metals

Article
Microstructure and Wear Properties of Electron Beam
Melted Ti-6Al-4V Parts: A Comparison Study against
As-Cast Form
Wei Quan Toh 1 , Pan Wang 2 , Xipeng Tan 1, *, Mui Ling Sharon Nai 2 , Erjia Liu 1, * and
Shu Beng Tor 1
1 Singapore Centre for 3D Printing, School of Mechanical and Aerospace Engineering,
Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798, Singapore;
tohw0023@e.ntu.edu.sg (W.Q.T.); msbtor@ntu.edu.sg (S.B.T.)
2 Singapore Institute of Manufacturing Technology, 73 Nanyang Drive, Singapore 637662, Singapore;
wangp@simtech.a-star.edu.sg (P.W.); mlnai@simtech.a-star.edu.sg (M.L.S.N.)
* Correspondence: xptan1985@gmail.com (X.T.); mejliu@ntu.edu.sg (E.L.); Tel.: +65-6790-5504 (X.T. & E.L.)

Academic Editor: Manoj Gupta

Received: 29 October 2016; Accepted: 15 November 2016; Published: 18 November 2016

Abstract: Ti-6Al-4V (Ti64) parts of varying thicknesses were additively manufactured (AM) by the
powder-bed-based electron beam melting (EBM) technique. Microstructure and wear properties of
these EBM-built Ti-6Al-4V parts have been investigated in comparison with conventionally cast Ti64
samples. Sliding wear tests were conducted using a ball-on-disc micro-tribometer under ambient
conditions. Experimental results reveal that EBM-built Ti64 samples exhibited higher microhardness
and an overall larger coefficient of friction as compared to the as-cast counterpart. Of interest is that
the corresponding specific wear volumes were lower for EBM-built Ti64 samples, while the as-cast
Ti64 showed the poorest wear resistance despite its lower coefficient of friction. Wear mechanisms
were provided in terms of quantitative microstructural characterization and detailed analysis on
coefficient of friction (COF) curves.

Keywords: additive manufacturing; 3D printing; electron beam melting; titanium alloys;

microstructure; wear properties

1. Introduction
Metal additive manufacturing (AM), popularly known as metal three-dimensional (3D) printing,
is changing the way how metals or alloys are manufactured. Powder-bed fusion is the latest developed
metal AM technology, which opens up new opportunities to create complex metallic components with
relatively high resolution and good dimensional accuracy control [13]. Ti-6Al-4V (Ti64) is the most
commonly investigated metallic material in AM because of its high specific strength, excellent corrosion
resistance, and good biocompatibility, which are highly demanded in aerospace and biomedical
industries [4,5]. Electron beam melting (EBM ) is a representative powder-bed fusion metal AM
technique that is being increasingly employed to process Ti64. It utilizes an electron beam to selectively
melt a metallic powder bed given an input of a computer-aided design (CAD) model [6]. The distinct
advantages associated with EBM are its ability to fabricate metallic parts more rapidly and with
greater energy-efficiency as compared to its comparative technique of selective laser melting (SLM).
Moreover, EBM-built parts were shown to have less residual stress than their counterparts fabricated
by laser-based systems [69]. Hence, post-heat treatment may not be required for EBM-built metal
parts, giving an added advantage that leads to greater saving of resources.
Many studies have reported on the processing, microstructure, and mechanical properties of
powder-bed fusion AM Ti64 parts [57,913]. It has been found that some of the mechanical properties,

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Metals 2016, 6, 284 2 of 13

particularly for tensile properties of metal AM Ti64, are comparable to those of wrought material and
much better than its as-cast form [12,13]. However, there are still very limited studies involved in their
wear properties that are critical for some specific applications under wear and friction conditions [14].
As known, Ti64 possesses poor wear resistance under dry sliding due to low protection exerted by
tribo-oxides formed at the surface [15,16]. Therefore, it is imperative to study on wear behavior of
AM Ti64 parts and know their wear properties in comparison with the counterparts manufactured via
conventional methods. In our previous works published elsewhere [5,6,1721], the microstructure and
mechanical properties of the EBM-built Ti64 parts have been systematically studied. The present work
aims at investigating the wear properties of EBM-built Ti64 parts with various thicknesses and making
a comparative study against commercially as-cast Ti64 sample. It is supposed to be an important
supplementary study to achieve better understanding for practical applications of EBM-manufactured
Ti64 parts.

2. Experimental Section

2.1. Materials, Fabrication, and Sample Preparation

All the EBM-built samples were fabricated via an Arcam A2XX (Arcam AB, Mlndal, Sweden)
EBM machine, which has a build chamber of 420 mm 380 mm. A schematic diagram of a typical
EBM machine is illustrated in Figure 1. The powder used in this process was Ti-6Al-4V ELI (Grade 23)
(Batch No. 877) supplied by Arcam AB, and was mainly spherical in shape, as shown in Figure 2a. The
spherical nature of the powder assures good followability and thus consistency in the spreading of
powder during raking. The powder had a size distribution ranging from 45 to 105 m, while the mean
particle size was 61.8 m 23.8 m. A summary on the powder size distribution of Ti64 used during
fabrication is as depicted in Figure 2b. The nominal composition of the Ti64 powder is as follows:
6.0Al-4.0V-0.03C-0.1Fe-0.1O-0.01N-<0.003H and the balance being Ti (wt. %). The EBM-built samples
of varying thicknesses of 0.5 mm, 1 mm, 5 mm, 10 mm, and 20 mm by 100 mm in length and 30 mm in
height are shown in Figure 3a. They were termed 0.5 mm, 1 mm, 5 mm, 10 mm, and 20 mm samples,
respectively. The build chamber was under a controlled vacuum environment having a temperature
range of 600 to 650 C. The samples were built on a 210 mm 210 mm stainless steel (SS) start plate.
The samples were subsequently removed from the SS start plate via knocking on the backside of the
SS plate and cleaned with the use of the powder recovering system (PRS). PRS primarily functioned as
a grit blaster where blasting media (Ti64) were accelerated towards the sample surface with the aid of
high velocity compressed air with the aim to remove any residual partially-sintered and unmelted
powder particles surrounding the samples surface. The as-cast samples were supplied in the form of a
rod by Titan Engineering Pte. Ltd. (Singapore, Singapore), cast to the specification ASEM B348 GR5
and had a dimension of 25.4 mm 1500 mm. The EBM-built samples were sliced from the middle
section (XZ plane) into squares of 20 mm 20 mm, while the as-cast sample was sliced into a disc of
25.4 mm 5 mm. All the samples were then hot mounted with phenolic polymer and subsequently
polished to a mirror-like finish.
 Metals 2016, 6, 284 3 of 13
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EBM Gun

Filament

Astigmatism
Lens

Focus Lens

Deflection
Lens

Heat Shield

Powder
Hopper
Rake Built
Part

Start
Plate

Figure 1. 1.Schematic
Figure Schematicof
ofan
an Arcam A2XXEBM
Arcam A2XX EBMmachine.
machine.

Figure 2. (a)2.SEM
Figure image
(a) SEM and
image (b)(b)
and powder
powdersize
sizedistribution ofTi64
distribution of Ti64powder
powder supplied
supplied by Arcam
by Arcam AB. AB.
Metals 2016, 6, 284 4 of 13
Metals 2016, 6, 284 4 of 13

(a) 10 mm
20 mm
1 mm

0.5 mm
5 mm

(b) Counter Weight Ball

Load
Holder

Arm

Radius Gauge 100Cr6 Ball

Rotating Platform Sample

Figure 3. (a) Schematic of EBM-built Ti64 samples with thicknesses of 0.5, 1, 5, 10, and 20 mm. (b)
Figure 3. (a) Schematic of EBM-built Ti64 samples with thicknesses of 0.5, 1, 5, 10, and 20 mm;
Schematic configuration of the ball-on-disc micro-tribometer.
(b) Schematic configuration of the ball-on-disc micro-tribometer.

2.2. Powder Analysis

2.2. Powder Analysis
Morphological characteristics of the Ti64 powder were determined using a Malvern Morphologi
Morphological characteristics of the Ti64 powder were determined using a Malvern Morphologi
G3 S (Malvern Instruments Ltd., Worcestershire, UK). Powder samples of 5 mm3 in volume were
G3 S (Malvern Instruments Ltd., Worcestershire, UK). Powder samples of 5 mm3 in volume
dispersed on the glass plate. A 5 objective was used for the measurement of this study. Four
were dispersed on the glass plate. A 5 objective was used for the measurement of this study.
parameters of particle size viz. D10, D50, D90, and Daverage (size below which 10%, 50%, 90%, and average
Four parameters of particle size viz. D10 , D50 , D90 , and Daverage (size below which 10%, 50%, 90%, and
particle size are present, respectively) were calculated from the particle size distribution curve.
average particle size are present, respectively) were calculated from the particle size distribution curve.
2.3. Surface
2.3. Surface Analysis
Analysis
Surface roughness of
Surface roughness of as-built
as-built and
and as-polished
as-polished Ti64 samples, and
Ti64 samples, and worn
worn surfaces
surfaces were
were examined
examined
using a
using a surface
surface profilometer
profilometer (Talyscan 150) (Taylor
(Talyscan 150) (Taylor Hobson
Hobson Inc.,
Inc., Rolling
Rolling Meadows,
Meadows, IL, IL, USA)
USA) with
with aa
diamond stylus of 4 m in diameter. Chemical compositions of as-built and as-polished surfaces were
diamond stylus of 4 m in diameter. Chemical compositions of as-built and as-polished surfaces were
analyzed with the aid of X-ray photoelectron spectroscopy (XPS; Kratos AXIS Ultra, Kratos
analyzed with the aid of X-ray photoelectron spectroscopy (XPS; Kratos AXIS Ultra, Kratos Analytical Analytical
Ltd., Manchester,
Ltd., Manchester,UK).UK).Both
Boththe theas-built
as-builtand
andthe
theas-polished
as-polishedsamples
samples were
were sliced
sliced from
from thethe other
other side
side of
of the squares and cut into pieces of 10 mm 10 mm 2 mm. All of the Ti64
the squares and cut into pieces of 10 mm 10 mm 2 mm. All of the Ti64 samples were ultrasonically samples were
ultrasonically
cleaned cleaned
in acetone and in acetone
ethanol forand ethanol
30 min for 30 min
respectively andrespectively andbox
stored in dry stored in drybefore
overnight box overnight
analysis
before analysis
was carried out. was carried out.

2.4. Microstructural
2.4. Characterisation Techniques
Microstructural Characterisation Techniques
Microstructure, wear
Microstructure, wear morphology
morphology and and wear
wear debris
debris were examined using
were examined a scanning
using a scanning electron
electron
microscope (SEM;
microscope (SEM;JEOL-JSM-5600LV;
JEOL-JSM-5600LV;2020kV, kV, JEOL
JEOL Ltd.,
Ltd., Akishima,
Akishima, Japan).
Japan). Chemical
Chemical composition
composition of
of the
the wear debris was examined by energy-dispersive X-ray spectroscopy (EDX) (Oxford
wear debris was examined by energy-dispersive X-ray spectroscopy (EDX) (Oxford Instruments Plc.,Instruments
Plc., Abingdon,
Abingdon, UK) equipped
UK) equipped within within
the SEM. theInSEM. In addition,
addition, X-ray diffraction
X-ray diffraction (XRD; PANalytical
(XRD; PANalytical Empyrean;
Empyrean;
Cu Cu K;
K; 40 mA; 40 mA;
40 mV; 40 mV;
step size step
of 0.01 ) size of 0.01) (PANalytical,
(PANalytical, Almelo, The was
Almelo, The Netherlands) Netherlands)
employedwasfor
employed for phase
phase identification. identification.

2.5. Mechanical Properties Evaluation

Vickers microhardness tests were carried out on the slightly-etched samples using a Vickers
micro-indentor (Future-tech FM-300e) (FUTURE-TECH Corp., Fujisaki, Japan) with an applied load
of 1 kg and a dwell time of 15 s. Sliding wear tests were carried out on polished surfaces, using a ball-

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Metals 2016, 6, 284 5 of 13

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a dwell time of 15 s. Sliding wear tests were carried out on polished surfaces, using 5 of 13
a
ball-on-disc micro-tribometer (CSM model, Anton Paar Gmbh, Graz, Austria) as shown in Figure 3b
on-disc
at roommicro-tribometer
temperature of 23(CSM C and model,
in theAnton
ambientPaarenvironment.
Gmbh, Graz, A Austria)
100Cr6as shown
steel ball inof Figure
6 mm3b wasat
room
used as temperature
counter-face of with
23 Can and in the load
applied ambient
of 1 environment.
N on the rotating A 100Cr6 steel ballinofa 6
Ti64 samples mm was
circular pathused
of 3
as
mm in diameter at a linear sliding velocity of 2 cm/s for 50,000 laps. For all of the EBM-built 3samples,
counter-face with an applied load of 1 N on the rotating Ti64 samples in a circular path of mm in
diameter at a linear sliding velocity of 2 cm/s for 50,000 laps. For all of the EBM-built samples, the X
the XZ plane was wear tested. Based on the measured wear width and wear depth, wear volume
Z plane was wear tested. Based on the measured wear width and wear depth, wear volume was
was calculated via a simple geometrical equation. Specific wear rates [22] were then evaluated by
calculated via a simple geometrical equation. Specific wear rates [22] were then evaluated by
normalizing the wear volume with the load applied (N) and sliding distance (m).
normalizing the wear volume with the load applied (N) and sliding distance (m).
3. Results and Discussion
3. Results and Discussion
3.1. Microstructure
3.1. Microstructure
Figure 4 shows the microstructure of the EBM-built and as-cast Ti64 samples. It can be clearly
seen Figure
that both 4 shows
the 0.5the
mmmicrostructure
and 1 mm samples of thehave
EBM-built
similarand as-cast
alternate Ti64
/ samples. It canmixed
microstructures be clearly
with
seen
acicular 0
thatboth the 0.5 mm
martensite, and
which is 1different
mm samplesfrom thehave restsimilar
of the alternate
EBM-built/ microstructures
samples and the as-cast mixed with
sample,
acicular
which have martensite, which is different
/ microstructures. fromdifference
Of particular the rest of the EBM-built
is that coarse was samples
observed andinthe
the as-cast
sample,
sample. which have /the
Additionally, microstructures.
results obtained Offrom
particular
the XRD difference
patterns is shown
that coarse was 5observed
in Figure revealedinpeakthe
as-cast
shiftingsample.
phenomenonAdditionally, the results1obtained
in the EBM-built mm sample fromasthe XRD patterns
compared to the shown
20 mm in and Figure 5 revealed
the as-cast Ti64
peak
sample.shifting phenomenon
This peak in the EBM-built
shifting phenomenon is in1line
mmwith sample
the as compared
studies by Zeng to the 20[23]
et al. mmthat andsuggest
the as-cast
the
Ti64 sample.
presence 0
of This peak shifting
martensite. The phenomenon 0
appearance ofisin phase line with themm
in 0.5 studies
andby Zengwas
1 mm et al. [23]confirmed
also that suggestby
the
TEM presence
observationof [5,18].
martensite.
In theThe caseappearance of phase
of the EBM-built samplesin 0.5
two mm andof1 typical
types mm was also confirmed
transformed /
by TEM observation
structure was observed, [5,18]. In the case
namely, of the EBM-built
the colony samples two types
and the basket-weave of typical
(also known as transformed
Widmansttten) /
structure
morphologies. was observed,
As a resultnamely, the colony
of the difference and the basket-weave
in microstructure, they have (also known
different as Widmansttten)
microhardness values
morphologies.
which will be given As a inresult of the difference
the following sections. inFrommicrostructure,
the results, itthey have that
is known different 0 phase
microhardness
the acicular
values
causes which
a higher will be given
hardness in the
value following sections.
as compared to the / From the results,seen
microstructure it is known
in the restthatofthe
the acicular
EBM-built
phase
samples. causes a higher the
In addition, hardness value as compared
microhardness of EBM-built to the
Ti64/ microstructure
samples decreases seen
with in the
the increase
rest of thein
EBM-built samples.
sample thickness. Inisaddition,
This due to thethe fastmicrohardness
cooling rate coupledof EBM-built
with theTi64EBMsamples decreases with
build temperature, the
favoring
increase
the formation of 0 martensite
in sample thickness. inThis is due
the thin to the[10,18].
samples fast cooling rate sample
The as-cast coupledhas with the EBM
the lowest build
hardness
temperature,
value due to favoring
its coarsethe/formation of martensite
microstructure, which isinlargelythe thin samples
caused by [10,18]. The as-cast
the moderate sample
cooling rate
has the the
during lowest hardness
casting processvalue due to its coarse / microstructure, which is largely caused by the
[14,24].
moderate cooling rate during the casting process [14,24].

Figure 4. (af) SEM

SEM micrographs
micrographsofofEBM-built
EBM-builtTi64
Ti64samples
sampleswith thicknesses
with of 0.5,
thicknesses 1, 5,1,10,
of 0.5, 5, and 20 mm
10, and 20
and the as-cast Ti64 samples, respectively. Microstructural features are indicated by arrows.
mm and the as-cast Ti64 samples, respectively. Microstructural features are indicated by arrows.

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Metals 2016, 6, 284 6 of 13
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1.8
1.8 As-cast
1.6 20As-cast
mm 1.0
1.6 1 20
mmmm 1.0

Relative Intensity
0.8

Intensity
1.4 1 mm

Relative Intensity
0.8

RelativeIntensity
1.4 0.6
1.2 0.6
0.4
1.2
0.4
1.0 0.2
1.0 0.2
0.0
0.8 40.0 40.2 40.4 40.6 40.8

Relative
0.0
0.8 40.0 40.2 2 40.4
Theta 40.6 40.8
0.6 2 Theta
0.6
0.4
0.4
0.2
0.2
0.0
0.0 35 40 45 50 55 60 65 70 75 80
35 40 45 50 55 60 65 70 75 80
2 Theta (deg)
2 Theta (deg)
Figure
Figure 5.
5. XRD
XRD patterns
patterns for
for 11 mm
mm and
and 20
20 mm
mm EBM-built
EBM-built and as-cast Ti64 samples.
Figure 5. XRD patterns for 1 mm and 20 mm EBM-built and as-cast Ti64 samples.
3.2.
3.2. Surface Conditions
3.2.Surface
SurfaceConditions
Conditions
Figure
Figure 6 shows 3D surface mappings ofofthetheEBMEBMas-built 2020mm sample and thetheas-polished 20
Figure66shows shows 3D 3D surface
surface mappings
mappings of the EBM as-built
as-built 20 mmmm sample
sample and
and as-polished
the as-polished 20
mm
20 mm sample
sample forfor drydry sliding
sliding wear
wear tests.
tests. ToToourour authors
authors best
best knowledge,
knowledge, the
the rough
rough build
build surface
surface of
of
mm sample for dry sliding wear tests. To our authors best knowledge, the rough build surface of
AM-fabricated
AM-fabricated parts may be the main obstacle tototheir
theirdirect
directpractical
practicalapplications. From Figure 6, it
AM-fabricatedparts partsmay may be be the
the main
main obstacle
obstacle to their direct practical applications.
applications. From
From Figure
Figure 6,6,it
can
itcan be obtained
canbebeobtained
obtainedthatthat EBM
thatEBM as-built
EBMas-built Ti64
as-builtTi64 samples
Ti64samples
sampleshavehave an average
haveananaverage
average surface
surface roughness
roughness of 34.4
of m.
34.4 In
m.
surface roughness of 34.4 m. In
order
In order to to
avoid
avoid thetheinfluence
influenceofof ofrough
rough surfaces on wear properties,
properties, allofofthe thesamples
sampleswere were polished
order to avoid the influence rough surfaces
surfaceson onwear
wear properties,allall of the samples were polished
polishedto
to
ato a mirror-like
mirror-like finish
finish with
withwith roughness
roughness of
of ~0.3 ~0.3 m. XPS
XPS XPS survey
survey spectra
spectra for
for both both the EBM-built
the EBM-built 20 mm 20 mm
a mirror-like finish roughness m. m.
of ~0.3 survey spectra for both the EBM-built 20Ti64
mm
Ti64
sample sampleand and powder
Ti64 Ti64 powder used used
for EBM for EBM fabrication
fabrication are are shown
shown in in Figure
Figure 7. In 7. InXPS
both bothspectra,
XPS spectra,
it was
Ti64 sample and Ti64 powder used for EBM fabrication are shown in Figure 7. In both XPS spectra,
it was dominated
dominated by strong by strong signals of titanium (Ti), carbon (C), and oxygen
(O). Of(O). Of particular
interestinterest
it was dominated by signals of titanium
strong signals (Ti), carbon
of titanium (Ti), (C),
carbonand oxygen
(C), and oxygen particular
(O). Of particular is that
interest
is
the that the
signal signal
for for
aluminum aluminum
(Al) was (Al) was
detected detected
on the on
Ti64 the Ti64
powder powder
surface. surface.
But not But
on not
the on the sample
sample surface.
is that the signal for aluminum (Al) was detected on the Ti64 powder surface. But not on the sample
surface.
This may This may suggest
suggest the that the surfaceform oxide onform on thesamples
EBM samples were predominately Ti and Ti
surface. This maythat suggest surface
that theoxide surface oxide the EBM
form on the EBM samples were predominately
were predominately O.Ti
and
The O. The
presence presence
of carbon of carbon
on both on both
instances instances
were were
not not
unusual unusual
based based
on on
previousprevious literatures
literatures [25] [25]
and
and O. The presence of carbon on both instances were not unusual based on previous literatures [25]
and
the the detection of carbon is amainly a adsorption
result of adsorption of organicfrom molecules from the
anddetection of carbon
the detection of is mainly
carbon result of
is mainly a result of of organic molecules
adsorption of organic molecules the environment.
from the
environment.
Aenvironment.
detailed scan A detailed
of the scan of the
elements elements
present on present
the on the
surface of surface
the Ti64ofsamples
the Ti64were samples wereout
carried carried
and
A detailed scan of the elements present on the surface of the Ti64 samples were carried
out and
illustrated illustrated
in Figure 8a,b,in Figure 8a,b,
where8a,b, where
the Tiwhere 2p andthe Ti
O Ti 2p
1s peak and O
of the1s peak
EBM-builtof the EBM-built
20 mm sample 20 20 mm
were sample
revealed,
out and illustrated in Figure the 2p and O 1s peak of the EBM-built mm sample
were revealed,The
respectively. respectively.
Ti 2p peak The
has Tisymmetrical
2p peak haspeak symmetrical
shapes, peak shapes,
which is in linewhich
with isthe
in line with the
formation of
were revealed, respectively. The Ti 2p peak has symmetrical peak shapes, which is in line with the
formation
titanium of titanium
dioxide dioxide
(TiO2 ).dioxide (TiO
Correspondingly, 2). Correspondingly, the asymmetrical shape of the O 1s peak put
the asymmetrical shape of the Oshape 1s peak put Oforward
formation of titanium (TiO2). Correspondingly, the asymmetrical of the 1s peakthat put
forward
oxide was that oxidewith
formed wasmoreformed than with
one more
metal than
element.one metal
Followingelement.
the Following the of
decomposition decomposition
the O 1s peak of inof
forward that oxide was formed with more than one metal element. Following the decomposition
the
Figure O 1s 8b peak in Figure
revealed that 8b revealed
both TiO and that
Al both
O TiOformed.
were 2 and Al2O3 were formed. However, since Al is not
However, since Al is not detectable via XPS
the O 1s peak in Figure 8b revealed 2 that2 both
3 TiO2 and Al2O3 were formed. However, since Al is not
detectable
on the via XPSsurface,
EBM-built on the EBM-built
it is strongly surface, it is strongly
suggested that thesuggested
surfaces of thatallthe
the surfaces of all the EBM-
detectable via XPS on the EBM-built surface, it is strongly suggested that the EBM-built
surfaces ofsamples
all the EBM-are
built
mainly samples
comprised are mainly
of TiO comprised
. The of
instantaneous TiO 2. The instantaneous formation of a surficial TiO2 layer is
formation of a surficial TiO layer is supposed to be theis
built samples are mainly2 comprised of TiO2. The instantaneous formation 2 of a surficial TiO2 layer
supposed
influential to be the influential factor inducing poor wear resistance of Ti64.
supposed factor to be the inducing poorfactor
influential wear resistance
inducing poor of Ti64.
wear resistance of Ti64.
(a) mm (b) m
(a) mm0.30 (b) m
0.30
0.25 15
0.25 15
0.307 mm 0.20 17.7 m
0.307 mm 0.20 17.7 m
10
0.15 10
0.15
0.10
0.10 5
5
0.05
5 mm 5 mm 0.05 5 mm 5 mm
5 mm 5 mm 0 5 mm 5 mm 0
0 0
Figure 6. Representative surface profiles of the EBM Ti64 20 mm samples of (a) as-built and (b) as-
Figure 6.6. Representative
Figure Representativesurface
surfaceprofiles
profilesof of
thethe
EBM Ti64Ti64
EBM 20 mm samples
20 mm of (a)ofas-built
samples and (b)
(a) as-built as-
and
polished.
polished.
(b) as-polished.

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55
3.0x10
3.0x10
20
20mm
55
(a)
(a) OO1s
1s mm
2.5x10
2.5x10
55
2.0x10
2.0x10

Counts
Counts
55
1.5x10
1.5x10 TiTi2p
2p
55
1.0x10
1.0x10
Name
Name Position
Position At%
At%
44 OO1s
1s 529.80
529.80 55.9
55.9 CC1s
1s
5.0x10
5.0x10 CC1s
1s 285.80
285.80 30.4
30.4
Ti
Ti2p
2p 457.80
457.80 13.5
13.5
0.0
0.0

1200
1200 1000
1000 800
800 600
600 400
400 200
200 00
Binding
Binding Energy
Energy (eV)
(eV)

44
8.0x10
8.0x10 (b) OO1s
1s Ti64
Ti64Powder
(b)
(b)
(b) Powder

44
6.0x10
6.0x10
Counts
Counts

44
4.0x10
4.0x10 TiTi2p
2p
Name
Name Position
Position At%
At% CC1s
1s
44 OO1s1s 529.80
529.80 39.8
39.8
2.0x10
2.0x10 CC1s1s 284.80
284.80 47.0
47.0
TiTi2p
2p 457.80
457.80 8.4 8.4 Al
Al2p
2p
Al
Al2p2p 73.80
73.80 4.6
4.6
0.0
0.0
1200
1200 1000
1000 800
800 600
600 400
400 200
200 00
Binding
Binding Energy
Energy (eV)
(eV)

Figure
Figure
Figure 7.
7. XPS
7. XPS XPS survey
survey
survey spectra
spectra
spectra for
for (a)
(a)
for the
(a)the 20
the20 mm
mm EBM-built
20mm EBM-built Ti64
EBM-built Ti64sample
Ti64 and
sample
sample (b)
and
and the
(b)(b) Ti64
thethe powder.
Ti64
Ti64 powder.
powder.

60000
60000 100000
100000
Ti
Ti2p
2p OO1s 1s
(a)
(a) Name
Name Position
Position At%
At%
(b)
(b) TiO
TiO22
50000
50000 Ti
Ti2p
2p3/2
3/2 459.00
459.00 72.2
72.2 Al
Al2OO3
80000
80000 2 3

Name
Name Position
Position At%
At%
Counts
Counts

40000
40000 TiO 530.33
530.33 60.7
Counts

TiO22 60.7
Counts

Al
Al2OO3 531.86 39.2
531.86 39.2
Name
Name Position
Position At%
At% 60000
60000
2 3

30000
30000 Ti
Ti2p
2p1/2
1/2 464.60
464.60 27.7
27.7

20000
20000 40000
40000

10000
10000
20000
20000
470
470 468
468 466
466 464
464 462
462 460
460 458
458 456
456 538
538 536
536 534
534 532
532 530
530 528
528 526
526
Binding
Binding Energy
Energy (eV)
(eV) Binding
Binding Energy
Energy (eV)
(eV)

FigureFigure
Figure 8.
8. XPS
8. XPS XPS spectra
spectra
spectra of
of the
of the (a)(a)
the Ti Ti
(a) 2p2p
Ti 2p peak and
peakand
peak (b)
and(b) O
(b)O 1s
1s peak
O 1s peak on
peak onthe
on thesurface
the surface
surfaceof the
of of 20
20 mm
thethe EBM-built
mmmm
20 EBM-built
EBM-built
Ti64
Ti64 sample.
sample.
Ti64 sample.

3.3.
3.3. Dry
Dry Sliding
Sliding Wear
Wear Behaviour
Behaviour
3.3. Dry Sliding Wear Behaviour
The
The representative
representative coefficient
coefficient of
of friction
friction (COF)
(COF) curves
curves are
are displayed
displayed in
in Figure
Figure 9a.
9a. Similar
Similar wear
wear
The representative
characteristics
characteristics were coefficient
wereobserved,
observed, of friction
regardless
regardless of
ofthe(COF)
the curves
different
different are displayed
microstructures
microstructures in Figure
existed
existed inside 9a.EBM-built
insidethe
the Similar wear
EBM-built
characteristics
and
and the weresamples.
the as-cast
as-cast observed,
samples. In regardless
In the
the insert of thein
insert shown
shown indifferent
Figure microstructures
Figure 9a,
9a, itit is
is noted
noted that existed
that the
the wearinside
wear the EBM-built
characteristics
characteristics of
of
and thetheas-cast
the Ti64 samples.
Ti64 sample
sample can Inclassified
can be
be the insertinto
classified shown
into four in Figure
four major
major 9a, it is noted that the wear characteristics of the
stages:
stages:
Ti64 sample can be classified into four major stages:
(I)
(I) Wearing-in
Wearing-in period,
period, where
where the
the friction
friction coefficient
coefficient increases
increases rapidly
rapidly when
when the
the ball
ball is
is in
in direct
direct
(I) contact
contact with
Wearing-in with the
the oxide
period, oxide
wherelayer
theof
layer sample
sample surface.
offriction surface.
coefficient increases rapidly when the ball is in direct
(II)
(II) Cushioning
with theof
Cushioning
contact the
the oxide
ofoxide oxide layer,
layerlayer, which
which is
of sample characterized
characterized by
issurface. by aa slight
slight decrease
decrease in
in COF,
COF, probably
probably due
due
(II) to
to surface
Cushioningsurfaceofoxide
oxide that
that prevents
the oxide prevents direct
direct metal-metal
layer, which metal-metal
is contact
contact
characterized bybetween
a slightthe
between the ball
ball and
decrease inthe
and the Ti64 sample.
Ti64probably
COF, sample. due
(III)
(III) Breakage
to surface
Breakage of
ofthe
oxide the oxide
that layer
layerinto
prevents
oxide fragments,
direct
into which
whichwas
metal-metal
fragments, indicated
contact
was between
indicated by
byaasignificant
the ball and
significant increase in
inCOF.
the Ti64
increase sample.
COF.
In
(III) BreakageIn this stage,
thisof the
the oxide
the oxide
stage, layer
oxide debris
intogenerated
debris fragments,
generated were fragmented
which
were as
as aa result
was indicated
fragmented byof
result a repeated
of repeated cycles
significant of
of stress
increase
cycles in COF.
stress
In this stage, the oxide debris generated were fragmented as a result of repeated cycles of stress
and load
Metals
Metals2016,
2016,6,
during
6,x;
x;doi:
doi:FOR
sliding.
FOR PEER
This, coupled with the complete removal of
PEERREVIEW
REVIEW
the oxide layer, allows the
www.mdpi.com/journal/metals
www.mdpi.com/journal/metals
direct metal-metal contact and, as such, causes the increase in COF.
(IV) Stabilization of COF, which occurs after ~10,000 laps.
friction coefficient [22]. A higher shear strength defines a higher ability to resist plastic shearing
during sliding and as such a higher wear resistance [22]. Therefore, it may suggest that the thinner
EBM-built
Metals 2016,sample,
6, 284 which has a higher hardness because of the fast cooling rate as compared to 8 ofthe
13
as-cast sample, exhibits high wear resistance and, as such, reduces the roughening of the surface
Metals and
during load
rubbing
2016, during
6, 284and, sliding.
thus, This, lesser
produces coupled with
wear the complete
debris. removal of the
This, consequently, oxideinlayer,
results allows
a lower 8 ofthe
specific
13
wear ratedirect
butmetal-metal
a high meancontact
COF. and, as such, causes the increase in COF.
(IV) (a)
Stabilization of COF, which occurs after ~10,000
(b) laps.

Mean coefficient of friction,

0.80
0.80 IV
Figure 9b shows the mean COF values calculated from three groups of experimental data. It is
0.75 0.75
Coefficient of friction

revealed0.70 that the thin 1 mm sample has a higher COF than the 10 mm sample, and the lowest being
the as-cast0.65 sample. The larger deviation of COF values in 0.5 mm sample is mainly attributed to the
0.70
obvious0.60 martensite protrusions within its microstructure. Moreover, we observed that the mean COF
0.55 0.650.64

of the 20 mm sample was nearly I II the same

III as the as-cast sample, while COFs of the rest of the EBM-
0.62
0.60

Coefficient of friction
0.50 0.58

built samples increased with the decrease in sample thickness. Interestingly, the thinnest EBM-built
0.56
0.600.54
0.45 0.52
0.50

sample with0.40 the highest

0.5 mm mean COF has the lowest specific wear
0.55
0.48
0.46
0.44
rate (as seen in Figure 10a). Moreover,
0.35 10 mm 0.42

the specific wear rate increased with increase in sample thickness. Figure 10b reveals the 2-D depth
As-cast
0.40
0 50 100
No. of laps
150 200

0.30
profiles of the 0 samples
10000 wear tracks
20000 30000 correspondingly.
40000 50000 The0.50
decrease
0.5mm in1mmspecific
5mm wear
10mm rate with
20mm decrease
As-cast
No. of laps
in sample thickness is mainly due to the increased hardness as a result of the finer microstructure Samples
and the presence of in the thinner EBM-built samples. In general, an increase in hardness will
Figure
Figure9.9.(a)(a)COF
COFcurves curvesofofTi64
Ti64samples
samplesas as aa function
function of number of sliding
sliding laps.
laps. (b)
(b)Mean
MeanCOFs
COFsofof
correspondingly lead to an increase in shear strength of the material, and it possibly results in a higher
EBM-built
EBM-builtand andas-cast
as-castTi64Ti64samples.
samples.
friction coefficient [22]. A higher shear strength defines a higher ability to resist plastic shearing
during sliding and as such a higher wear resistance [22]. Therefore, it may suggest that the thinner
Figure 9b shows the mean COF values calculated from three groups of experimental data. It is
EBM-built sample, which has a higher hardness because of the fast cooling rate as compared to the
revealed that the thin 1 mm sample has a higher COF than the 10 mm sample, and the lowest being
as-cast sample, exhibits high wear resistance and, as such, reduces the roughening of the surface
the as-cast sample. The larger deviation of COF values in 0.5 mm sample is mainly attributed to the
during rubbing and, thus, produces lesser wear debris. This, consequently, results in a lower specific
obvious martensite protrusions within its microstructure. Moreover, we observed that the mean COF
wear rate but a high mean COF.
of the 20 mm sample was nearly the same as the as-cast sample, while COFs of the rest of the EBM-built
samples(a) increased with the decrease in sample thickness. (b) Interestingly, the thinnest EBM-built sample
Mean coefficient of friction,

0.80
with the highest
0.80 mean COF has IV the lowest specific wear rate (as seen in Figure 10a). Moreover, the
0.75 0.75
Coefficient of friction

specific wear 0.70

rate increased with increase in sample thickness. Figure 10b reveals the 2-D depth
profiles of 0.65
the samples wear tracks correspondingly. The 0.70 decrease in specific wear rate with decrease
in sample 0.60 thickness is mainly due to the increased hardness as a result of the finer microstructure
0.55 0.65
of 0 in theI thinner
0.64

and the presence II III

EBM-built samples. In general, an increase in hardness will
0.62
0.60
Coefficient of friction

0.50 0.58
0.56

correspondingly0.45 lead to an increase in shear strength of the0.60 material, and it possibly results in a higher
0.54

Figure 10. (a) Specific wear rates and microhardness values of EBM-built and as-cast Ti64 samples. 0.52
0.50
0.48

friction coefficient0.5[22].
0.40 mm A higher shear strength defines a higher 0.55 ability to resist plastic shearing during
0.46

(b) Surface
0.35
profiles
10 mm measured across the wear tracks of the worn Ti64 samples.
0.44
0.42

sliding and0.30 as such a higher wear resistance [22]. Therefore, it may suggest that the thinner EBM-built
As-cast
0.40
0 50 100
No. of laps
150 200

0.50
sample, which0 has 10000 a higher 20000 30000
hardness 40000
because 50000
of the fast cooling0.5mm
rate as
1mmcompared
5mm 10mm to the as-cast
20mm sample,
As-cast
No. of laps Samples
exhibits high wear resistance and, as such, reduces the roughening of the surface during rubbing
and, thus,
Figure produces lesser wear debris. This,
as consequently, resultsofinsliding
a lower specific wear rateofbut a
Metals 2016, 6, x; 9. (a)FOR
doi: COF PEERcurves
REVIEWof Ti64 samples a function of number laps. (b) Mean COFs
www.mdpi.com/journal/metals
high mean COF.
EBM-built and as-cast Ti64 samples.

Figure 10.
Figure 10. (a)
(a) Specific
Specific wear
wear rates
rates and
and microhardness
microhardness values
values of
of EBM-built
EBM-built and
and as-cast
as-cast Ti64
Ti64 samples;
samples.
(b)Surface
(b) Surfaceprofiles
profilesmeasured
measuredacross
acrossthe
thewear
weartracks
tracksofofthe
theworn
wornTi64
Ti64samples.
samples.

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Metals 2016, 6, 284 9 of 13
Metals 2016, 6, 284 9 of 13

The global wear rate (Wglobal

The ) )ofofaaTi64
global Ti64sample
samplecancanbe be depicted
depicted by
by the
the combination
combination of
of oxidative
oxidative
wear (Woxidative
oxidative ) and delamination wear (W
) and delamination wear (Wdelamination ) and is given by [16,26,27]:
) and is given by [16,26,27]:
delamination

C r2CA2 A
Ar A F F
Wglobal = WWoxidative
Wglobal W
oxidative + Wdelamination
delamination= k+ Nk N (1)
Q

vz exp Q H H (1)
vzc exp
c
f
RT
RTf
where Ar is the real area of contact, C is the material constant, A is the Arrhenius constant for oxidation,
where Ar is the real area of contact, C is the material constant, A is the Arrhenius constant for
v is the sliding speed, zc is the critical thickness of oxide film, Q is the activation energy for oxidation,
oxidation, v is the sliding speed, zc is the critical thickness of oxide film, Q is the activation energy for
R is the molar gas constant, Tf is the flash temperature, k is the wear coefficient, FN is the normal
oxidation, R is the molar gas constant, Tf is the flash temperature, k is the wear coefficient, FN is the
load, and H is the hardness. Figure 11a,b reveal the SEM images of the wear debris and the wear
normal load, and H is the hardness. Figure 11a,b reveal the SEM images of the wear debris and the
track of the 0.5 mm sample respectively. The indication of the transfer layers and oxide particles in
wear track of the 0.5 mm sample respectively. The indication of the transfer layers and oxide particles
Figure 11a and the surface cracks that are perpendicular to the sliding direction in Figure 11b give
in Figure 11a and the surface cracks that are perpendicular to the sliding direction in Figure 11b give
a valuable insight into the wear mechanism of Ti64, which is consistent with the global wear rate
a valuable insight into the wear mechanism of Ti64, which is consistent with the global wear rate
proposed by Al Molinari et al. [16]. Nevertheless, a simple calculation of the theoretical delamination
proposed by Al Molinari et al. [16]. Nevertheless, a simple calculation of the theoretical delamination
wear rate using the samples respective average hardness value obtained from the earlier Vickers
wear rate using the samples respective average hardness value obtained from the earlier Vickers
hardness measurement as shown in Table 1, even without consideration of oxidative wear, revealed
hardness measurement as shown in Table 1, even without consideration of oxidative wear, revealed
a higher wear rate as compared to the experimental obtained global wear rate value by two factors.
a higher wear rate as compared to the experimental obtained global wear rate value by two factors.
This may be owning to the formation of a tribo-layer that avoids the direct metal-metal contact between
This may be owning to the formation of a tribo-layer that avoids the direct metal-metal contact
the asperities of the steel ball and the asperities of the Ti64 sample, thereby preventing further wear
between the asperities of the steel ball and the asperities of the Ti64 sample, thereby preventing
through sliding.
further wear through sliding.

SEM micrograph
Figure 11. (a) SEM
Figure micrograph ofof the transfer
transfer layers
layers generated
generated byby sliding
sliding on
on the
the 0.5 mm EBM-built
sample; (b) SEM
sample. SEM micrograph
micrographofofthe
thewear
wear track
trackonon
thethe
0.50.5
mmmm EBM-built
EBM-builtsample afterafter
sample wearwear
test; test.
(c) EDX
(c)
spectrum and inserted XRD patterns of the transfer layers and (d) EDX spectrum and
EDX spectrum and inserted XRD patterns of the transfer layers and (d) EDX spectrum and inserted inserted XRD
patterns
XRD of theof
patterns oxide particles
the oxide that were
particles thatgenerated duringduring
were generated slidingsliding
on the 0.5
on mm EBM-built
the 0.5 sample.
mm EBM-built
The detection
sample. locationslocations
The detection of (c) and
of(d)
(c) were
and (d)indicated in (a). in (a).
were indicated

Metals 2016, 6, x; doi: FOR PEER REVIEW www.mdpi.com/journal/metals

Metals 2016, 6, 284 10 of 13

Table 1. Comparison between the calculated theoretical delamination wear rate (W d ) and the actual
global wear rate (W G(exp) ).

Samples W d (1012 m3 /m) W G(exp) (1012 m3 /m)

0.5 mm 198.3 1.1
1 mm 195.6 1.2
5 mm 200.9 1.3
10 mm 195.3 1.3
20 mm 194.4 1.3
As-cast 208.7 1.4

The tribo-layer is commonly formed on a metal surface when rubbed by a counterface during
a sliding wear test [28]. In order to further explore the wear characteristics and mechanisms of the
EBM-built and as-cast Ti64, it is first necessary to delineate the terms of the non-oxide tribo-layer and
tribo-oxide layer. In the case of non-oxide tribo-layer, it merely refers to the oxides that could not be
identified by XRD and are not completely absent of an oxide on the Ti64 sample surface. On the other
hand, the tribo-oxide layer refers to the formation of a strong and compact oxide layer during sliding
process that serves as a protection to the worn surface [2830]. Inherently, in an EBM process where
the built condition is under high vacuum environment, the thickness of surface oxide layer only ranges
from 5 to 7 nm [31]. Moreover, all the wear tests were conducted at room temperature. As a result, the
formed oxide layer was weak and incompact, thus allowing the ease of delamination of the oxide layer.
In our experiment, white fragmented particles were observed from both the SEM images of the 0.5 mm
sample in Figure 11a, where the white particles indicate the breakdown of the oxide layer into oxide
particles. This observation can be reinforced from the EDX spectra in Figure 11c,d. Moreover, due to
the harsh nature during sliding, the wear debris formed was black and powdery in nature. Subsequent
XRD analysis of the wear debris suggests that the oxide particles were mainly amorphous in nature.
On the contrary, EDX was unable to detect the presence of oxygen on the transfer layer (see Figure 11c)
that was removed from the bulk sample lying beneath the oxide surface.
Making reference to all the results obtained in the analysis, a wear mechanism was proposed
and exemplified in Figure 12. Because of the reactive nature of titanium, TiO2 was subsequently
formed as an oxide layer on the sample surface, which has been proven by the XPS results in Figure 8.
During dry sliding, the TiO2 layer which serves as a protection layer of the substrate surface was
first removed, thus generating flakes of oxide debris. Consequently, under loading and repeated
rubbing, coupled with the brittle nature of the oxide debris, some of these debris were further broken
up into fragmented oxide particles. Further sliding results in the compete removal of the oxide layer,
thereby allowing the direct metal-metal contact between the asperities of the counter ball and the
sample surface. Accordingly, bulk metal material was removed, which formed the metal debris. As the
removal of the bulk metal from the substrate surface is continuous and instantaneous, oxide may not
be able to form readily on the metal debris surface and as such allowing these metal debris layers
to adhere (transfer layer) together. However, as the sliding process in the experiment was relatively
slow to the ones reported in the literature, the centrifugal force induced during sliding was not able
to remove the oxide debris, particles, and transfer layer from the sample surface. Therefore, these
remaining materials allow for the formation of a compact tribo-layer that subsequently prevents further
removal of the metal material from the substrate surface.
In our present experiment of low speed sliding (2 cm/s), the non-oxide tribo-layer was formed
as a result of both oxide particles and metal debris. Additionally, our current experiment results also
reveal that the global wear rate is two orders lower compared to that from the theoretical calculation.
This could be owing to the fact that the theoretical equation may not take into account the actual
physical condition during sliding. With reference to the proposed wear mechanism illustrated in
Figure 12, at a very low speed of 2 cm/s, it was observed that the oxide particles and metal debris still
remain on the wear track surface. Hence, this tribo-layer was not pushed away through centrifugation
Metals 2016, 6, 284 11 of 13

Metals 2016, 6, 284 11 of 13

movement during the sliding process and thus acted as a protection layer between the counter ball
counter
and Ti64ball and Ti64
sample, sample,
thereby therebydirect
preventing preventing direct contact,
metal-metal metal-metal contact,
leading leading
to a lower to arate.
wear lower wear
rate.

Figure 12. Schematic road-map on the formation of tribo-layer during sliding

sliding wear
wear of
of Ti64
Ti64 samples.
samples.

4. Summary
4. Summary
Due totothe
Due thefast
fast cooling
cooling raterate
thatthat
was was inherently
inherently involvedinvolved in a EBM
in a typical typical EBM it
process, process, it was
was observed
observed
that that the
the thinner thinner Ti64
EBM-built EBM-built
samples Ti64
(0.5samples
mm and(0.5 1 mm mm and had
thick) 1 mm much thick)
finerhad much finer
microstructure
microstructure and higher microhardness as compared to the as-cast
and higher microhardness as compared to the as-cast form. However, they showed similar form. However, they showed
wear
similar wear characteristics, regardless of the different microstructures within the
characteristics, regardless of the different microstructures within the EBM-built and the as-cast samples. EBM-built and the
as-cast
The samples.
higher hardness The higher
of the hardness
EBM-built of the
samples EBM-built
resulted in theirsamples resulted
higher wear in their
resistance andhigher wear
intrinsically
resistance and intrinsically lower wear rate. It is worth noting that all of the
lower wear rate. It is worth noting that all of the wear rates obtained in our experiment were lower wear rates obtained in
our experiment were lower as compared to the theoretical estimation. It could
as compared to the theoretical estimation. It could be due to the mild wear conditions (e.g., a very be due to the mild
wearsliding
low conditions
speed(e.g.,
of 2 acm/s)
very low
and sliding speed of
the formation of 2the
cm/s) and thethat
tribo-layer formation
remained of the
on tribo-layer that
the wear track,
remained on the wear track, acting as a protection barrier between the counter
acting as a protection barrier between the counter ball and the Ti64 substrate. We can conclude that the ball and the Ti64
substrate.
EBM Weis
process can conclude
capable that the EBM process
of manufacturing is capable
Ti64 parts of manufacturing
with superior Ti64 parts
wear properties with superior
compared to the
wear properties compared
as-cast counterparts. to the as-cast counterparts.

Acknowledgements:The
Acknowledgments: Theauthors
authorsare
aregrateful
gratefulfor
forfinancial
financial support
support provided
provided by
by A*Star
A*Star Industrial
Industrial Additive
Additive
Manufacturing
Manufacturing Program: Work Package 3. We We acknowledge the use of resources in Singapore Centre for 3D 3D
Printing
Printing (SC3DP)
(SC3DP) funded
funded by
by the
the National
National Research
Research Foundation
Foundation(NRF),
(NRF),Singapore.
Singapore.
Author Contributions: W.Q.T. examined the specimens and wrote the main paper. X.T. designed the experiments
Author Contributions: W.Q.T. examined the specimens and wrote the main paper. X.T. designed the
and fabricated the Ti64 samples using EBM. W.Q.T., X.T., P.W. and M.L.S.N. performed specimen preparation and
experiments and E.L.
characterization. fabricated the Ti64
and S.B.T. samples
supervised theusing EBM.
project. AllW.Q.T.,
authorsX.T., P.W. and
discussed M.L.S.N.
the results performed
and specimen
finalized the paper.
preparation and characterization. E.L. and S.B.T. supervised the project. All authors discussed the results and
Conflicts of Interest: The authors declare no conflict of interest.
finalized the paper.

Conflicts of Interest: The authors declare no conflict of interest.

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