
He
termed his process Activated Reaction Evaporation (ARE), and incorporated
a positive 'probe'
electrode to draw electrons emitted from the vapour
source, thereby increasing ionization of the reacting
species (Fig. 1).2 Unlike other 'ion plating' methods,
the components
are not biased negatively
in
ARE, and it might therefore be assumed that they
do not receive ions. This is not the case, however; the
Surface Engineering

1985 Vol. 1 No.2

93

94

Matthews

TiN PVD coating technology


negativ<a bias
h<aat<ar
substrate

substratC2
positive
el~rode

negative bIas

vapour
source

vapour
source

1 ARE system layout2

presence of the positive electrode makes the


specimens cathodic in the resulting gas discharge so
that they could be said to be ion plated, in that a
proportion of the arriving atoms are ions. In ARE a
supplementary direct heating source is utilized on the
samples. Bunshah3 has also reported a technique
known as Biased Activated Reaction Evaporation
(BARE) which combines ARE with a negative bias
on the specimens. This is similar to a system used by
Koboyashi and Doi (Fig. 2).4 Matthews and Teer
have reported56 a Thermionically Assisted Triode
ion plating system (Fig. 3) which incorporates a
negatively biased sample and a thermionic electron
source (with or without an additional positive
electrode). Again, ionization
enhancement
is
considerable; the benefit of this system being that it
can offer plasma control which is independent of the
vapour source.
The ARE and thermionically assisted triode
processes usually use a conventional self-accelerated
electron beam gun to vaporize the evaporant, and
add discharge modifying electrodes to enhance
ionization. Certain other vapour generation sources
are available which intrinsically produce greater
ionization due to their mode of operation. All of the
successful commercial producers use sources which
provide this benefit, as discussed below.

applications details in Ref. 9. Precise process details


(beyond the patent specification) are not available for
publication, though some information has become
generally available. For example, the specimens are
heated by electron bombardment before coating.
This seems to be a unique feature of the Balzers
process. It is believed that the crucible is reciprocated
vertically during coating, in order to achieve more
uniform deposits. Specimens, mounted around the
perimeter of the chamber, are rotated during coating.
Other than these factors, it is probable that the
ionization conditions, etc. are similar to those
achieved by the Ulvac, Tecvac, Multi-Arc, and VacTec processes described below. Given the widely
differing approaches adopted by these companies, it
is interesting to note that they all seem to operate
under similar specimen bias and ionization conditions, pressures, and substrate temperatures. One
feature of the Balzers operation which seems to set it
apart from other companies is an insistence on high
quality substrates. Thus, for example, they prefer
tools which have been only recently ground. Items
which have been in store, or 'do not meet Balzers'
metallurgical requirements, are not coated and this
helps to ensure consistent results.
The Balzers company pioneered the introduction
of PVD TiN technology into manufacturing industry.
In March 1983, for example, it was claimed that
Balzers had already coated 3-4 million tools in the
preceding 6 years.! 0 The first company to offer
titanium nitride coatings on its standard range of
tools was Guhring of the Federal Republic of
Germany (in 1980) using the Balzers process (which
was the only one available in Europe at that time).
Tecvac of Cambridge is the only wholly UK
owned company offering its own industrial
evaporative TiN coating system. It utilizes both an
ionization increasing electron beam gun system and
additional thermionic assistance to enhance the
discharge. This -improves the control of the process,
by ensuring that variables can be independently

I ndustrial evaporative source systems


Table 1 lists some of the features of commercially
available evaporative units. The Balzers company
utilizes a system which incorporates an electron
source operating under medium vacuum conditions,
resulting almost in an 'arc' mode of discharge passing
through the chamber to impinge on the crucible. The
net effect is to increase ionization in the coating
chamber. The arrangement is shown in Fig. 4, which
is based on a patent specification.7 Figure 5 shows a
photograph of the plant. Some of the strategic
history of the process is outlined by Vogel and
Scherrer in Ref. 8. Buhl et al. discuss some

Thermionically assisted triode system layoutS'

negativ<abias
substrate
substrate
negative bias
positive el ectrode
vapour

vapour
source
2

BARE system layout4

Surface Engineering

1985 Vol. 1 NO.2

source
4

Schematic of Balzers system 7

Matthews

6
5

Balzers
Balzers

BAI 730 evaporative

source

coating

plant:

courtesy

changed. This, for example, permits argon Ion


bombardment
heating before coating, without the
need to have the vapour source in operation, or
direct radiant heating.

TiN PVD coating technology

Tecvac evaporative source coating plant: courtesy

95

Tecvac

The thermionically
assisted triode arrangement
was first used for ion plating by Baum 11 in 1967. He
saw the attraction
of this technique as fourfold.
Firstly,
greater
control
over the discharge
is
obtained.
Secondly,
comparatively
low negative
voltages (e.g. < 400 V) need to be applied to the
sample, improving stability. Thirdly, the process can

Table 1 Summary of typical commercial evaporative source PVD unit specifications

Supplier
Unit
Type
Evaporation method (typical
no. of sources)
Independent ionization
enhancement
Substrate preheat?
Substrate temperature during
deposition, C
Substrate bias
voltage, - V
Substrate rotation?
Deposition pressure, )lbar
Cycle time
Typical coating thickness,
)lm
Maximum effective working
volume:J:,m3
Maximum load, kg
Approximate plant cost
Total power consumed per
cycle, kVAh
No. of 6 mm drills/batch
No. of 100 mm dia. x 100 mm
hobs/batch

Balzers,
Liechtenstein

Multi-Arc, USA

Vac-Tec, USA

Ulvac, Japan

Tecvac, UK

BAI730
Single chamber
Electron beam (1)

MAV 40
Single chamber
Electric arc (4)

ATC 400
Single chamber
Electric arc (4)

IP 35L
Single chamber
Electron beam (1)

Yes

No

No

IPB 45
Single chamber
HCD* electron
beam (1)
No

Yes: electron
beam

Yes: Ti ion
bombardment

Yes: radiant
heating?

Yes: argon ion


bombardment

450

Yes: Ti ion
bombardment
(200-485C)
350-500

450

500

350-500

<1000

Unknown

Unknown

<400

Yes
1-4
2 h 20 min
15-4

Yes
4-8
2 ht
3-6

450 (preclean)
150 (coating)
Optional
4-8
1 h 10 mint
3-5

Yes
4-8
2 h 20 min
2-6

Yes
4-8
2 h 20 min
2-4

01

02

0102

0072

014

600
500000-660 000
100

225
250000- 300 000
50

Unknown
400000
120

Unknown
250000- 300 000
90

300
150000-170000
50

700-800
Unknown

600
40

Unknown
Unknown

Unknown
16

1000-1600
30

Yes

The table is based on information supplied by companies.

* HCD =

hollow cathode discharge.


t Heating and cooling times may be extended for items of larger mass, e.g. a 5 h cycle time for a 115 kg hob (quoted for MAV 40).
t The shape of this volume may differ depending on the process, e.g. in the Balzers system, the working volume has an annular shape,
whereas in the Leybold-Heraeus system the region is more planar.
Surface Engineering

1985 Vol. 1 No. 2

96

Matthews

TiN PVD coating technology

nQgativQbias
substrate

----

.........

"7

vapour

sou rca

HCD system layout15

be carried out at lower pressure, and fourthly,


unwanted substrate heating can be reduced over
conventional diode discharge techniques, as the ion
power is lower due to the reduced bias voltage.
Tecvac has the greatest number of PVD TiN
machines in operation in the UK, with installations
in Cambridge, Skelmersdale (Torvac Processing Ltd),
and Halifax (Holt Bros Heat Treatment Ltd).
Agreement has also recently been reached with the
major CVD company Bernex which will be
representing Tecvac in various regions of the world.
The basic specification for the Tecvac IP 35L system
is shown in Table 1, using information from Refs. 12
and 13. Figure 6 shows a Tecvac installation.
The major Japanese company in this field is Ulvac,
which employs a Hollow Cathode Discharge (HCD)
electron beam gun in its process. The ionization
benefits of this were first highlighted by Morley and
Smith (e.g. Ref. 14). Figure 7 shows a schematic view
of the system, based on an Ulvac paper.15 It seems at
this time that Ulvac has the greatest number of
plasma assisted TiN coating machines out in the
field. The figure certainly exceeds 30 worldwide on
titanium nitride deposition plants alone, some going
into Ulvac group companies. Mitsubishi and several
other Japanese tool companies also have Ulvac plant
installed. In Europe, Samputensilli in Italy has Ulvac
equipment. Several US companies have plant, e.g.
Star Hobs 16,17 and General Magnaplate.18 Ulvac
offers two main production plants: IPB 30 and
IPB 45. Some information on the IPB 45 from
Ref. 18 is presented in Table 1.
In the USA the technique currently favoured for
TiN deposition appears to be that based on arc
evaporation. There are at least three companies
offering this technology: Multi-Arc, Vac-Tee, and Cat
Arc (a division of Metco). Multi-Arc operates its
process under licence to the USSR owners of a US
patent dated 1974.19 Vac-Tec bases its technology on
nagativa bias

substrate

magn~tic coil

vapour
source

Schematic view of arc evaporation process

Surface

Engineering

1985

Vol. 1

NO.2

Vac-Tec ATC 400 arc source deposition unit: courtesy Vac-Tec

a US owned patent dated 1971.20 The schematic view


in Fig. 8 is based on the latter patent. It is interesting
that one of the earliest patents on arc source
deposition was filed by the Metropolitan-Vickers
company of Manchester, England in 1958.21 This
appears to embody the important arc source features.
Figure 9 shows the latest Vac-Tee unit.
The principle of the arc source is very simple. A
titanium cathode is configured so as to operate in an
arc mode. The are, once initiated, emits a dense metal
plasma whose ions have high intrinsic energy. One or
more arc spots are formed which move randomly
over the cathode surface. Typical spot diameters are
of the order of 10 Jlm, giving current densities per
spot of 106-108 A em - 2. It is believed that no molten
pool is formed on the titanium source, which can
thus be operated in an inverted mode. The plasma
conditions generated lead to increased ionization of
metal and non-metal species (as do the Ulvac HCD
gun, the Balzers gun, and the Tecvac system).
In the UK, Multi-Arc (Europe) Ltd was
established in Co. Durham in 1982. Recently, an
arrangement has been reached with Siemens which
has resulted in a transfer to the Federal Republic of
Germany for the company's main operations. A
company called Vidionique has been formed in
France, jointly by Vide et Traitement and Multi-Arc.
A similar joint arrangement has recently been
reached with two Japanese companies, one a tool
manufacturer, the other a vacuum equipment
company; they will handle Far East sales. In the USA
Multi-Arc has joined with Cleveland Twist Drill in
joint ownership of Scientific Coatings, a company
formally specializing in CVD. Multi-Arc has also
sold rigs to other companies such as TRW in the
USA and JJ Castings (Investments) in Wales.
Multi-Arc advertises three models: MAV 20, 40,
and 48. The numbers refer to the chamber diameter

Matthews

and height (in inches) which are equal in each case.


These dimensions do not define the usable volume,
since the arc sources must be positioned in the
chamber to avoid macroparticle
deposition on the
samples, thus constraining possible locations for the
latter items. There are typically four arc sources
installed in each of the two larger units, while the
MA V 20 usually has two. Various developments are
available,
but the quoted
specification
for the
MAV 40 unit is shown in Table 1. Some details are
also gIven about the Vac- Tec ATC 400 system
(Fig. 9).
Sputtering source processes
As discussed above, the sputtering mechanism can be
used to produce the depositing species. Rather than
evaporating the titanium, atoms are removed from
the titanium source or target by ion and neutral
bombardment,
through
a momentum
transfer
process. The target is usually cooled, and the
sputtering
processes in general operate at lower
substrate
temperatures
than
those
involving
evaporation.
Sputtering is also (usually) a much
slower deposition rate process. There are, however,
ways to increase the rate, such as by magnetically
confining the bombarding
species and, electrons at
the target or by increasing the size of the source
compared to that of the samples.

I ndustrial sputter source systems


Table 2 lists some of the features of commercially
available sputtering units. The Dowty Electronics
company offers a variant of its 'hot rod' process for
ceramic deposition, which has been under development since the early 1960s.22 Duckworth23,24
has
given details
of the technique.
Unlike
other
sputtering processes, the target is heated until it
glows hot (at a temperature of about 1000C), which
is said to aid compound synthesis on the target.
Some process features are given in Table 2. Dowty

TiN PVD coating technology

97

/8lectrodQ5
v substrate

vh~at~r

I..-----~

p...

o
P

vsource

jr'"

p
b

g
'"'"

10

Sputter ion plating system layout

has tended to concentrate on multilayer deposition


based on zirconium nitride, claiming that this gives
improved oxidation resistance and a lower friction
coefficient than titanium nitride.22 Cycle times for the
Dowty
production
unit (DSC 91) are typically
between 100 min and 3 h.25,26 The system uses a
double in-line chamber incorporating
an air lock.
Dowty
states25
that the price for coating
a
component averages at less than 25% of the original
component price. This will depend greatly on the size
and value of the component. Perhaps a more useful
guide is that it costs about 11 cents to coat a 025 in
drill.25 This indicates a total cost per batch of
200-300,
figures which agree quite well with
unofficial quotations from several manufacturers.
The TI Abar company
has licensed UKAEA
Harwell's
'Sputter
Ion Plating'
process for the
deposition of titanium nitride. This was described by
Coad and Dugdale In 1977.27,28 More recently
Newberry et al.29 have given details of TI Abar's
production unit; Fig. 10 is based on an illustration
in that paper. The operating pressure is rather higher
than the other processes, and can be maintained
without the need for a diffusion or turbomolecular
pump, which simplifies the pumping arrangement. By
using electrodes at a slightly higher positive potential
than the samples during coating, sputter cleaning can

Table 2 Summary of typical commercial sputter source PVD unit specifications


Dowty, UK

TI-Abar,

Z 700 P2/2
dc magnetron sputtering, single chamber

DSC 91
RF sputtering,
double in-line chamber
with air lock

Glo- Tine 24 x 36
dc sputtering,
single chamber

Two target pairs,


each 12 m x 06 m
500-600
No

One target pair

Multiple

300-1000
Unknown

Yes, 300-600C

Optional

2000 RF
Yes: discharge
heating
No

06 m dia. x 1 m
cylinder
Unknown
Yes: radiant
heating
Yes: indirect
radiant heating

300-500
250
Optional
25
40 min to 1 h
2-3

50-300
Unknown
Yes
Unknown
Ih
0'3-05

250 max.
0-1000
Yes
Unknown
1 h 40 min to 3 h
0'2-3'0

450-500
::::;1000
No
15-28
8h
2-4

041
400000

015
170000

004
Unknown

017
275000

Unknown
6000

40
800

Unknown
4200

10-20
1200

Supplier

Leybold-Heraeus,

Unit
Type

ZV 1200
dc magnetron sputtering, 3 chamber in-line

Target
Geometry
Applied voltage, - V
Auxiliary heating?
Substrate

preheat?

Substrate temperature during


deposition, C
Substrate bias voltage, - V
Substrate rotation?
Deposition pressure, Jlbar
A verage cycle time
Typical coating thickness, Jlm
Maximum effective working
volume, m3
Approximate plant cost
Total power consumed per
cycle, kVAh
No. of 6 mm drills/batch

The table is based on information

FRG

Leybold-Heraeus,

FRG

rod

UK

supplied by companies.
Surface

Engineering

1985

Vol. I

NO.2

98

Matthews

TiN PVD coating technology

nQgativQ bias

source
cold coating plasma

substrate
magnat
hot coati n9 plasma

11 Leybold-Heraeus

double magnetron

layout30

take place. Also, the target material is at earth


potential, which simplifies construction. The coating
rates are much lower than for the other techniques
described in this review, typically l}.lm h -1 for
titanium nitride. It is believed that the company is
seeking to achieve a cycle time of 8 h. In spite of this
apparent drawback, it seems that the process can be
competitive.
Due to the good 'throwing
power'
achieved, many components can be uniformly coated
simultaneously, without the need to rotate.
The Leybold-Heraeus
company
of FRG has
developed several sputtering systems; the main one
has two planar magnetron targets vertically opposed,
as shown in Fig. 11. This produces the highest
deposition rate currently available using sputtering.
Since this system is rather unconventional,
it will be
described in some detail, using information
from
Ref. 30. It is evident that specimens are biased to
ensure ion bombardment
heating. They are situated
between the high rate cathodes. The 'cold' and 'hot'
deposition modes are defined by the spatial extension
of the confined plasma in front of the target, which
depends on the power dissipated at the cathode, the
magnetic field strength, and the gas pressure. Munz
and co-workers30 have carried out experiments to
determine the possibility of drawing an ion current
from a high rate cathode, as a function of the
distance between substrate and target. From that
work it is clear that, for the system to be effective, the
two cathodes must be close enough together. It must
then only be possible to locate samples within a well
defined planar region for uniform results. Nevertheless, it is claimed 30 that good uniform rate
distribution
has been achieved.
The deposition
pressure quoted is 25 }.lbar*, which should indeed
ensure good throwing power.
M unz goes on to describe details of one of the
Leybold-Heraeus
production plants. It utilizes an inline load lock system. Initial heating up of the
substrates to between 400 and 500C occurs in the
input vacuum interlock. They then move to the
process chamber in which there are two pairs of
cathodes, each 16 m long and 23 em wide, allowing
100-200 drills to be coated, by mounting them in
a frame 12 m x 06 m. The distance between the
cathodes is adjustable to the size of the substrates
(max. dia. 200 mm). Specimens greater than 25 mm in
diameter must be rotated. The substrate carrier frame
is oscillated during sputtering, to improve uniformity.
After coating, the substrate carrier moves to the exit
vacuum interlock, where samples are cooled to at
least 200 e in a non-reactive
atmosphere.
System
0

1 bar = 105 Pa.

Surface Engineering

1985 Vol. 1 No.2

12

Leybold-Heraeus
Leybold- H eraeus

sputter

source

coating

plant:

courtesy

features for two types of Leybold-Heraeus


plant are
summarized in Table 2, the Z 700 being shown in
Fig. 12.
PROCESS PROBLEMS
It would be wrong, in a guide of this kind, to give the
impression that no problems exist in PVD TiN
technology. Most engineers and designers who have
tried these processes will be aware that problems can
arise. Before going on to describe
successful
applications of the techniques we will therefore try to
indicate
the potential
problems,
and
suggest
solutions where possible.
Most problems relate to variability and inadequate
process control. The main coating properties which
can vary are the thickness,
composition/phase,
preferred crystal orientation, morphology, structure,
and hardness. These dictate the friction and wear
performance
and are influenced by the process
variables: pressure, specimen voltage, current density,
metal to gas ratio, source to specimen distance,
evaporation/deposition
rate,
and
temperature.
Adhesion is another coating property, influenced by
the above and also by substrate factors.
Property variability
Consider first the most basic of properties, thickness.
It is known that the pressure and hence the degree of
gas scattering can have an important bearing on the
uniformity of deposits. In Ref. 31 some results were
reported for coatings on tubes, deposited at different
total pressures. At a pressure of 20 }.lbar coatings
were almost uniform both on the outside and inside
(to a depth of 8 em) of a 2 em dia. tube. The same size
of tube showed a fourfold increase in thickness nearer
to the source when coated at 33 }.lbar. Why, then, do
most producers not utilize higher pressures? There
are two basic reasons: the first is that certain vapour
sources can be operated only at low pressure. For
example, arc sources operate most effectively at less
than about 10- 2 }.lbar20,31 and hence low pressures
and multiple arc sources with specimen rotation are

Matthews

preferred. High voltage electron beam guns also


require a good vacuum (less than about 01 Jlbar),
in order to avoid unwanted discharges. They must
thus be differentially
pumped,
using a divided
chamber
system,
to permit
higher
deposition
pressures.33 Hollow cathode discharge guns can also
present problems, since a switch in discharge mode
may be observed at certain pressures.33 Another
reason why low pressures are preferred is that the
coating structure tends to become more columnar
and friable as the pressure increases.34 To counteract
this, higher specimen temperatures
and current
densities must be used, which -may result in
deleterious substrate softening and distortion. The
tendency
then is to compromise
on operating
pressure. Many operate in the 4-8 Jlbar range and, as
discussed in Ref. 31, even at the top of this range
there is a need to rotate specimens so that all areas
receive the same net coating flux.
Only thickness variations have been referred to
above, with no mention of stoichiometry and phase
uniformity, a subject of possibly greater significance.
The metal flux is greater nearer to the vapour source,
while the gas species are assumed to be more
uniformly
dispersed. This obviously leads to a
tendency to deposit metal rich coatings nearer to the
source. Additionally,
since nitrogen tends to be
sputtered
from the specimen more readily than
titanium,
any non-uniformity
in bombardment
(produced, for example, by field effects) can lead to
composition variations. Sharp edges of knives and
cutting tools are especially prone to this. Certain
types of component, therefore, require careful jigging
and precise control of the bias voltage and currents
to ensure that the coating is not sputtered away at
the edge. Another influencing factor is that re-entrant
features in components
can result in abnormal
discharge effects, leading to coating inhomogeneity.
The effect on preferred orientation
or crystal
texture under different ionization
conditions
has
recently received greater attention,
and is now
recognized as critical to the tribological performance
of coatings. Some important findings on this topic35
are presented
in this review. Firstly, although
increased hardness tends to improve wear resistance,
the correlation is not direct. For example, TiN films
in which the (200) crystal planes are preferentially
aligned to the surface are more wear resistant than
TiN films showing a (111) texture and the same
hardness. The improvement may be due in part to
the increase in coating densification which occurs
under the higher ion bombardment conditions giving
the (200) texture. Another interesting result is that
films with a hexagonal
close packed titanium
structure containing interstitial nitrogen and having
a (110) orientation demonstrate
levels of hardness
and wear resistance not previously encountered with
titanium rich coatings. These films require high ion
current densities for their formation. Excellent results
are also achieved with coatings containing Ti2N;
these, too, need enhanced ionization. The degree of
enhancement
may be defined by the ionization
efficiency, which gives the percentage
of atoms
arriving
at the
specimen
that
are
ionized.
Conventional
non-enhanced
dc diode ion plating
systems typically achieve ionization efficiencies of less
than 01%. Levels greater than 07% are recom-

TiN PVD coating technology

99

mended for optimum titanium nitride coatings.35


Hence, preferred orientation is yet another coating
variable which must be controlled.
Furthermore,
achieving the optimum
phase composition
and
orientation on all surfaces of a component during
each run, and from run to run, can be a major
challenge for process operators.
Process control
The
problems
relating
to coating
variability
discussed above are common to most if not all PVD
methods,
though
there are certain
differences
between
techniques
in the control
of process
variables. The need to ensure that parameters can be
controlled independently is a particularly significant
factor, as discussed below.
Consider first the need for repeatable evaporation/
deposition
rates. It is important
to reduce any
variability, both to ensure effective thickness control
and to allow control of the reactant balance and
ionization level.
There are certain inherent evaporation
problems
peculiar to arc sources; probably the main difficulty
is the control
of macroparticles.
According
to
Daalder, particles are ejected from the cathode
source which have sizes ranging
from several
hundred angstroms to several tens of micrometres.36
Although ejected primarily at low angles to the
cathode plane, they have been found both in the
coating and below the cathode
plane.3? These
macroparticles
may not be a problem
in the
deposition of single element coatings, but could cause
degradation in ceramic compound coatings such as
TiN. If, for example, droplet size particles of titanium
form in the coating they will be softer than the
surrounding
TiN matrix, and detrimental
to the
performance of the coating and the surface finish of
the components. For example, in one application, a
component with a 01 Jlm CLA base finish, when
coated by an arc technique, gave a 04 Jlm CLA finish;
other techniques replicated the 01 Jlm CLA finish.
Several solutions
to the problem
have been
suggested. Daalder37 found that the lower limit of
mass loss from an arc source cathode is defined by
the ion current, suggesting source operation at low
current levels. It seems that operation of commercial
arc sources at sufficiently low currents may cause
problems, probably because of arc instabilities,38 and
also because
of a consequential
reduction
in
deposition rate. Another possibility for macro particle
elimination is electrostatic repulsion. Boxman and
Goldsmith 39 have shown that macro particles assume
a negative charge with respect to the plasma, and this
may offer a means of limiting droplet transfer to the
specimen.
Two important
process control variables in all
techniques are ionization enhancement and heating.
As discussed earlier, ion current density and pressure
can have a marked effect on coating properties.
These two variables combine to define the ionization
efficiency. This influences crystallographic
texture,
structure, hardness, and even composition.
Early
research illustrated the difficulty in depositing good
coatings without enhancement.
Modern processes
now utilize vapour generation sources which increase
ionization, thereby reducing this problem; however,
there remains a need to heat the specimen before
Surface Engineering

1985 Vol. 1 No.2

100 Matthews

TiN PVD coating technology

coating. This is achieved by a variety of means,


including
direct
radiant
heating,
electron
bombardment, argon ion bombardment, or metal ion
bombardment. The first of these may be inconvenient
when different components and jigging arrangements
are used from batch to batch; also, some energy may
be wasted in heating the chamber walls. Electron
beam heating is more 'line of sight' -and potentially
non-uniform. Argon ion bombardment is effective,
but the simple dc diode arrangement must be
supplemented in order to achieve the power input
levels needed for adequate heating.40-42 Systems
incorporating independent ionization enhancement
are well suited to this requirement, in that full control
is achieved throughout the process, even when the
vapour source is not active. The intrinsic advantage
of ionization enhancement may thus also be seen as a
possible drawback. Consider the arc source: if this is
operated before the coating stage (to enhance
discharge heating) then it is important to select an
initial specimen bias level above the sputtering
threshold for titanium, to avoid titanium deposition
and ensure effective cleaning; but this also heightens
the risk of overheating. The process should become
more controllable as the cleaning is completed and
the bias level can be reduced to a level that will allow
the coating to be deposited, and avoid overheating
the item being coated.
In all processes it is particularly difficult to ensure
uniform
bombardment
and
heating
when
components of different size are being coated
simultaneously. The discharge power input on a
small diameter component will be greater than on a
large diameter one;40 small components will then be
more prone to overheating. Additionally, as thermal
radiation is the dominant heat transfer mechanism in
most systems,41 components not within line of sight
of the cooled chamber walls will get hotter than
those that are. When multicomponent jigging is used
this factor must be taken into account, and is another
reason why specimen rotation, and even reciprocation, is often desirable.
Cooling, before removal of components from the
coating chamber, can be another problem, which
adds considerably to the process time for
components with a large thermal mass. A forced
cooling system has therefore been developed by at
least one company.12
An important implication of effective heating
control is that the adhesion achieved is critically
dependent
on
the
deposition
temperature.
Helmersson et al.43 have shown that optimum
adhesion is achieved with coating temperatures of
400-500C. Temperatures below this give reduced
bond strength, while above this a brittle carbide
phase may be produced at the interfaces, reducing
the effective adhesion. Other factors which influence
adhesion include the precleaning procedure.44 Recent
work by Hibbs et al.45 has also shown that the
substrate material can influence epitaxy and the
microstructure of the coating; Helmersson et al.43
confirm a consequent improvement in adhesion if
certain substrates are used, sintered high speed steels
being better than those produced conventionally.
Other process factors
There are a number'
Surface Engineering

considerations when usingPVD coating methods for


industrial applications. One is the problem of
masking areas which do not require coating. The
provision of an earthed shield close to (but not
touching) these areas can be effective but does not
provide a precise division between coated and
uncoated regions, and can present problems on
complex shapes. If a mask is clamped to components
then there may be problems due to gas entrapment.
This can be particularly harmful in systems operating
in a high ionization mode. Bursts of gas (as well as
point defects) can induce arcing on the component,
with very detrimental effects on surface finish and
performance.
A different type of problem arises when there is a
need to fully coat a component. Because it is usually
necessary to clamp the item to a jig or electrode,
there will always be an uncoated region. Although
work is proceeding into barrel coating systems,
these have presented problems for titanium nitride
deposition, and it is then necessary to coat
components more than once. Pin-hole defects
especially can cause serious corrosion problems when
the substrate is anodic with respect to titanium
nitride and the component operates in a damp
environment. The need for a dense and pore-free
coating structure is thus a prime requirement.
In spite of these cautionary comments on process
problems, it is still clear that ionization assisted PVD
methods for depositing ceramics such as titanium
nitride offer tremendous potential in many areas of
surface engineering, as will be shown in the following
section.
APPLICATIONS INFORMATION
There have been many industrial and laboratory
trials conducted on coatings deposited by the various
plasma assisted techniques, the literature being
dominated by titanium nitride. Since it would be
impossible to record every reported test result, what
follows is a selection of representative information
aimed at highlighting the more interesting observations about the use of these, coatings in industrial
situations.
The two main applications areas are metal forming
and metal cutting tools (Fig. 13). In both types of
process the most severe load is placed on the tool
surface when the workpiece is rendered fully plastic,
as occurs, for example, in extrusion and at the chip
during cutting. The author has reported46 a

13

of

1985 Vol. 1 No.2

important

practical

TiN coating on M42 high speed steel cutting tool, deposited by


Multi-Arc process: courtesy Wolfson Institute for Surface
Engineering

Matthews

laboratory test which was devised to simulate such


elastic-plastic contact, based on a repeated plane
strain compression test. After 5000 indentations into
mild steel strip at 50% deformation there was
virtually no wear of the titanium nitride coated dies,
while uncoated dies subjected to the same test
showed severe scoring in the direction of metal flow.
This test, and others based on the pin-on-disc35 and
abrasive wheel techniques47 have indicated the
suitability of the coatings for industrial processes,
and this promise has since been borne out in many
practical applications.
Table 3

Dia. x depth, in

1045 steel, HRC 15

05312 x 225

0,2656 x 10

Copper

bronze

H-13 tool steel, BHN 200

12L14 steel, BHN 200-250

41L40 steel, BHN 200-250

Hastelloy,

101

Mention has been made above of the Guhring


company, which offers a range of coated twist
drills, under the title S-Drill. A number of claims
are made for these, including an average 400%
increase in life. Of greater importance, however, has
been the potential to increase cutting feeds and
speeds. An additional benefit is that the holes
produced often have a much better surface finish
than those made by an uncoated drill; frequently a
finishing reamer operation is thus avoided. Perhaps a
surprising result is that coated drills (and indeed
other tools) still provide an extended life even after

Drill performance increased by PVD TiN coating: courtesy American Machinist10

Work material

Aluminium

TiN PVD coating technology

BHN 240-310

304 stainless, BHN 225-275

316 stainless, BHN 300

4130 steel, HRC 18-22

4140 steel, HRC 20

4140 steel, HRC 20

4140 steel, HRC 22

4140 steel, BHN 235

4140 steel, BHN 32

0,6562 x 150

0,5625 x 350

04062 x 325

04062 x 30

02812 x 025

0375 x 550

0375 x 175

03125 x 088

01875 x 10
Uncoated is
cobalt HSS
0-2188 x 10
Uncoated is
cobalt HSS
0125 x 10

0125 x 10

0250 x 20

feed, in rev - 1
rev min - l/surface
in min-1
no. holes
feed, in rev - 1
rev min - l/surface
in min-1
no. holes
feed, in rev - 1
rev min - l/surface
in min-1
no. holes
feed, in rev - 1
rev min - l/surface
in min-1
no. holes
feed, in rev - 1
rev min - l/surface
in min-1
no. holes
feed, in rev - 1
rev min - l/surface
in min-1
no. holes
feed, in rev - 1
rev min - l/surface
in min-1
no. holes
feed, in rev - 1
rev min - l/surface
in min-1
no. holes
feed, in rev - 1
rev min - l/surface
in min-1
no. holes
feed, in rev - 1
rev min - l/surface
in min-1
no. holes
feed, in rev - 1
rev min - l/surface
in min-1
no. holes
feed, in rev - 1
rev min -1 jsurface
in min-1
no. holes
feed, in rev - 1
rev min - l/surface
in min-1
no. holes
feed, in rev - 1
rev min - l/surface
in min-1
no. holes
feed, in rev - 1
rev min - l/surface
in min-1
no. holes

ft min -

ft min -

ft min -

ft min -

ft min -

ft min -

ft min -

ft min -

ft min -

ft min -

ft min -

ft min-1

ft min -

ft min -

ft min -

Uncoated

TiN coated

0010
300/41
30
185
0-008
1200/83
96
200
manual
1100/188
manual
2
0005
350/52
175
9
0008
800/85
64
800
0006
900/95
54
380-400
0004
430/30
17
36
0008
500/48
40
6
0010
425/41
42
7
0008
500/41
4
100
00045
1400/69
63
230
0-005
1200/69
60
230
0002
1200/39
24
30
0002
1200/39
24
45
0002
600/40
12
36

0010
429/60
42
405
0009
1748/121
157
300
manual
1100/188
manual
51
0005
350/52
175
36
0008
800/85
64
3000
0-000
900/95
81
900
0004
430/30
17
186
0008
500/48
40
130
0010
425/41
42
172
0005
1200/98
6
300
00045
2000/98
90
312
0005
1800/103
90
588
0002
1550/51
31
152+
0-002
1700/56
34
180
0002
600/40
12
293

Surface

Engineering

1985

Vol. 1

NO.2

102 Matthews

TiN PVD coating technology

150

150

100

:-.."

"

Lt..

:J

....J

.-.

t \.~
50

10

\'

'~

02
FEED,mmrav-1

~~ :\

-, ,,-

~~

,,

008

\\

\\

\,,
(a)

~r\

\\

~'

'\ :\

10

'\.

\ '\ \.

'\

'"0
\)".

"\

~
E..50

100
.\

1\\

\..'

t~

05

\
(b)
40
80
020
CUTTING SPEED, m min-1

~ uncoated drill
Balinit coated drill (new)
~ nitrided drill
Balinit coated drill (reground)
Workpiece: plates made of 42CrMo4 (AISI 4140), tempered to
1000 MN m-2, blind hole, 16 mmdrilling depth.
Test tool: Balinit coated drill, DIN 338, dia. 8 mm.
Cooling by emulsion 1: 20.
Criterium for determining toollife: constant squeal.
14 Improvements in drill life by TiN coating for a constant cutting
speed of 25 m min - 1 showing improvement in life for indicated
feed rates; b constant feed rate of 0] mm rev- 1, showing
improvement in life for indicated cutting speeds; courtesy
Balzers

being reground (Fig. 14).


There are now many published test results for
coated drills, with several manufacturers offering
their own products. In Ref. 10 data are presented
which illustrate some comparative information on
coated and uncoated drills (Table 3). Improved
performance of the coated drills was obtained across the
whole speed range, though when resharpened they
maintained their advantage better at lower speeds. It
was also shown that a coated drill can achieve longer life
even when operated at a higher speed than an uncoated
one. Other results indicated that, for a certain range of
feeds, the life actually increases as the feed rate is
increased.
Sprou148 has made an extensive comparative study
of sputter and reactively evaporated titanium nitride
coatings on twist drills. He found that the sputtered
deposits did not achieve the highest level of life
increase given by the evaporative processes, but the
spread of results on the latter coatings was very wide.
Furthermore, it was found that the type of cutting
fluid used could markedly affect tool life. Naturally,
especially for companies employing advanced
computer controlled manufacturing
techniques
(where tool life must be predictable to within a few
per cent), these types of result are of great concern. If
the maximum life increase cannot be assumed in each
case, it may be preferable to use a technique with a
lower average improvement, if that improvement is
more consistently achieved. Hopefully, though,
repeatability in all processes will continue to
improve, as the process variability problems
mentioned above are overcome.
While drills are an important potential market for
ceramic coatings, it appears that the more immediate
success is being achieved on larger tools, particularly
gear cutting hobs. There are several reasons for this.
Surface Engineering

1985 Vol. 1 No.2

Firstly, there is a clearer economic benefit in coating


(say) a 100 hob for 30 and making it last 4-5 times
longer than in achieving the same sort of saving and
performance improvement on a 1 twist drill. The
latter items have traditionally been 'disposable' and
less subject to performance monitoring. Also, it seems
that the scatter in results mentioned above is wider
on small tools like drills than on larger cutting tools.
This has been attributed to several factors, including
an increased risk of overheating and softening small
diameter, low thermal mass items during coating.40
The results of Sproul's tests certainly seem to support
this (sputtering being a lower temperature process).
Some variation may result from substrate material
variability, which influences both coating adhesion
and bulk strength. Indeed, it has been demonstrated
that the maximum benefit of coatings can be
achieved by paying special attention to the substrate
material, especially by utilizing the latest PM high
speed steels produced by sintering processes. The
best known of these are the ASP grades.49 Kloster
Speedsteel of Sweden recommends that the metal
carbides within the bulk structure should be finely
distributed, and the hardening temperature must not
be so high as to cause these carbides to be dissolved.
These recommendations are based partly on the
results of Swedish researchers such as Sundgren,50
and Hibbs et al.,45 who (as discussed above) claim
that adhesion is also improved. Some results
achieved by the David Brown Gear company, using a
coated ASP grade material rather than uncoated M2,
were reported in Ref. 51. The tool was a gear cutting
hob and this was operated at 50% higher speed when
coated. The results can be summarized as follows: a
reduction in machine time of 33%, an increase in
components per cycle of 900%, and a reduction in
tool wear of 20%. The total increase in cost on this
hob was 89%. Had the tool been used to its full wear
life, the increase in output bought for this additional
expense would have been of the order of1080%. This
is the immediate benefit and does not include
'hidden' advantages associated with reduced set-up
costs and down time savings. These results should
not necessarily be considered as the norm, but they
do indicate what can be achieved with ionization
assisted PVD TiN coatings. It is also interesting to
note that the Toshiba Tungalloy Division has stated
that there is an important role for PVD coatings in
the traditional domain of CVD coating - that of
cemented carbide inserts (Fig. 15).52 Where high
cutting forces are experienced (as in milling stainless
steel) the PVD coated carbide is said to be less prone
to chipping than CVD coated carbide.
There are many other reports of excellent results
using coated cutting tools. It is probable, though,
that the maximum benefit of coatings has not yet
been fully achieved. This is because tool geometries
can be further optimized to suit coatings. It is known,
for example, that Ti- N coatings can reduce friction
forces and tool heating. Built-up edge formation is
reduced and this allows rake angles to be changed.
This can provide a stiffer, more rigid tool giving
higher machining stability and the potential for
higher feeds and speeds and improved product
quality. Another probable development is that more
advanced coatings (including multilayered combinations) will soon become available, and they will

Matthews

15

TiN coating on cemented carbide cutting insert, deposited by


TI Abar sputter ion plating technique: courtesy
Waf/son
Institute for Surface Engineering

allow the tool surface to be matched directly to the


needs of the workpiece material being machined.
Metal cutting applications
have been stressed
above,
but
there
have also been significant
performance improvements
using coatings in imetal
forming processes. Sundquist et al. 53 cite a sheet
bending operation in which the useful life of a tool
was extended by x 50 compared to the uncoated
case. The product was a hinge, and uncoated tools
had to be reground and polished after producing
1000 hinges. Coated tools first produced
10000
hinges without any scratching, and after removal of
adherent wear residues they went on to produce
50 000 hinges before the coating wore through.
Again, the benefit is far greater than the obvious tool
cost saving, as a considerable amount of down time
and setting-up cost was avoided. Other applications
reported include extrusion dies, piercing punches,
plastic moulding dies, and paper cutting knives, as
well as many novel uses outside the field of industrial
cutting tools. For example, Torvac Processing Ltd
reports that a nozzle for abrasive slurry achieved a
sixfold increase in life when coated with titanium
nitride. 51 Other reported uses for titanium nitride
coatings include surgical tools in the USSR 54 and
wood cutting tools in Finland.55 It seems also that
these coatings have several potential applications in
fusion reactors (e.g. Ref. 56).
The applications information above covers just a
few of the many reported successes with PVD TiN
coatings. The technology is in its infancy, and the
careful monitoring of new applications developments
in this field is important.

CONCLUSIONS
The purpose of this paper has been to provide an
introduction
to PVD coating technology for those
interested in making use of the new commercial TiN
deposition processes. Information
has been given
about the main techniques, some of their potential
problems, and applications.
The objective has not
been to identify an optimum technique, since each
one has strengths and weaknesses which may make it
more or less appropriate
for certain applications.
Some processes, for example, may be more suitable
for repetitive production
of similar items, while
others are inherently more flexible both for different
sizes and shapes of component and also for changes

TiN PVD coating technology

103

in the coating material. The sputter ion plating


process, for example, is probably best suited to repeat
runs of similar components and coatings, whereas an
evaporative process with a faster turn-round
time
and simple evaporant change procedure might be
considered more suitable when component sizes and
shapes vary. Even so, this generalization
might be
disputed by some manufacturers.
Price comparisons
also are not straightforward.
There are capacity and throughput differences, some
of which are evident in Tables 1 and 2. In addition,
the terms and conditions of sale can vary depending
on the manufacturer. Some may offer an all-inclusive
turnkey operation,
others may charge extra for
certain necessary plant or technology transfer. A
component
cleaning plant, for example, can cost
from 10000 to 100000. Some companies have
requested royalty payments or even an equity stake
from
customer
companies.
Any
organization
considering
the purchase
of TiN
deposition
equipment must therefore consider factors such as
these before making a final decision. For those
merely seeking a coating service, the selection
procedure is rather more straightforward,
the main
decision criteria then being price and delivery,
provided the quality obtained
is satisfactory.
It
should certainly not be assumed, though, that all TiN
coatings are the same; and, as we have seen, there are
sufficient process variables to ensure that even
coatings from the same manufacturer
can possess
very different
properties.
Constant
vigilance is
therefore needed by both producers and users to
ensure consistent quality levels. Once confidence in
the product is established, then (as with all coating
processes) its use can be expected to increase
dramatically. Also, new coating materials will emerge
and this will further widen the range of applications
for ionization assisted PVD technology.

The information provided in this article is based on


our best knowledge at this time. It is important that
potential users should contact companies directly to
obtain or confirm specific information. To assist in
this a list of companies involved in this technology is included in the Appendix.

ACKNOWLEDGMENTS
The author is indebted to several individuals and
organizations for help in the production of this guide,
which is based in part on a report produced by the
author for the National Centre of Tribology PACT
(Plasma Assisted Coating Technology) programme.
Special thanks go to Dr Peter Dearnley of the
Wolfson Institute
for Surface Engineering
who
helped in the compilation of Tables 1 and 2.

REFERENCES
1.

2.
3.
4.
5.
6.
7.

Electrochem. Technol., 1964,2,295.


and A. C. RAGHURAM:
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1972, 9, 1385.
R. F. BUNSHAH:
Thin Solid Films, 1981,80,255.
M. KOBOYASHI and Y. 001: Thin Solid Films, 1978, 54, 17.
A. MATTHEWS
and D. G. TEER: Thin Solid Films, 1980,72, 541.
A. MATTHEWS
and D. G. TEER: Thin Solid Films, 1981, 80, 41.
E. MOLL and H. DAXINGER:
US Patent 4197 175, 1980.
D. MATTOX:

R.

F.

BUNSHAH

Surface

Engineering

1985

Vol. 1

NO.2

104 Matthews
8.

TiN PVD coating technology

VOGEL and s. SCHERRER: Information


folder no. 5004,
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44. D. MATTOX: in Proc. ICTF-6, Stockholm, August 1984, to be
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Diego, USA.

APPENDIX: SUPPLIERS OF PVD TiN


EQUIPMENT
Balzers Aktiengesellschaft,
Abteilung 51,
FL-9496 Balzers,
Fiirstentum
Liechtenstein.
Balzers High Vacuum Ltd,
Northbridge Road,
Berkhamstead,
Herts HP4 lEN,
UK.
Bernex AGO lten,
Industriestrasse 36,
CH-4600 Olten,
Switzerland.
Dowty Electronics Ltd,
136 Mansfield Road,
Acton,
London, W3 ORT,
UK.
Leybold-Heraeus GmbH,
Willhelm-Rohn-Strasse 25,
POB 15555,
.
D-6450 Hanau 1,
Federal Republic of
Germany.
Leybold-Heraeus Ltd,
16 Endeavour Way,
Durnsford Road,
London SW19 8UH,
UK.
Metco Inc.,
Cat Arc Division,
6509 Flying Cloud Drive,
Eden Prairie,
MN 55344,
USA.

Multi-Arc Vacuum Systems


Inc.,
261 East 5th Street,
St Paul,
MN 55101,
USA.
Multi-Arc (Europe) Ltd,
Number 1 Industrial Estate,
Medomsley Road,
Consett,
Co. Durham DH8 5HU,
UK.
Tecvac Ltd,
Main Street,
Stow-cum-Quy,
Cambridge CB5 9AB,
UK.

TI Abar,
TI Reynolds Ltd,
PO Box 232,
Hay Hall,
Redfern Road,
Tyseley,
Birmingham B11 2BG,
UK.

Ulvac Corporation,
1-10-3 Kyobashi,
Chuo-ku,
Tokyo 104,
Japan.
Vac-Tec Systems Inc.,
2590 Central Avenue,
Boulder,
CO 80301,
USA.