Novel Materials Processing (MAPEES'04)

S. Miyake (Ed.)
9 2005 Elsevier Ltd. All rights reserved

Research of TiN Coatings by Means of Gas Tunnel Type

Plasma Reactive Spraying
Wei Jiang" and Akira Kobayashi

Joining & Welding Research Inst., Osaka University11-1 Mihogaoka, Ibaraki, Osaka 567-0047, Japan

Abstract:The titanium nitride (TIN) sprayed coating with thickness of 1 0 0 - 2 0 0 /m

could be obtained in a short time of 10s by means of gas tunnel type plasma reactive
spraying. In the present paper, in order to investigate the properties of TiN sprayed
coating, the cross-section of TiN coating was observed by an optical microscope and
also the structure of TiN coating was discussed. Vickers hardness of TiN coatings was
measured when the spraying distance was l=60 mm and l=70 mm. The relations
between the spraying distance l and Vickers Hardness Hv on the cross-section of TiN
sprayed coating was clarified. The adhesive strength of TiN coating was measured and
discussed.

Keywords: Gas tunnel typeplasma reactive spraying, Vickers hardness, Adhesive

strength, Titanium nitride coating, Wear resistance; Nitriding.

1. I N T R O D U C T I O N the high quality coating produced by the gas tunnel

Titanium nitride (TIN) coatings have a widely range
of applications due to the practical properties such as
high hardness, good corrosion resistance, heat
resistance and excellent wear resistance etc. [1-3]. In
general, it can be deposited by physical vapor
deposition (PVD) evaporation, sputtering, ion
plating and chemical vapor deposition (CVD). In the
present article, the TiN coating was deposited by gas
tunnel type plasma reactive spraying which was
developed by A. Kobayashi[4]. The gas tunnel type
plasma jet [5], being a new one of the plasma
spraying methods, has the characteristics of high
temperature and high energy density. In the
conventional case, the sprayed Ti particle was
deposited as a thin film of 10 t.tm or less on the
substrate by the other plasma spraying methods.
On the other hand, a high quality ceramic coating
could be obtained by the gas tunnel type plasma
spraying such as ZrO2 coating, A1203 coating and
the mixture coating of ZrO2 and A1203, etc. Those
are all series of high hardness coatings.[6-9]. Thus,
"Corresponding author. Tel.: +81-6-6879-8684;
fax: +81-6-6879-8689
E-mail address:kyoi@jwri.osaka-u.ac.jp
type plasma spraying methods was much denser and
harder than those by the common methods.
Moreover, a thick titanium nitride (TIN) coating of
more than 100 ttm could be formed by means of gas
tunnel type plasma reactive spraying; the various
performances of the TiN coating obtained by this
method is superior to those by the conventional
spraying methods. As a typical example of titanium
nitride film [10], TiN coating for which was 100-200
um thickness and the Vickers hardness of which was
Hv: 1300--1800 [11], could be obtained in a short
time of 10s.
In this paper, the TiN coatings were formed on the
traverse substrate by gas tunnel type plasma reactive
spraying in a short time of about 8s. Experiments
were carried out by changing the traverse numbers
and the spraying distance. The cross-section of the
TiN coatings was observed by an optical microscope
and the structure of the TiN coatings was analyzed.
Vickers Hardness of the TiN sprayed coating was
measured when the spraying distance was/=60, 70
mm respectively. The adhesive strength of the TiN
coatings was tested by tension tester and the wear
weight of the coating was also measured.

427
 Fig.2. Schematic of tension tester, the tested
Fig.1. Block diagram of gas tunnel type plasma range, 0-200 kg
reactive spraying torch for the TiN coatings.
the perpendicular to the axis at speed of v [13-16].

Titanium powder was supplied into the gas tunnel

2. EXPERIMENTS
Fig.1 shows a block diagram of gas tunnel type
reactive spraying torch for the formation of titanium
nitride (TIN) coating in this experiment. As details
of the gas tunnel type plasma jet was described by A.
Kobayashi in the previous papers[4]. Here, it is for
only a brief spraying procedure of the TiN coating as
the following described.
The experimental conditions for the formation of the
TiN coatings were shown in Table 1. The chemical
composition of the sprayed titanium powder was in
shown Table 2. Here, the titanium powder was the
type of T-459. The substrate used the stainless steel
which was sand-blasted beforehand. A substrate
was located at a certain position on the rotating
sample holder [12]. The substrate was traversed in
Table 1 Experimental conditions.
Powder: Ti-459
Traverse number N: (pass) 10, 20, 30
Power input P: (kW) 25,27
Working gas flow rate Q:(I/min) 180
Spraying distance 1: (mm) 60, 70
Traverse speed v: (mm/s) 60-200
Gas diverter nozzle diameter : (mm) 20
Spraying time e: (s) 8-8.5
Environmental gas flow rate:(1/min) 100
plasma jet from sideways in the vertical direction of
plasma flow and was reactively sprayed onto the
traversed substrate for the spraying time of t. During
the plasma spraying time, the titanium particle was
nitrided by the excited Nz in the plasma flow, then
deposited onto the surface of the substance. A TiN
thick coating was generated on the stainless steel
which size was 50x50x2.5 mm. The sprayed
titanium powder was Ti: 99.7% with a diameter of
10 -- 40 um.
For this study, we selected the sprayed TiN coatings
under the conditions of the traverse numbers of 10,
20, 30, respectively with the spraying distance of
/=60 mm and /=70 mm. First, the surface of the
specimens of the TiN coatings was observed by
naked eyes. Then, the cross-section of the TiN
coatings was observed by an optical microscope to
make an analysis to the inner structure of the
coatings. Vickers Hardness (Hv) was measured at
the non-pore region on a cross-section of the TiN
coating in order to compare the hardness value at the
various spraying conditions. The Vickers hardness
was measured for the conditions: loading weight,
100g; holding time, 30s and number of measuring
point, more than 5.

Table 2 Chemical composition of titanium powder (wt %).

Chemical component Ti Fe Si N O
Ratio of composition 99.7 0.03 0.01 0.02 0.24

428
Fig.3. Photomicrograph of the cross-section of TiN coatings at the different traverse number and the
spraying distance; for the other conditions: P=25kW, v=62, 127, 193mm/s, e=8s; the range of the
thickness value of the coatings: 100-140 tzm.
The Vickers Hardness on the cross-section of the
TiN coating was measured at each distance [17]
from the coating surface side to the substance side in
the thickness direction.
The adhesive strength between the coating and the
substrate was measured using by the tension tester
shown in Fig.2. The tested piece for adhesive
strength was made to approximate 10 mm square
and it was attached to each holder for the coating
surface side and the opposite side of the coating by
polymer type glue. The load of the tester was
changed in a range of 0--200kg. It was kgf/cm 2 used
for adhesive strength of the TiN coatings as a unit.
3. RESULTS AND DISCUSSION
3.1 Observation to surface of coatings and
comparison of coating thickness
The surface color of the sprayed coatings
appeared a white-gray after spraying, which
indicates that it was covered by titanium powder in
the surface of the coatings. When the white-gray
surface was erased, it appeared gold color at the
center of plasma spraying axis which indicated a
large TiN content. The coating surface color was
compared at the different traverse number when the
spraying distances were /=60 mm and l=70 mm,
respectively. The compared result was that the
surface color of the coatings got dark golden over a
certain traverse numbers. The reason was thought
that the titanium sprayed onto the substrate was
superheated by the sprayed plasma when the sprayed
time got longer in the chamber.
3.2. Analysis of the cross-section for the TiN
coating
Fig.3 shows the six pieces of the photomicrographs
of the cross-section for the TiN coatings which were
observed by an optical microscope. The thickness
value of the coating was marked below each photo
which the whole range was between 100 and 140 Urn.
There were some pores on the cross-section of the
coatings as shown in Fig.3. The density of the
coating became a little higher as the traverse number
was increased at the same spraying distance. In
general, the properties of the coatings might be
better when the sprayed coating became denser,
however it was well known that the size of the TiN
crystalloid in the coating was much larger than that
of Ti crystalloid. Therefore, there exists a possibility
that Ti powder which had not transformed TiN
429
 Fig.5. Dependence of Vickers hardness of the TiN
coatings measured on the coating thickness. (from
the surface side to the substrate side ).at a condition
of different traverse number with the same spraying
distance.

~" 200
+ 70ram 20times
160
Fig.4. Dependence of Vickers hardness of the TiN
coatings measured on the coating thickness (from = 120
the surface side to the substrate side) at a
-g 80
condition of different spraying distance with the
same traverse number. "~ 40
.c
< 0
remained in the coating. In this case, despite the
95 135 145 209 223
structure of the formation was denser, the
mechanical properties might become worse. The Coating thickness (/2 m)
coating thickness was increased as the spraying Fig.6. Relationship of the adhesive strength and
distance decreased at the same traverse number and coating thickness between coating and substrate
spraying time. The coating thickness was also at traverse number, N=20. The spraying
increased as the traverse number was rising at the conditions: spraying distance 2.=70 mm, traverse
traverse speed of v=193mm/s; the spraying time of speed v=62, 127, 193 mm/s; spray time t=8.2s;
around t=8s; the spraying distance of/=60,70 mm power input P=25kW.
respectively.

3.3 Distributions of Vickers hardness in coating
thickness direction
The Vickers hardness Hv, was measured at 5 points
every distance of 20/tm. on a cross-section of TiN
coatings. Fig.4 shows Vickers hardness (Hv) from
the surface side to the substrate side of the coating
at the same traverse number and the different
spraying distance. It was shown that the Vickers
hardness of the coatings was in the range of
Hv=l100-1450, the conditions of the coatings
sprayed for the test were as follows: the power input
P=25kW, traverse number N=10, 20, 30, spraying

430
 distance 2=60, 70 mm at the spaying time of about
t=8s. These results show that the Vickers hardness
value of the TiN coatings hardly changed in the
range of the surface side to inner side of the coatings.
However, the hardness value near to the surface side
f the coatings became lower than those of other parts.
Fig.5 shows the distribution of Vickers hardness of
the different traverse number at the spraying
distance o f / = 6 0 , 70 mm. It is observed that the
Vickers hardness is the highest for when the traverse
number was N=10 among the different traverse
number. One reason of this result can be due to the
internal stress of the coating was decreased with
increasing of the traverse numbers increasing.
Another reason might be thought that the residual
stress in the surface was increased as the traverse
numbers increasing. The residual stress caused the
Vickers Hardness of the coating lower.
3.4 Relationship between adhesive strength and
coating thickness
Fig.6 shows the relationship of adhesive strength
and the coating thickness at traverse number N=20 at
the spraying distance of 2.=70 mm under the
condition of P=25kW. It appears that the value of
the adhesive strength decreases as the coating
thickness was increases in the case of the same
traverse number. In this case, the highest adhesive
strength was approximate 145kgf/cm 2 at the coating
thickness of 100 tzm or so.
3.5 Relationship between wear resistance and
spraying number
Fig.7 shows the relationship of wear weight loss of
the sprayed coating and the traverse number when
the traverse number was changed from 10 to 40
respectively at the spraying distance 2 =70mm. The
Fig.7 Relationship of the wear resistance and traverse
number as well as stainless steel at the condition of
the spraying distance ./.=70 mm, traverse speed
v=62, 127, 193 mm/s; spray time t:=8.2s; power
input P=25kW
wear weight loss of the stainless steel was also
indicated in this figure. It appears the fact that the
wear weight becomes larger as the traverse number
increasing.
These results show that wear resistance of the
sprayed coating is much stronger than that of
stainless steel. Specially, we can estimate the
proportion that the wear resistance value of the
sprayed coating at the traverse number of N=10 was
around 30 times than that of the stainless steel.
4. CONCLUSIONS
The following results were obtained in this study:
1) It was possible for the coating of more than
100 /Ira thickness produced by the gas tunnel
type plasma reactive spraying. In this study, the
thickness value reached approximate 140 ttm.
2) The coating was thicker when the traverse
number was large at the same spraying distance.
The coating structure was similar under various
conditions.
3) The Vickers hardness of the coatings was
H v = l l 0 0 - - 1 4 5 0 , and it became lower as the
traverse number became larger.
4) The value of the adhesive strength was highest
of 145kgf/cm 2 at the coating thickness of
around 100 tzm. The adhesive strength became
lower with increase of the thickness which was
over 200/zm.
5) As the traverse number was increased, the wear
resistance of the sprayed coating became lower,
however, the wear resistance of the coating was
still much stronger than that of the stainless
steel.
ACKNOWLEDGEMENTS
The authors wish to thank to Mr. Kotera for his
assistance during the experiment.
REFERENCES
Y.Arata, A.Kobayashi and Y. Habara(1987).
Ceramic Coatings Produced by Means of Gas
Tunnel Type Plasma Jet. J. Appl. Phys. 62(12)
4884-4889
L.A.Cyster(2002).
The Effect of Surface Chemistry and Structure
of Titanium Nitride Films on Primary
Hippocampal Cells, Biomolecular Engineering
19, 171-175Y. Arata, A.
M. Scho11(1977).
Abrasive Wear of Titanium Nitride Coatings,
wear 203-204,57-64
431
Y.Arata and A.Kobayashi(1986).
Application of Gas Tunnel to High-energy-
density Plasma Beams, J. Appl.Phys. 59-9,3038-
3044
A.Kobayashi(1992).
Property of an Alumina Coating Sprayed with a
Gas Tunnel Plasma Spraying, Proc. of ITSC,57-
62
A.Kobayashi(2000).
Formation of TiN Coatings by Gas Tunnel Type
Plasma Reactive Spraying, Surf Coat. Technol.
132,152-157
A.Kobayashi and T.Kitamura(2000).
Effect of Heat Treatment of High Hardness
Zirconia Coatings Formed by Gas Tunnel
Plasma Spraying, Advances in Applied Plasma
Science, Vol.59,194-202
A.Kobayashi(2003).
Adhesive Strength of Zirconia Composite
Coatings by Gas Tunnel Type Plasma Spraying.
J. of lAPS, Vo14, 101-106
A.Kobayashi, K.Yamafuji and T.Kitamura(1991).
Effect of Thermal Process on High Hardness
Zirconia Coating by Means of Gas Tunnel Type
Plasma Spraying. Tran. JWRI Vol.20, 19-25
A.Kob ayashi(1997).
Formation of High Hardness Zirconia Coatings
by Gas Tunnel Plasma Spraying, Surface and
Coating Technology, Vol. 90,197-202
432
A.Kobayashi(1996).
Characteristics of High Hardness Alumina
Coatings Formed by Gas Tunnel Plasma
Spraying, J. Thermal Spray Technology, Vol.5-
3,298-302
A.Kob ayashi(1998).
Properties of Functionally Graded Zirconia
Coating by Gas Tunnel Plasma Spraying, Proc,
of International Thermal Spray Conference,
Nice, France, May,1657-1662
A.Kob ayashi(1985).
Development of Gas Tunnel Type High Power
Plasma Jet (in Japanese), J. High Temp. Soc.
11(3) ,124-131
A.Kobayashi(2003).
Properties of TiN Thick Coating Formed by Gas
Tunnel Type Plasma Reactive Spraying, Journal
of lAPS, Vol.11,51-54
A.Kob ayashi(1977).
Study on the Formation of TiN Coating by
Plasma Reactive-spraying (in Japanese), Plasma
Applies Hybrid Functionally Mater 6,71-74
A.Kobayashi(1990).
Formation of High Hardness Zirconia Coatings
by Gas Tunnel Plasma Spraying, Surface and
Coating Technology, VI.90, 197-202
A.Kobayashi(1996).
Surface Nitridation of Titanium Metals by
Means of Gas Tunnel Type Plasma Jet, J. Mater.
Eng. & Performance, Vol.5, No.3,373-380