Wea~ 169 (1993) 195-200 195

Sliding wear resistance of TiCN coatings on tool steel made by

plasma-enhanced chemical vapour deposition

H.L. Wang, J.L. He and M.H. Hon

Department of Materials Science and Engineering (MAT32), National Cheng Kung University, Tainan (Taiwan)

(Received January 12, 1993; accepted May 27, 1993)

Abstract

In order to facilitate a proper choice of coating parameters for a wear-resistant TiCN coating on tool steel by
plasma-enhanced chemical vapour deposition (PECVD), the sliding wear resistance of PECV deposited TiCN
on tool steel was evaluated by the washer-on-disc method. A Taguchi array was employed to reveal the influence
of coating parameters on wear resistance. The results showed that the deposition temperature and the flow rates
of Ar and CH4 were the dominant coating parameters for a TiCN coating for wear resistance. Optimizing the
coating parameters of a TiCN coating for better load-carrying capacity and reducing the chance for deep galling
resulted in the improvement of wear resistance beyond that of TiN and TiC coatings. Controlling the constituents
of the TiCN coating proved to be easy, so that TiCN can be applied to meet the requirements if different wear
conditions are needed.

1. Introduction is used as either a transition layer between TiN and

TiC deposits Or as a single layer of hard coating on
The application of titanium nitride (TIN) or carbide tool steel.
(TIC) coatings by conventional CVD and PVD processes
to extend the life and performance of tools has been
demonstrated to be very successful [1-8]. Efforts have
2. Experimental
also been made using plasma-enhanced chemical vapour
deposition (PECVD) to obtain TiN o r TiC coatings
[9-16]. Great advantages are easily obtained from the 2.1. Substrate preparation
P E C V D process, including good controllability of the JIS SKD61 tool steel was u s e d as a substrate, which
constituents of the deposited films, the possibility of was shaped according to the A S T M D3702-78 washer-
not needing t o rotate the substrate [15] and good on-disc wear test method, as shown in Fig. l(a), and
throwing power [16]. The first advantage is particularly then heat treated as indicated in Fig. 2. A hardness
important when forming a TiCN coating which is ex- of about Hv740 was obtained. The disc substrate was
pected to have an adjustable microstructure and me- ground, polished to a surface roughness of R a = 0 . 1 / z m
chanical properties between those of a TiN coating and then the substrate was precleaned before coating.
with high fracture toughness and high temperature
stability and a TiC coating with high hardness and
better adhesion [17,18]. This enables the more versatile
TiCN coating to be applied on various substrates and
to be used in different wear conditions.
To date, few reports have paid attention to the wear
behaviour of a TiCN coating formed by PECVD. A
systematic evaluation of the wear resistance of TiCN
by P E C V D has also not been reported. The present
study evaluates the influence of coating parameters on
the sliding wear resistance of TiCN coatings on tool
steel made by P E C V D and also makes a comparison
among TiN and TiC coatings so that a proper choice
L -° ' -ILJ. 'L-
of coating parameters can be facilitated whenever TiCN Fig. 1. Dimensions of (a) the disc and (b) the washer.

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

196 H.L. Wang / Sliding wear resistance of TiCN coatings

1030 oC TABLE 2. Chemical composition of the $45C washer

90 rain
850 oy N8 quench 5%0°C 550°C C Mn Fe
650 °C/
/ 0.45 0.80 Balance

Fig. 2. Heat treatment of the SKD61 specimen.

-- - Gem .~-~ Rotary spindle

(with drive pin)
Substrate
Substrat~
~ - Washer holder
flow
controller
~ Wuher

older
R.F.
Generator

Fig. 3. Experimental apparatus for P E C V D coating.

Load direct.ion
TABLE 1. Chemical composition of the SKD61 substrate
Fig. 4. Installation of the washer and disc for wear test.

C Si Mn Cr Mo V Ni P S
0.42 1.03 0.40 5.13 0.99 0.62 0.06 0.016 0.002
The chemical composition of the SKD61 substrate was
measured, and is listed in Table 1.
2.2. Deposition process
Coatings were formed in a P E C V D apparatus as
shown in Fig. 3, using capacitively coupled electrodes.
One of the electrodes, connected to a 13.56 MHz r.f.
generator, was also used as a substrate table, while the
other, with ground status, was used as a gas shower.
TIC14 liquid in a vaporizer was carried by H2, N2 and
CH4 as gas sources, the flow rates of which were carefully
controlled. External substrate heating was supplied by
a graphite heater u n d e r the substrate table, capable
of heating the substrate up to 600 °C. When deposition
began, reaction gases were admitted into the reaction
bell jar to maintain the working pressure at about 4
Torr, and r.f. power was initiated to enhance the
deposition reaction.
2.3. Wear test
The wear resistance of coated specimens was eval-
uated by a Falex 6 multi-function wear tester using the
A S T M D3702-78 washer-on-disc method. The washer
was made of JIS $45C medium carbon steel with
hardness Hv280, without further heat treatment. Its
dimensions and chemical composition are shown in Fig.
l(b) and Table 2, respectively. The washer and the
Fe
disc were installed on the wear tester shown in Fig.
Balance 4 and wear test conditions were at a load of 0.38 lb
mm -2 ( = 1.69 N mm-2), with a sliding speed of 42.4
m min -1 and a total distance of 800 m. Weight loss
measured by a digital balance before and after the
wear test was used as an indication of wear resistance.
The wear scar profile was measured by a profile meter.
2.4. Evaluation method
A Taguchi array was used to evaluate the influence
of coating parameters on wear resistance of the coated
specimens. On the basis of a survey of the reports
[9-16] concerning TiN and TiC coating by PECVD, as
well as our own experience [19-21], those parameters
listed in Table 3 were suitably assigned to have three
levels and (except for deposition time with two levels)
to form an L18 orthogonal array, as shown in Table
4. The weight loss of specimens coated under the same
conditions was tested twice and listed in Table 4. Being
a reciprocal indicator of wear resistance, weight loss
was expected to have as small a value as possible. The
r/value listed in Table 4 was calculated from the weight
loss (AW) using eqn. (1) and can be a positive indication
of wear resistance.
~/= - 10 log(1/2)(AW12 + AW22) (1)
where AWl is the weight loss of sample 1 and AW2 is
the weight loss of sample 2.
Response charts of wear resistance as a function of
coating parameter were made to reveal the influence
of the coating parameters.
 H.L. Wang / Sliding wear resistance of TiCN coatings 197

TABLE 3. Coating parameters and the levels of the TiCN deposition process

A B C D E F G H
Coating Deposition Deposition r.f. Vaporization Flow rate Flow rate Flow rate Flow rate
parameter time temperature power temperature of H2 of Ar of CH4 of N 2
(h) (°C) (W) (°C) (sccm) (sccm) (sccm) (secm)

Level I 2 500 100 30 100 50 10 40

Level 2 3 550 200 40 150 100 20 80
Level 3 - 600 300 45 200 150 30 160

TABLE 4. Result of the L18 orthogonal array. The symbols A, B, ..., E represent the coating as indicated in Table 3

A B C D E F G H AWi AW2 -q Film Substrate

(10 -4 g) (10 -4 g) thickness hardness
(/~m) (Hv)

1 1 1 1 1 1 1 1 1 194 210 34 2.41 737

2 1 1 2 2 2 2 2 2 217 159 34 0.83 749
3 1 1 3 3 3 3 3 3 221 191 34 0.36 742
4 1 2 1 1 2 2 3 3 78 58 43 2.22 684
5 1 2 2 2 3 3 1 1 369 318 29 1.88 458
6 1 2 3 3 1 1 2 2 36 86 44 1.89 555
7 1 3 1 2 1 3 2 3 850 878 18 1.67 345
8 1 3 2 3 2 1 3 1 491 405 27 3.53 325
9 1 3 3 1 3 2 1 2 411 588 26 1.16 314
10 2 1 1 3 3 2 2 1 75 10 45 2.58 623
11 2 1 2 1 1 3 3 2 191 175 35 1.44 746
12 2 1 3 2 2 1 1 3 70 10 40 0.59 730
13 2 2 1 2 3 1 3 2 52 60 42 3.04 428
14 2 2 2 3 1 2 1 3 188 90 37 4.34 540
15 2 2 3 1 2 3 2 1 158 207 35 1.16 585
16 2 3 1 3 2 3 1 2 716 678 23 2.79 284
17 2 3 2 1 3 1 2 3 561 494 26 1.9 293
18 2 3 3 2 1 2 3 1 303 336 30 3.69 336

2.5. Observation and characterization a r e i m p o r t a n t for w e a r r e s i s t a n c e (see T a b l e 4). R e -

S E M was u s e d to m e a s u r e t h e film t h i c k n e s s f r o m
a f r a c t u r e d m i c r o v i e w a n d to o b s e r v e t h e w e a r scar.
A n X - r a y d i f f r a c t o m e t e r was e m p l o y e d to c h a r a c t e r i z e
t h e m i c r o s t r u c t u r e o f t h e coating.
3. Results and discussion
T a b l e 4 shows t h e r e s u l t o f w e a r tests o f t h e c o a t e d
s p e c i m e n s at t h e levels d i c t a t e d . T h e t h r e e m o s t in-
f l u e n t i a l p a r a m e t e r s i n d i c a t e d in T a b l e 5 by M a x - M i n
a r e t h e d e p o s i t i o n t e m p e r a t u r e a n d t h e flow r a t e s o f
CH4 a n d A r . R e s p o n s e c h a r t s for e a c h p a r a m e t e r as
a f u n c t i o n o f t h e i r o w n level a r e s h o w n in Fig. 5, w h i c h
offers an e s t i m a t i o n o f t h e i n f l u e n c e o f t h e s e p a r a m e t e r s
o n t h e w e a r r e s i s t a n c e in t h e c o m m o n l y e m p l o y e d r a n g e
o f P E C V D T i N o r T i C coatings. T h e S / N v a l u e s h o w e d
a positive d e p e n d e n c e o n t h e d e p o s i t i o n time, v a p o r -
i z a t i o n t e m p e r a t u r e , a n d H2 a n d CH4 flow r a t e s , as
o b s e r v e d in Fig. 5.
C h a n g e s in t h e levels o f c o a t i n g p a r a m e t e r s l e a d to
c h a n g e s o f film t h i c k n e s s a n d s u b s t r a t e h a r d n e s s , w h i c h
s p o n s e c h a r t s o f film t h i c k n e s s w e r e also m a d e b u t a r e
n o t s h o w n h e r e . A m o n g t h e s e r e s p o n s e charts, film
t h i c k n e s s vs. d e p o s i t i o n time, a n d A r , CH4 a n d N2 flow
r a t e s s h o w e d t h e s a m e t r e n d as t h e w e a r resistance.
T h i s i l l u s t r a t e s t h e i m p o r t a n c e o f film thickness. R e -
sponse charts of substrate hardness were not made,
for it is c l e a r f r o m T a b l e 4 t h a t t h e s u b s t r a t e h a r d n e s s
was i n f l u e n c e d exclusively by t h e d e p o s i t i o n t e m p e r -
a t u r e . A h i g h e r level o f d e p o s i t i o n t e m p e r a t u r e l e a d s
to s o f t e r s u b s t r a t e s . T h e h a r d n e s s fell f r o m Hv740 at
level 1 d o w n to Hv300 at level 3.
I n c r e a s i n g t h e d e p o s i t i o n t i m e i n c r e a s e d the film
thickness. This i n c r e a s e s t h e w e a r r e s i s t a n c e a n d d e m -
o n s t r a t e s t h e positive d e p e n d e n c e in Fig. 5(a). T h e
d e p o s i t i o n t e m p e r a t u r e n o t o n l y a f f e c t e d t h e film p r o p -
erties, b u t also t h e s u b s t r a t e . T h e d e p o s i t i o n t e m p e r -
a t u r e r e q u i r e d to o b t a i n a c r y s t a l l i n e T i N film by P E C V D
is a p p r o x i m a t e l y 300 °C w h i l e it is at l e a s t 500 °C for
T i C [10]; h e n c e it is b e t w e e n 300 a n d 500 °C for
TiCxNl_x, d e p e n d i n g on t h e f r a c t i o n s o f C a n d N. It
is t r u e t h a t a b e t t e r q u a l i t y film is o b t a i n e d w h e n
198 H.L. Wang / Sliding wear resistance of TiCN coatings

T A B L E 5. Response table for the LI8 orthogonal array

A B C D E F G H
Deposition Deposition r.f. Vaporization Flow rate Flow rate Flow rate Flow rate
time temperature power temperature of 1-12 of Ar of CH4 of N2
(h) (°c) (w) (°c) (seem) (seem) (seem) (seem)

Level 1 32 37 34 33 33 35 31 33
Level 2 35 38 31 32 34 36 34 34
Level 3 - 25 35 35 34 29 34 33
Max-min 3 13 4 3 1 7 4 1

40 401 ._____~\ deposition temperature is increased. A side-effect of

35 j high deposition temperature would be substrate soft-
35 i \\\ ening. Wear resistance therefore increased at first, as
J
=- 30 ao \\ shown in Fig. 5(b). On further increasing the deposition
temperature up to 600 °C at level 3, beyond the softening
25 25 \' ;
temperature (approximately 580 °C) of SKD61, the
20 20 substrate becomes significantly softer, from Hv600 down
2 3 500 550 600
Deposition t i m e ( h r ) Deposition temperature (°C) to Hv300, and no longer has enough load-carrying

40
capacity [22] to support the TiCN film against wear.
Thus an abrupt decrease in wear resistance was ob-
served. Micrographs of the wear scar edge of worn
40 specimens deposited at 550 °C and 600 °C are shown
in Figs. 6(a) and (b) respectively. These illustrate the
35 3s
result of the catastrophic wear mode after losing the
30 3O load-carrying capacity of the substrate for the film
deposited at 600 °C.
25 es! The second important deposition parameter for wear
2O
t00 200 300
eol 30 40 45
resistance was the flow rate of Ar. The response chart
of wear resistance v s . A r flow rate in Fig. 5(f) shows
R.F.power (W) Vaporizer temperature (°C)
the same trend as the response chart of film thickness
v s . A r flow rate. It is therefore suggested that the Ar

4O 40;

35 J,,
\\
30 Sliding
30 I direction
25

2O 20 L
\
100 150 200 50 100 150
Flow r a t e of H2 ( s e e m ) Flow r a t e of Ar ( s e e m }
(a) 30 ]am

40r 40t
t[ I
aa~ 3~p
] [ Sliding
~ 30~ u- 3o~ direction
i
25~

10 20 30
20 l
40 80 160 (b) a0 ~-n
Flow r a t e of CH 4 ( s e e m ) Flow r a t e of Nz ( s e e m ) Fig. 6. Wear scar edge of TiCN-coated specimens deposited at
Fig. 5. Response charts for the coating parameters. (a) 550 °C and (b) 600 °C.
 H.L. Wang / Sliding wear resistance of TiCN coatings 199

gas influences the growth rate and the subsequent wear

resistance. The effect of adding Ar during TiN coating
1200 [ [] Apparent hardness ] 120
by PECVD, investigated by Hilton et al. [23], suggests |I Weight lo-,-, |_1100
that NE-H2-based films have nothing but a decrease in A 1000 ~- 1-7
growth rate, because Ar behaves as an inert gas diluting
the reactive species. However, the effect of admixing
Ar during TiC coating by PECVD is well known to oot|ll
I
enhance the film growth rate because of the Penning
effect [17]. The response of wear resistance on TiCN
growth is thus a competition between the two effects.
| _-:
Increasing the flow rate of Ar would cause the Penning -t
effect at first, leading to an increase in film thickness
and subsequent wear resistance. Further increasing the
/
Ar flow rate dilutes the reactive species, causing a
decrease in film thickness and wear resistance, as shown
in Fig. 5(f). The ~7 value response to the C H 4 flOW
I BI~ir TI_C TiN TLCN
rate was greater than for the Na flow rate. This might Fig. 7. Apparent hardness and weight loss of blank, TIN-, TiC-
come from the difference in activity between the two and TiCN-coated specimens.
gases. The reaction of the titanium source with N2
molecules with less dissociation energy is controlled by
the decomposition process, leading to a lesser depen-
dence of growth rate on flow rate. The film thickness
and the subsequent wear resistance is therefore less
dependent on the NE flow rate than on the CH4 flow ,= :~ (b)
rate.
A confirmation experiment on the optimized param-
eters shown in Table 6 indicated a high wear resistance
and thus a high ~7value. It reveals the accurate prediction © (d)
of the influence of coating parameters using the Taguchi
method. I I I I
Figure 7 compares the apparent hardness and weight 0 0.5 1.0 1.5 2.0 2.5
loss of blank, TIN-, TiC- and TiCN-coated specimens.
Scar profile length: (mm)
The TiCN was deposited with the optimized coating
parameters shown in Table 6. The deposition tem- Fig. 8. Surface profiles of the wear scars of (a) blank, (b)
TIC-, (c) TiN- and (d) TiCN-coated specimens.
perature was kept the same and the film thicknesses
were all kept at 3 /xm. All the coatings promoted the
apparent hardness and wear resistance as expected; of the coatings that determine the wear resistance.
nevertheless, the TiC coating, with the highest apparent Considering the TiC coating with the highest intrinsic
hardness, had the lowest wear resistance, while the hardness among the three coatings, the benefit from
TiCN coating, with apparent hardness between that of a harder coating, such as TiC, is a higher load-cart-ying
the TiN and TiC coatings, had the highest wear re- capacity of the coating itself, but the disadvantage of
sistance, which was apparently not a direct reflection a harder coating is the formation of galling wear when
of the apparent hardness as observed in this figure. delametlation of the coating occurs. The delamellated
Since the film thickness and deposition temperature aspirates of the coating layer cause weight loss and
were kept the same, the influence of the substrate on local penetration through to the substrate, as observed
wear resistance for the three coated specimens was in Fig. 8(b). The TiN coating, with the lowest hardness
undoubtedly the same. It is exactly the film properties and the highest toughness, released the shear, stress
more easily and avoided deep galling, as shown in Fig.
TABLE 6. Coating parameters and the wear resistance response 8(c), resulting in better wear resistance. TiCN; with
of the conformation experiment / moderate hardness and brittleness (between TiC and
TIN), had a better load-carrying capacity and reduced
A B C D E F G H AW AW r/ the chance for deep galling; hence the highest wear
(10 -4 g) ( 1 0 - ' g) resistance was obtained.
From the results and discussion above, the TiCN
3 550 100 45 150 100 30 80 6 2 70
coating can be optimized to obtain better wear resistance
200 H.L. Wang / Sliding wear resistance of TiCN coatings

3. The constituents of TiCN coatings made by PECVD

TIN(200)
can be easily controlled to meet the requirements
I
[ PECVD-TiN /\ of different wear condition.

/ /
j/: \.~CH,=4 s c e m !
I l Acknowledgments
~,..__CH4=8 seem!
1
I
] The authors wish to thank the National Science
,4 CH4--15 s e e m
Council for partial support of this study under the
I
~ " ~ _ _ _ C H 4 = 30 s e e m project NSC77-0405-E006-08, and Professor Lin who
I
provided the wear tester.
L PECVD-TiC TIC(200)
i
J i ' i ~ , i i l

37 38 3'9 40 41 42 43
Spectral angle
Fig. 9. X-ray diffraction patterns of TiCN films deposited at
different CH4 gas flow rates.
than TiC or TiN coatings using the PECVD process.
The constituents of TiCN coatings with properties in
between those of TiC and TiN could be easily adjusted
by adjusting the flow rates of CH4 and N2 to be close
to TiN or TiC, as demonstrated in Fig. 9. This shows
that an increase in the CH4 flow rate leads to a peak
shift in the XRD pattern of the coated specimens from
a 20 angle of 42.6 ° to 41.6 ° which are the (200) char-
acteristic angles of TiN and TiC, respectively. This
implies that it allowed a modulation of the TiCN film
properties to meet the requirement of either a tougher
more TiN-like film that can carry a heavier load or a
harder more TiC-like film that can bear a higher sliding
speed with a lighter load.
4. Conclusions
1. The deposition temperature and the flow rates of
Ar and CH4 were the major influential coating
parameters for TiCN coatings for wear resistance.
The deposition temperature affects the substrate
hardness, while the Ar and CH4 flow rates affect
the film thickness. Optimizing the coating parameters
of TiCN coatings improved the wear resistance of
TiCN-coated specimens beyond that of TiN- and
TiC-coated specimens.
2. TiCN, with moderate hardness and brittleness (be-
tween those of TiC and TIN), had a better load-
carrying capacity and reduced the chance for deep
galling; hence the highest wear resistance was ob-
tained.
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