Surface & Coatings Technology 218 (2013) 62–70

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Surface & Coatings Technology

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Production of in-situ hard Ti/TiN composite surface layers on CP-Ti using reactive
friction stir processing under nitrogen environment
Ali Shamsipur, Seyed Farshid Kashani-Bozorg ⁎, Abbas Zarei-Hanzaki
School of Metallurgy and Materials Engineering, College of Engineering, University of Tehran, P.O. Box 11155-4563, Tehran, Iran

a r t i c l e i n f o a b s t r a c t

Article history: Reactive friction stir processing was carried out on a commercially pure titanium substrate by blowing
Received 2 August 2012 nitrogen gas into the stir zone. Surface layers were produced having non-uniform banded-type microstructures
Accepted in revised form 23 December 2012 of TiN precipitates in a transformed titanium matrix. Using additional passes, near uniform dispersion of TiN
Available online 31 December 2012
precipitates (~2 μm) in a matrix of fine grains (~4.5 μm) with α′-Ti martensite sub-structure was achieved.
Dissolution of nitrogen in the stir zone and formation of TiN-based structure were confirmed by energy-
Keywords:
Titanium
dispersive X-ray spectroscopy, X-ray and electron diffraction, respectively. The fabricated Ti/TiN (2.3 vol.%)
TiN composite layer showed an average microhardness value of ~972 HV, which is about six times greater
Nitrogen gas than that of its underlying titanium substrate; this is attributed to the formation of hard TiN reinforcements at
Scanning electron microscopy boundaries of fine dynamically restorated grains with α′-Ti martensite sub-structure.
Transmission electron microscopy © 2012 Elsevier B.V. All rights reserved.
Vickers hardness test

1. Introduction
Surface nitriding of titanium alloys has been investigated for near
half of a century; diffusion and remelting methods were used for
producing hard layers [1]. Diffusion methods, like gas nitriding, are
independent of sample geometry. In addition, these methods need
no special equipments [2]. However, they require a temperature in
the range of ~ 850–1000 °C and a lengthy time of ~ 9 h for the
completion of the process [3]. Remelting methods, like laser
nitriding, provide an excellent metallurgical bond between surface
layer and its underlying substrate [4,5]. Relatively thicker layers
can be produced using remelting methods. However, the associated
surface cracking is a problem. In addition, these techniques require
special equipments.
Recently, researchers have paid much attention to a new surface
modification method, named friction stir processing (FSP). In this
technique, a non-consumable cylindrical tool with a shoulder and
pin is used. The pin is inserted into a substrate while the shoulder
is in contact to substrate surface. The tool rotates and advances in a
direct line; a surface layer is plasticized and simultaneously severely
hot deformed. Thus, a fine microstructure is achieved due to the
occurrence of dynamic recrystallization phenomena [6,7]. Formation
of various composite and nano-composite surface layers were
reported on Al [8–10], Mg [11–16], Cu [17] and Ti [18,19] substrates
by introduction of hard ceramic particles such as SiC [11,16–19],
Al2O3 [9,20], B4C [10], C60 [13], multi-walled carbon nano-tubes
⁎ Corresponding author. Tel.: +98 21 82084105; fax: +98 21 88006076.
E-mail address: fkashani@ut.ac.ir (S.F. Kashani-Bozorg).
[12] and SiO2 [14] into the stir zone; particles were mainly pre-
placed in a groove in front of the tool. Further works showed
significant increases in microhardness and wear resistance of the
fabricated composite surface layers compared to those of their
underlying substrates [19,20]; these were related to uniform disper-
sion of hard ceramic particles and fine matrix grain size.
The novel idea of surface nitriding using FSP came from the oxidized
tracks produced as a result of weak environmental protection in our
previous investigation on titanium [19]. To the best of our knowledge,
there is no published work on the preparation of composite layers by
blowing active gases during friction stir processing. In the present
study, we wish to report the fabrication of Ti/TiN composite surface
layers on a commercially pure titanium (CP-Ti) substrate with and with-
out groove by blowing nitrogen gas into the stir zone. Microstructural
characterization of the fabricated layers was carried out. In addition,
the microhardness of the composite surface layer was measured and
compared to that of its underlying titanium substrate.
2. Material and methods
Friction stir processing method was used to produce surface layers
on CP-Ti work pieces under two various environments; neutral argon
and reactive nitrogen gases with a flow rate of 10 L/min. A blowing
gas system was used in front of the advancing tool to introduce
nitrogen gas to the stir zone generated on substrates with or without
groove. A groove of width and depth of 1 and 3 mm was made in the
middle of substrate in a straight line, respectively. The substrate with
groove provides extra exposed area of stir zone to nitrogen gas.
The effect of nitrogen addition on microstructure and hardness was

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 A. Shamsipur et al. / Surface & Coatings Technology 218 (2013) 62–70
Fig. 1. A schematic diagram of FSP experiment under the flow of nitrogen gas.
investigated and compared to those of the processed layer under
argon gas and the underlying substrate.
Rolled CP-Ti plate, oxygen-free argon and nitrogen gases were
used with a thickness of 6 mm, purities of 99.999 and 99.8% as the
substrate and blowing gases for the preparation of modified surface
layers, respectively.
Fig. 2. Top views of the FSPed work piece under argon gas (a) and work piece with
groove under nitrogen gas (b).
63
Work pieces were prepared with a length of 100 and width of
50 mm. A conventional vertical milling machine was employed for
FSP experiments. The FSP tool was made of a hardened H13 tool
steel shoulder (28 mm diameter) and a tungsten carbide pin (6 mm
diameter, and 3 mm length). The tool was tilted 3° with respect to
vertical line; this enables substantial exposure of plasticized material
to nitrogen gas. The process parameters were selected according to
our previous investigation on FSP of CP-Ti (defect-free surface layers
were achieved using a tool rotation and substrate advancing speeds
in the ranges of 800–1250 rpm and 35–55 mm/s, respectively [18]).
In order to increase the possibility of nitrogen pick-ups by the
plasticized material, a relatively high heat input was considered.
Thus, the highest tool rotation, i.e., 1250 rpm, and lowest advancing
speed, i.e., 35 mm min −1 of the previously found results [18] were
applied to the present FSP experiments.
Initially, work pieces were subjected to friction stir processing
under an argon shrouding system. This protected the stir zone from
ambient environment. Then, FSP was carried out on work pieces
with and without groove under nitrogen gas. Nitrogen was intro-
duced to the top surface of stir zone or top surface and case depth
of stir zone using work pieces without and with groove, respectively.
The schematic diagram of FSP system is shown in Fig. 1. In order
to achieve a homogeneous stir zone, the fabricated surface layer
was subjected to three more passes at the same tool rotation and
substrate advancing speeds under an argon shrouding system.
The stir zone temperature was measured using a K-type thermo-
couple, which was inserted in the middle length of the work piece,
i.e. 2 mm below the surface. Temperature was recorded as a function
of time. It should be stated that the thermocouple tip was in the pin
path. Thus, it was cut as the tool passed the middle length of the
work piece since the pin tool length was 3 mm.
The microstructures were characterized employing optical and
scanning electron microscopy (SEM, model CamScan MV2300)
equipped with an energy dispersive spectrometer (EDS) device. Samples
were taken from cross sections perpendicular to the tool advancing
direction. Crystal structures were identified by X ray diffraction (XRD,
model Philips X'Pert Pro), using a monochromatic Cu–Kα radiation
between 20 and 80° (2θ), with a step size of 0.02° and a counting time
of 0.8 s per step. Clemex image processing software was used to obtain
volume fraction of the second phase precipitates [21]. Thin foil speci-
mens were prepared from the fabricated layers after four FSP passes
64 A. Shamsipur et al. / Surface & Coatings Technology 218 (2013) 62–70

10mm

Fig. 3. Transverse section of the FSPed work piece with groove under nitrogen gas.

areas from environmental atmosphere. Fig. 2a shows top view of a

Fig. 4. X-ray diffraction patterns of the as-received CP-Ti substrate (a), and Ti/TiN
composite layer produced on work piece with groove from top surface (b).
selected FSPed surface layer under argon gas that reflects a bright
metallic color. On the other hand, the processed layers produced on
work pieces (with or without groove) under nitrogen gas reflect a
yellowish golden color (e.g., Fig. 2b). All layers exhibited no defects
such as voids or cracks. Top surface of the fabricated layers under
nitrogen gas was gradually polished. It was found that only the
layer produced on work piece with groove keeps its yellowish golden
color. In other words, surface color of the other layer which was
produced on work piece with no groove turned to bright metallic
color; this can be an indication of relatively low nitrogen content of
inner regions of the processed layer.
Fig. 3 shows scanning electron micrograph of the transverse section
of the fabricated surface layer on work piece with groove. No defect
such as pore or tunnel was observed, which indicates formation of a
proper surface layer. However, inhomogeneity was observed; a newly
formed phase was observed in stir zone center in a non-uniform fashion.

3.2. X-ray diffractometry analyses of the processed layers

parallel to their surface. Perforation of thin foils was carried out by ion
milling technique. Finally, thin foils were studied using a field emission
transmission electron microscope (model Jeol 2100F) operating at
200 kV; the microscope was linked to an EDS, as well.
Microhardness measurement was carried out using a micro-
Vickers indenter under a load of 200 g for 12 s along layer depth in
a line from the base material, heat affected zone, entire stir zone
towards the surface.
3. Results and discussion
3.1. The processed layers macrostructures
X-ray diffraction patterns of the top surface of the work piece before
and after FSP under nitrogen atmosphere are shown in Fig. 4; in fact, the
X-ray diffraction pattern of the as-received CP-Ti substrate shows two
strong peaks at 2θ values of 38.3 and 40.0° (Fig. 4a). However, the corre-
sponding α-Ti peaks were diminished considerably (down to ~100
count per second). In addition, they were found to be shifted to higher
2θ values. These can be attributed to the associated process features
(i.e., texture and strain). Moreover, two new peaks were detected at
36.6 and 42.7° that found to be consistent with TiN crystal structure
(Fig. 4b). It is important to state that no peaks related to Ti oxides
were detected.

Top views of the processed layers were examined by eye. First

series of tracks produced under argon gas had dark appearance.
Thus, the number of nuzzles of the shrouding gas system was
increased to maintain suitable protection of the whole tool/substrate

400

300 TiN
Ti
CPS

200

100

0
20 30 40 50 60 70 80
2Theta

Fig. 5. X-ray diffraction pattern of Ti/TiN composite surface layer produced on work
piece with groove at a depth of 3 mm. Fig. 6. The microstructure of the as-received CP-Ti substrate.
 A. Shamsipur et al. / Surface & Coatings Technology 218 (2013) 62–70
a b
FSPed CP-Ti
in argon atmosphere
25µm
Fig. 7. The microstructure of the FSPed layer under argon gas; scanning electron (a) and bright field transmission electron (b) micrographs.
Fig. 5 shows X-ray diffraction pattern taken from the depth of
~3 mm beneath the top surface of the processed layer on work piece
with groove. Two peaks related to TiN crystal structure were present
with relatively low intensities in addition to those of Ti ones. Thus,
formation of TiN is confirmed even at a case depth of ~3 mm.
3.3. Microscopy of the as-received and FSPed substrates under argon gas
The as-received CP-Ti substrate showed an α-Ti grainy microstructure
(Fig. 6). The mean grain size was found to be ~75 μm using linear
intercept method.
The microstructure of the FSPed substrate (produced under argon
gas) was shown in Fig. 7a; a fine grain-structure with mean grain size
of ~18 μm was achieved due to thermo-mechanical treatment during
FSP. Although the measured temperature by internal thermocouple
was ~896 °C, the maximum stir zone temperature is expected to
be greater due to substantial heat loss and measuring problems
(thermocouple distance, time lag, etc.). Thus, stir zone temperature is
well beyond α-Ti → β-Ti transus temperature (~882 °C). This indicates
that CP-Ti was hot deformed in the β crystal structure state. The
observed equiaxed grain morphology reflects the occurrence of a
dynamic restoration phenomenon; these are prior β-Ti grains that
showed a transformed sub-structure of α′-Ti lath martensite (Fig. 7b).
3.4. Microscopy of the FSPed layers under nitrogen gas
The microstructures of the FSPed layers under nitrogen gas as
revealed by optical microscopy were shown in Fig. 8a and b (using
work pieces without and with groove, respectively). Both layers
showed non-uniform microstructures. In general, finer grains than
those of the substrate material were observed (e.g., ~4.5 μm in
Fig. 8b). These fine grains showed a transformed sub-structure of lath
and lens-type features (Fig. 8a and b). EDS analyses of the top surface
of the fabricated layers showed substantial nitrogen contents. However,
nitrogen concentration of the work piece with groove was found to be
much greater than that of the other one. In addition, it was considerable
in depth of the layer. Contrary to this, nitrogen concentration was
negligible in depth of the layer fabricated on the work piece without
groove. Nitrogen was reported to make relatively extended solid
solution in titanium. In addition, it acts as an α-Ti stabilizer element
by making an interstitial solid solution at a concentration up to
23 at.% [22]. A relatively fine equiaxed grain microstructure with
transformed sub-structure was reported in FSP and FSW of CP-Ti
65
FSPed CP-Ti
in argon atmosphere
α ′ -Ti laths
1 µm
[23,24]. In the case of transformed sub-structure of the present investi-
gation, it is likely that nitrogen increased the martensite transformation
temperature; this provides transformation of β-Ti → α′-Ti in a lath and
lens-type martensite formed upon cooling from high temperature.
Other observed features with faceted morphology were precipitates at
grain/sub-grain boundaries of the transformed grains as a minor
phase (Fig. 8a, b and c). However, their distribution is not uniform.
The layer on work piece with no groove exhibited less precipitates
with more non-uniform dispersion (Fig. 8a).
In the case of work piece with groove, the microstructure look likes
curvy bands (Fig. 8b and c). The bands seem to be in the direction of
material flow. Each band can be considered as a nitrogen-exposed-layer
that was taken inside the stir zone by complex material flow [25,26].
This scenario is in agreement with the observed banding microstructure
and inhomogeneous nitrogen concentration across its thickness.
EDS analyses on these features were indicative of considerable con-
centrations of nitrogen (Fig. 8d). The nitrogen content was found to be
beyond 27 at.%. A crystal structure with stoichiometric composition of
Ti2N is present in the binary phase diagram of Ti–N system when nitro-
gen content reaches 21 at.% [22]. By increasing nitrogen content to the
range of about 30 to 55 at.%, a new phase with TiN stoichiometry is
stable. Considering EDS limitations on detecting low atomic number
elements and the size of X-ray interaction volume that is greater than
the present precipitate dimension, the nitrogen concentration of the
precipitates is considered to be underestimated. This prediction is
reasonable due to the detection of TiN-based crystal structure by XRD
(Fig. 4b). Contrary to this, the dominant lens-type features exhibited
negligible nitrogen concentrations. Reflections related to Ti2N crystal
structure was not detected by XRD. It should be mentioned that this
phase was previously detected in layers produced by isothermal gas-
diffusion processes. Thus, its absence is believed to be due to the
relatively high cooling rate associated with FSP.
The thickness of the fabricated Ti/TiN composite surface layer
formed on work piece with groove is quite the same as that of the
groove (i.e. ~ 3 mm); this is relatively thicker than those produced
using diffusion and re-melting nitriding methods [1,2,27–30].
During FSP, severe plastic deformation is introduced into the mate-
rial at temperatures close to melting point. Hot plasticized material
shows strong affinity to nitrogen gas molecules. Thus, substantial
nitrogen molecules are trapped on hot surface of the stir zone.
The process of trapping or binding of molecules to the surface is called
adsorption. Due to strong affinity of titanium and nitrogen [31,32], ni-
trogen was picked-up. However, in this case, chemical adsorption is
66 A. Shamsipur et al. / Surface & Coatings Technology 218 (2013) 62–70

expected since bond energy is beyond the Vander-Waals forces.
The adsorption process can be activated due to exothermic nature of
TiN formation. It is expected that chemisorptions process proceeds at a
much greater rate than that of the conventional surface gas-nitriding
technique. The temperature of plasticized material is relatively greater
than those of solid state material in gas-nitriding techniques.
The maximum temperature of the stir zone in the production of Ti/TiN
composite surface layer by FSP was found to be ~890 °C. As mentioned
earlier, the actual temperature of the stir zone is well beyond this.
Nitrogen content of the fabricated layer is controlled by gradual
exposure of stir zone material to nitrogen gas. The chemisorbed nitro-
gen was then diffused into material. Diffusion process can proceed
even after the exposed material was taken inside the stir zone by
complex flow. In this case, crystal structure and its associated sub-
structure play important roles. Diffusion rate in the body centered
cubic arrangement of Ti atoms is greater than that of the closed
packed hexagonal one. In addition, relatively large areas of grain/
sub-grain boundaries were formed due to severe plastic deformation
induced by FSP, which open passages for easier diffusion of nitrogen
atoms into the plasticized material.
An example of a solid–gas system associated with deformation
is the synthesis of TiN using high energy ball milling of Ti in an
atmosphere of pure nitrogen [33]. It was proposed that nitrogen ab-
sorption in the milled product occurs at the moment of ball
collision; the extent of absorbed nitrogen during one collision event
is proportional to the supplied energy to powder. In addition, the

Formation of TiN near top

surface on substrate without
groove

20 µm

b c

Banding dispersion of TiN Banding dispersion of TiN

reinforcements in substrate reinforcements in substrate
with groove with groove

20 µm 20 µm

Fig. 8. The microstructures of Ti/TiN composite layer produced on work pieces without (a) and with groove (b and c) after first pass, and energy dispersive spectrum of a precipitate
at prior β-Ti grain/sub-grain boundary related to minor phase exhibiting considerable concentration of nitrogen (d).
 A. Shamsipur et al. / Surface & Coatings Technology 218 (2013) 62–70
a b
Uniform dispersion of TiN
reinforcements
50 µm
Fig. 9. The microstructures of the Ti/TiN composite layer produced on work piece with groove after four passes as revealed by scanning electron microscope (a and b).
phase evolution in systems under mechano-chemical treatment is
influenced by the initial pressure of nitrogen gas.
A nitrided layer is expected due to exposure of hot plasticized
material to nitrogen stream. However, the whole stir zone material
was not exposed to nitrogen gas. In order to have a homogenized
composite surface layer, additional passes were applied [9,18,34].
After three additional passes, a composite surface layer with uniform
dispersion of precipitates was achieved (Fig. 9a and b). The volume
fraction of the precipitates was measured to be ~ 2.3% (Fig. 9b)
using Clemex software [21].
Previous result showed that transitional phases on the surface of
the gas-nitrided sample are [1]:
α
Ti→α
TiðNÞ→Ti2 N→TiN;
Such trend is in agreement with the binary Ti–N phase dia-
gram [22]. In relatively low nitrogen concentration, interstitial solid
solution of N in α-Ti phase occurs, i.e. α-Ti(N). In gas nitriding
process, the nitrided layer thickness was found to be controlled kinet-
ically with the diffusion process according to Eq. (1) [35]:
D ¼ Do expð−Q =RTÞ:
Here, Do, Q, R, and T are the pre-exponential factor, activation
energy, gas constant and temperature in Kelvin, respectively. Nitrided
layer thickness depends on two main parameters in conventional
gas-nitriding techniques; temperature and time. In the present inves-
tigation, the process temperature is definitely greater than those of
the diffusion gas-nitriding processes [28,29]. However, the processing
time is several seconds that is nothing compared to several hours of
conventional diffusion techniques. No distinct diffused layer can be
achieved using conventional gas nitriding process at this limited
time. It should be born in mind that FSP is associated with high strain
rates [36], which in turn introduces various crystal defects into the
severely deformed material. These grain/sub-grain boundaries accel-
erate nitrogen diffusion into the plasticized material. Additional fac-
tor is material stirring in FSP. Due to stirring action imposed by the
rotating and advancing tool, new surface of hot plasticized material
is continuously exposed to nitrogen gas during the process. Thus,
the volume fraction of nitrogen atom in the plasticized material in-
creases, and consequently, true alloying can take place among the
constituent elements.
Thin foil examination exhibited a dominant martensitic microstruc-
ture (Fig. 10a) that is consistent with α′-Ti structure (Fig. 10b and c).
The laths showed a sub-structure of dislocation cell. In addition, precip-
itates were found (Fig. 10d); electron diffraction pattern was in agree-
ment with cubic TiN structure (e.g., Fig. 10e and f). Thin foil tilting
67
TiN reinforcements
2µm
at grain boundaries
experiments revealed a curvy contrast in the matrix close to TiN precip-
itate that reflects a coherent interface (Fig. 10e). This was confirmed by
the detected orientation relationship
h between
i the
 matrix and
 precipi-

tate (Fig. 10f and g); [001]TiN || 1011 α-Ti and 022Þ TiN || 1210 α-Ti.
In addition, dark field imaging using (200)TiN reflection of Fig. 10f
(Fig. 10g) showed a TiN precipitate in Ti matrix. Moreover, thin foil
tilting experiment revealed diffraction patterns in other zones; these
were in agreement with TiN crystal structure (e.g., Fig. 10h and i).
3.5. Microhardness evaluation of the processed layers
Fig. 11 presents the microhardness depth profile of the fabricated
surface layers; FSPed layer (under argon gas) after four passes and
Ti/TiN composite layer (using work piece with groove under nitro-
gen gas). The mean microhardness profile of the FSPed work piece
(under argon gas) was found to be ~ 301 HV; near twice of that of
the as-received substrate (~ 160 HV). The greater microhardness
value of the FSPed work piece under argon gas can be related
to grain refinement due to dynamic restoration process [6]. In the
case of nitrided layer, a remarkable increase in microhardness
value was detected. Relatively large discrepancy was found for the
ð1Þ Ti/TiN composite layer produced after one pass on work piece with
groove; this is related to non-uniform dispersion of TiN precipitates
in the matrix (Fig. 8b and c). However, discrepancy in results was
decreased after four FSP passes. A mean microhardness value
of ~ 972 HV was found for the fabricated Ti/TiN composite surface
layer with near uniform dispersion of reinforcements (Fig. 9a and
b), which is almost 6.4 times of that of the as-received CP-Ti sub-
strate. Formation of hard TiN structure and interstitial solid solution
of nitrogen in α-Ti structure increase the microhardness value of the
fabricated Ti/TiN composite layer. Extra contributions go to grain
refinement due to boundary pinning effect of TiN reinforcements
and their orientation relationship to CP-Ti matrix. Mridha reported
a maximum hardness value of ~ 2000 HV for the Ti/TiN composite
layer produced using tungsten inert gas processing of titanium in a
nitrogen reactive environment [27]. This remarkable result is related
to large volume fraction of TiN dendrites in the surface layer. In an-
other investigation, a greater value of ~ 3000 HV was recorded for
Ti/TiN composite layer fabricated employing laser surface processing
[5]. Such high hardness was found for a surface layer containing a
large TiN volume fraction of beyond 70%. While for a TiN dendrite
volume fraction of ~ 20%, the hardness value decreased to less than
800 HV. It should be noted that TiN volume fraction of the fabricated
Ti/TiN composite layer of the present work was found to be ~ 2.3%.
Here, hard and fine TiN reinforcements (~ 2 μm) were formed at
grain/sub-grain boundaries of a dynamically restorated titanium
matrix; these provide difficulties for the movement of dislocations.
68 A. Shamsipur et al. / Surface & Coatings Technology 218 (2013) 62–70

Under a shear stress, dislocations move on specific slip planes in a metal.
If the slip plane has obstacles such as precipitates or dispersoids, a dis-
location moving on this slip plane must interact with these obstacles.
The dislocation, under the action of an applied shear stress, bows be-
tween the obstacles in the slip plane. This mechanism of dislocation
bowing is called Orowan bowing around TiN particles. According to
Zener limiting grain size formula, the critical matrix grain size by a sim-
ple approach to estimate the pinning pressure by distribution of parti-
cles can be calculated using Eq. (2) [37]:
dz ¼ 4r=ð3Vf Þ
where, dz, r and Vf are Zener limiting grain size, the radius and vol-
ume fraction of reinforcement particles, respectively. As the particle
size decreases, at a relatively smaller volume fraction, a specific grain
size occurs (assuming a homogeneous dispersion of particles). Thus,
the fabricated Ti/TiN (2.3 vol.%) composite layer offers an average
hardness value of ~ 972 HV with relatively low TiN volume fraction
of ~ 2.3%; this was achieved by material stirring associated with FSP
technique.
4. Conclusions
1- Ti/TiN composite surface layer was achieved via reactive friction stir
processing by blowing nitrogen gas with a flow rate of 10 Lmin−1
ð2Þ into the stir zone of a CP-Ti work piece with groove using a tool rota-
tion and substrate advancing speeds of 1250 rpm and 35 mm min−1,
respectively.
2- TiN precipitates were formed in a non-uniform fashion. Ti/TiN
(2.3 vol.%) composite surface layer with near uniform dispersion
of TiN particles was achieved after three additional FSP passes in
argon environment.

Fig. 10. The microstructure of the Ti/TiN composite layer produced on work piece with groove after four passes as revealed by transmission electron microscope; bright field image
exhibiting the developing cell structure in Ti matrix (a), its electron diffraction pattern (b) and key to b (c), bright field imaging exhibiting TiN reinforcement in Ti matrix (d), its
electron diffraction pattern showing orientation relationship (e) and corresponding keys (f), dark field imaging using 200 reflection of TiN structure of e (g), diffraction pattern of a
TiN precipitate on another zone axis (h) and its key (i).
 A. Shamsipur et al. / Surface & Coatings Technology 218 (2013) 62–70 69

Fig. 10 (continued).

3- The fabricated composite surface layer had a thickness of ~ 3-mm 5- The composite surface layer offers an average microhardness
(quite the same size as that of the pin tool height). value of ~ 972 HV (about six times of that of the as-received
4- Uniform Ti/TiN composite layer exhibited a microstructure of CP-Ti substrate).
dominant fine dynamically restorated grains (~ 4.5 μm) with lath
and lens-type α′-Ti martensite sub-structure and minor TiN pre- Acknowledgment
cipitates. These showed orientation relationship to α-Ti matrix:
h i    Financial supports from the University of Tehran and the Iran
[001]TiN || 1011 α-Ti and 022Þ TiN || 1210 α-Ti.
Nano-technology Initiative are gratefully acknowledged.
70 A. Shamsipur et al. / Surface & Coatings Technology 218 (2013) 62–70

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