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Acta Materialia 83 (2015) 6174
www.elsevier.com/locate/actamat
Department of Materials Science and Engineering, University of North Texas, Denton, TX 76207, USA
Received 20 March 2014; revised 9 September 2014; accepted 12 September 2014
Available online 21 October 2014
AbstractSurface and subsurface structural evolution during sliding wear of two in situ nitrided titanium alloys, b Ti35Nb7Zr5Ta (TNZT) and
a/b Ti6Al4V (Ti64), was studied by cross-sectional transmission electron microscopy coupled with precession electron diraction. In situ nitriding
during the laser engineered net shaping (LENSe) process resulted in the formation of hard and wear-resistant Ti2N + TiN phases and nitrogenenriched a phase in TNZT and Ti64, respectively. Subsurface structural analyses of the worn nitrided TNZT revealed the tendency of a grains,
and to greater extent b grains, to undergo severe plastic deformation, forming a heavily grain-rened nanocrystalline a and b tribolayer. Corresponding precessionorientation imaging phase maps were used to determine the orientation and percentage of a and b-Ti in the worn nitrided TNZT. The
maps revealed that the nanocrystalline grains of soft/compliant b are much smaller (10100 nm) than hard/sti a grains (>100 nm). Wear reduction is
due to the combination of the above phases and the increase in the alignment of {0 0 0 2}-textured coarser a grains along the sliding direction in
absence of texture in the highly rened b grains. Conversely, nitrided Ti64 exhibited slightly increasing wear, despite higher hardness, due to the
change in sliding-induced deformation mechanism where shear bands formed and networked leading to brittle fracture and third body abrasive wear
particle generation.
2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Keywords: Titanium alloys; Nitriding; Wear; Transmission electron microscopy (TEM); Precession electron diraction (PED)
1. Introduction
Titanium (Ti) alloys have long been used in many
diverse applications ranging from orthopedic biomedical
implants (femoral stems) to aerospace gas turbine engine
components (compressor blade roots) [14]. While Ti alloys
such as the a + b alloy Ti6Al4V (Ti64) and the b alloy
Ti35Nb7Zr5Ta (TNZT) are well known for their corrosion resistance, adequate fracture toughness and fatigue
strength, they exhibit high wear rates, resulting in galling
(adhesive) failure and fretting fatigue [48]. Thus, they
require surface modication treatments to improve their
wear behavior [412]. One such approach is surface nitriding, which produces a high hardness and a chemically inert
layer that overcomes the poor wear resistance of Ti alloys.
The process involves heat treating at elevated temperatures
(7001100 C) in a nitrogen-enriched atmosphere or
implantation of nitrogen ions into the surface of Ti alloys
[8,10,11,1318]. Surface nitriding is a fast, inexpensive
and simple treatment to form a hardened, wear-resistant
case layer on the surface. However, the penetration depth
of nitrogen into the bulk alloy is limited, thus restricting
the thickness of the nitride layer to mitigate wear, and the
http://dx.doi.org/10.1016/j.actamat.2014.09.026
1359-6462/ 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
62
2. Experimental methods
A LENSe 750 system (Optomec, Inc.) with an Nd:YAG
laser at a wavelength of 1.064 lm and a power of 760 W
was used to deposit blends of elemental powders under
100% Ar and 100% N2 atmospheres for deposition of base
and nitrided (TNZT-N and Ti64-N) alloys, respectively.
The TNZT and Ti64 alloy powders (manufactured by
TIMET, Inc.) were mixed with a twin-roller ball mill in
the ratio of Ti35Nb7Zr11Ta and Ti6Al4V (wt.%).
More details of the LENSe processing parameters are
reported elsewhere [7,28]. As-deposited base and nitrided
TNZT and Ti64 alloys were subsequently surface polished
using 1200-grade SiC grinding paper followed by ne polishing down to 200 nm arithmetic surface roughness with
0.05 lm colloidal silica. X-ray diraction (Rigaku Ultima
III diractometer) with a Cu Ka source was used for phase
identication. Surface microstructural characterization was
carried out in a eld emission gun scanning electron
microscope (FEI Nova Nano SEM230).
Site selective, cross-sectional FIB-SEM studies were
performed on the alloys with an FEI Nova 200 Nanolab
dual-beam microscope. Cross-sectional lift-outs acquired
outside and inside worn areas were then analyzed with
bright-eld TEM (BFTEM) and energy-dispersive X-ray
spectroscopy (EDS) line proles and maps. These analyses
were performed in a FEI Tecnai G2 F20 S-twin transmission electron microscope operated at 200 keV. The rst step
Fig. 1. XRD patterns obtained from LENS deposited (a) Ti64 and
nitrided Ti64 (Ti64-N), and (b) TNZT and nitrided TNZT (TNZT-N)
alloys.
63
Table 1. Lattice parameters and d spacings of signicant planes of a and b phases in Ti64, Ti64-N, TNZT and TNZT-N alloys.
)
)
)
)
)
Alloy
d(1010)a (A
d(0002)a (A
aa (A
ca (A
c/a
d(110)b (A
Ti64
Ti64-N
TNZT
TNZT-N
2.526
2.535
2.587
2.335
2.345
2.408
2.917
2.927
2.987
4.651
4.686
4.816
1.59
1.60
1.61
2.342
2.333
)
ab (A
3.312
3.30
64
Fig. 2. (a) Low- and (b) high-magnication backscatter SEM images of LENS deposited Ti64 alloy. (c) Low- and (d) high-magnication backscatter
SEM images of LENS deposited nitrided Ti64 (Ti64-N) alloy. See text for explanation of Type 1 and 2 precipitates.
65
Fig. 3. (a) Backscatter SEM image of nitrided Ti64 alloy with corresponding EDS maps of (b) nitrogen, (c) aluminum and (d) vanadium. (e) Crosssectional BFTEM image of nitrided Ti64.
66
Fig. 5. Low-magnication backscatter SEM images of LENS deposited (a) TNZT and (b) nitrided TNZT (TNZT-N) alloys. (c) Cross-sectional
HAADF-STEM image of nitrided TNZT alloy with corresponding titanium, niobium and tantalum EDS maps.
precipitates forming in the liquid exhibit a dendritic morphology, and can act as heterogeneous nucleation sites
for the b grains during solidication, resulting in more
equiaxed b grains (Fig. 5b) as compared to the dendritic
b grains observed in LENSe deposited TNZT in the
absence of nitrogen (Fig. 5a). Despite the prior formation
of the d-TiN dendrites, at the elevated temperatures where
the b grains nucleate, they have a certain solubility of nitrogen, as evident from the TiN binary phase diagram in
Fig. 4. Thus on subsequent cooling this retained nitrogen
will facilitate the precipitation of a phase at both heterogeneous grain boundary sites as well as homogeneously
within the b grains. Furthermore, as soon as a precipitates
within the b matrix, the retained nitrogen within the b partitions to the a phase, resulting in an increase in the c/a
ratio of this phase.
To better understand the possible phase formation
sequence, isothermal sections of the TiNbN ternary system were simulated using PANDATe developed by Computherm LLC and are shown in Fig. 6ac, corresponding
to temperatures of 2000, 1000 and 100 C, respectively.
Nb was chosen as the third component since it is the most
abundant element in the alloy after Ti. This ternary phase
diagram can provide some valuable insights on the competing nature of the b stabilizing elements and a stabilizing
eects of nitrogen on the phase stability in this complex
alloy. From Fig. 6a, it evident that fcc rocksalt d-TiN is a
high-temperature phase and exists at 2000oC in conjunction
with bcc b phase and liquid for a nominal composition of
35 wt.% Nb and 10 wt.% nitrogen. Fig. 6b shows for
a similar average composition that bcc b, d-TiN and Ti2N
are the stable phases at 1000oC, indicating the possible formation of the second nitride, Ti2N phase. Further lowering
the temperature to 100 C results in the precipitation of the
hcp a phase in addition to the bcc b, d-TiN and Ti2N
phases, as shown in Fig. 6c. The retention of d-TiN dendrites, in the LENSe deposited TNZT at room temperature, is explained by the non-equilibrium cooling involved
67
68
Table 2. Summary of averaged Vickers microhardness values, wear track depth, width and wear factor for Ti64, Ti64-N, TNZT and TNZT-N alloys.
For nitrided Ti64 and TNZT alloys, adhesive wear of Si3N4 counterface transferred to the wear track prevented accurate wear depth and factor
calculations.
Alloy
Microhardness (HV)
Ti64
Ti64-N
TNZT
TNZT-N
419 32
1047 29
288 21
518 35
20.3 0.7
3.9 0.4
715 39
330 15
420 20
312 11
6.4 0.2 10
5.3 0.3 10
Fig. 7. Low- and high-magnication SEM images of (a) Ti64 and (b) TNZT wear tracks.
69
Fig. 8. Low- and high-magnication SEM images of nitrided (a) Ti64 and (b) TNZT wear tracks. Arrows in the higher magnication image in (a)
denote cracks.
70
TNZT are approximately the same despite their large dierences in wear values (Table 2). Thus, the dierences in surface and subsurface structural evolution during sliding
wear are also determining the wear behavior of these alloys.
Recrystallization due to sliding is unlikely since the computed interfacial ash temperature due to frictional heating
is low (40 C), due in part to the low contact stress and
sliding speed used in this study. Therefore, the wearinduced structural changes are a result of the high deformation strain during sliding, e.g. large plastic shear strains
exceeding 10 are common with sliding contact of metallic
materials [33]. In the case of nitrided TNZT, formation of
more stable nanocrystals of equiaxed a and b-Ti without
fracture, e.g. shear bands, indicates the potential to accommodate the interfacial shear stresses during sliding contact
that reduces wear. Detailed TEM-based orientation mapping of the severely deformed zone in nitrided TNZT will
be presented in the following section to explain what role
these rened a and b grains have on the wear behavior
and mechanism. The presence of nanocrystalline grain
renement has been determined to improve sliding wear
resistance in titanium when processed by a severe plastic
deformation (SPD) technique. For example, Stolyarov
et al. reported an improvement in the wear resistance of
commercially pure titanium after equal-channel angular
pressing (ECAP) that resulted in an ultrane-grained
(UFG) structure that was responsible for a decrease in
the adhesive component of friction and wear [34]. Similarly,
71
Fig. 12. Cross-sectional IPF maps of worn nitrided TNZT showing orientation map of (a) b-Ti, and (b) a-Ti and phase concentration maps of the (c)
top portion of the zone 1 worn region, and (d) bottom portion of the zone 2 unworn region. The insets show grain orientation color codes. The white
dashed lines represent the border between zone 1 and zone 2. In (c) and (d) phase maps, red represents b grains and green represents a grains taken
from zone 1 (yellow dashed line box) and zone 2 (brown dashed line box) regions. (For interpretation of the references to colour in this gure legend,
the reader is referred to the web version of this article.)
72
the IPF map in green in Fig. 12b. Not shown are IPF maps
rotated at 90 to the TD of the sample (viewed along the
ND) where the (0001) planes, red on the IPF map, are perpendicular to the ND. Therefore, the a-Ti (0002) planes are
parallel to the wear surface, i.e. lie in the sliding plane (SD
and TD). From these IPF maps, it is evident, at least based
on this particular TEM liftout, that a pronounced a-Ti texture of the basal type remains after sliding. More details of
this texture will be presented below with pole gure analysis. Furthermore, Fig. 12 shows there are clear dierences in
the b-Ti and a-Ti grain sizes in zone 1 compared to the
unworn grain sizes in zone 2, with the former exhibiting
more grain renement. This is due to the softer and more
compliant nature of the b grains in comparison to the surrounding hard/sti a grains [11], which results in signicant
b grain renement during the wear process. This grain size
comparison is more evident with viewing the combined b-Ti
and a-Ti phase maps of zones 1 (worn) and 2 (unworn) in
Fig. 12c and d, respectively. Clearly the b-Ti grains,
denoted in red, are more rened in zone 1, while the a-Ti
grains in green are less rened. Phase concentration
Fig. 13. Comparison of b-Ti and a-Ti pole gures acquired from worn (zone 1) and unworn (zone 2) nitrided TNZT viewed along ND. Units for the
texture scale bars are in multiples of random.
73
the case of nitrided TNZT, strain-induced plastic deformation resulted in the formation of a heavily grainrened tribolayer composed of both ultrane b-Ti grains
(10100 nm size) and larger a-Ti grains. Formation of
more stable nanocrystals of equiaxed a and b-Ti without
fracture, e.g. shear bands, indicates the potential to
accommodate the interfacial shear stresses during sliding
contact that reduces wear.
3. Orientation imaging analysis of nitrided TNZT using
TEM-PED revealed that the a-Ti grains exhibit basal
texture and become more aligned parallel to the sliding
direction during wear, while the softer and compliant
nanocrystalline b-Ti grains are randomly orientated
and likely prone to rotation during wear. These sliding-induced phenomena coupled with the hard phases
that form during solidication are responsible for
improvements in wear resistance with in situ nitriding.
Acknowledgements
The authors would like to acknowledge the support of the Air
Force Research Laboratory (AFRL)-sponsored UNT Institute for
Science and Engineering Simulation (ISES) with Grant FA865008-C-5226. We also acknowledge the UNT Center for Advanced
Research and Technology (CART), UNT College of Engineering
for sponsoring A.T. as part of its SUPER program, and Anchal
Sondhi for assistance with XRD acquisition.
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