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Acta Biomaterialia 5 (2009) 18311837

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Fabrication of compositionally and structurally graded

TiTiO2 structures using laser engineered net shaping (LENS)
Vamsi Krishna Balla, Paul Duteil DeVasConCellos, Weichang Xue,
Susmita Bose, Amit Bandyopadhyay *
W. M. Keck Biomedical Materials Research Laboratory, School of Mechanical and Materials Engineering, Washington State University,
Pullman, WA 99164-2920, USA
Received 27 August 2008; received in revised form 3 December 2008; accepted 6 January 2009
Available online 22 January 2009

Abstract
Novel structures with functional gradation in composition and structure were successfully made in TiTiO2 combination using laser
engineered net shaping. The addition of fully dense, compositionally graded TiO2 ceramic on porous Ti signicantly increased the surface
wettability and hardness. The graded structures with varying concentrations of TiO2 on the top surface were found to be non-toxic and
biocompatible. In addition, the higher wettability of surfaces with TiO2 can enhance their ability to form chemisorbed lubricating lms,
which can potentially lower the friction coecient against ultrahigh molecular weight polyethylene liner, thus reducing its wear rate.
These unitized structures with open porosity on one side and hard, low friction surface on the other side can eliminate the need for multiple parts with dierent compositions for load-bearing implants such as total hip prostheses.
2009 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Keywords: Functionally graded materials; Laser processing; Laser engineered net shaping (LENS); Biocompatibility; Osteoblast

1. Introduction
The high wear rate of ultrahigh molecular weight polyethylene (UHMWPE) liner used in traditional hip replacements is a cause of serious concern due to osteolysis.
Osteolysis and aseptic loosening has been identied as
major factors limiting the life of hip prostheses, with indications that ne UHMWPE wear debris [1,2], generated
primarily at the interface between the femoral head and
the acetabular cup, promotes this degradation. Thus,
wear-particle-induced bone loss is one of the main limiting
factors aecting the long-term stability of UHMWPE linerbased total hip replacements and other load-bearing
implants [3,4]. Several attempts have been made to minimize the wear-induced osteolysis including the use of
design modications [5], UHMWPE property modication

Corresponding author.
E-mail address: amitband@wsu.edu (A. Bandyopadhyay).

[6] and alternative bearing couples, such as metal-on-metal

and ceramic-on-ceramic, eliminating the use of PE [7,8].
Design modications can only change the contact stresses
and related fatigue wear of the UHMWPE; modication
of UHMWPE properties did not yield signicant improvement in wear performance [9]. In addition, roughening and
scratches on hard counterface of the femoral components
can increase UHMWPE wear via adhesive and abrasive
wear mechanisms [10,11]. An alternative and more eective
solution is to modify the hard counter surface articulating
with UHMWPE to reduce its wear and debris generation.
Therefore, a hard counter surface providing low friction
with UHMWPE and resisting roughening can reduce abrasive and adhesive wear, and thereby enhances the longterm stability and survival of load-bearing metal implants.
Hard ceramic surfaces appear to accomplish this long-term
performance goal most eectively [12] because of their
higher wettability than metals/alloys. Among the ceramics
TiO2, Al2O3 and ZrO2 have highly ionic character, therefore have higher wettability [13] than the passive oxide

1742-7061/$ - see front matter 2009 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.actbio.2009.01.011

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V.K. Balla et al. / Acta Biomaterialia 5 (2009) 18311837

lms on stainless steels or CoCrMo alloys used for biomedical applications. Also, these passive oxide lms on metals/
alloys can break o from the substrate during articulation
and do not provide sucient wear resistance or low friction
against UHMWPE. It has been reported that lubricating
compounds, such as water, readily chemisorbs to ceramics
surface than to metals and these lms can eectively reduce
the friction coecient and hence the wear of UHMWPE
due to their lubrication characteristics [1315]. Also, such
adsorption activities were found to increase with ionic
character of ceramics [13]. Therefore, a ceramic coating
on biocompatible metals such as Ti can provide a favorable
articulation surface with low friction coecient and high
wear resistance against UHMWPE to reduce its wear rate.
Recently there is a growing interest in the fabrication of
novel structures to mimic multiple tissues and tissue interfaces on the same implant, such as implants with gradients
in porosity and pore sizes that will allow on one side of the
implant high vascularization and direct osteogenesis, while
promoting osteochondral ossication on the other. In the
current context, innovative designs such as functionally
graded acetabular shells with open porosity on one side
(in contact with the bone) to improve cellmaterial interactions and a hard ceramic coating on the other side (in contact with UHMWPE liner) to reduce liner wear, can
signicantly improve the implants in vivo life. While creating a hard/low friction ceramic surface on metal substrates
seems plausible, there is a possibility of delamination or
cracking due to the mismatch in elastic moduli, coecient
of thermal expansion and hardness between the ceramic
coating and the metal substrate. Although functionally
graded coatings (FGCs) can overcome such diculties, it
is dicult, if not impossible, to fabricate net shape
implants/structures with spatial gradation in composition
and structure (porosity) with conventional processing
routes. Therefore, in this work we have used laser engineered net shaping (LENSTM)a solid freeform fabrication
techniqueto fabricate compositionally and structurally
graded TiTiO2 structures with sound interface between
the two materials and high surface hardness. Such gradient
structures provide useful mechanical support for the wearresistant, low friction exterior layers and minimize the likelihood of localized Hertzian failure during implant service.
This paper focuses on processing, coating characterization
and in vitro biocompatibility of these LENSTM-processed
functionally/structurally graded structures.
2. Materials and methods
2.1. Fabrication and characterization
Commercially pure titanium powder (Advanced Specialty Metals, Inc., NH) with particle size between 50 and
150 lm and 99% pure TiO2 powder (CERAC Inc., Milwaukee, WI) with particle size between 45 and 106 lm
was used in this study. Gradient samples with 10 mm diameter were fabricated on a substrate of 3 mm thick rolled,

commercially pure Ti plates using LENSTM-750 (Optomec

Inc., Albuquerque, NM) equipped with a 500 W Nd
YAG laser and double powder feeder system. The rst
hopper was lled with Ti powder and the second hopper
with TiO2 powder. Gradient structures with 50%, 90%
and 100% TiO2 on the top surface were made at 300 W
laser power and 22.5 mm s 1 scan speed. These compositionally graded structures consisted of 100% Ti in the rst
10 layers. The composition in the transition region of the
gradient structure was varied from 100% Ti at the rst
layer to various concentrations of TiO2 at the top layer
over 510 layers. The rst 10 layers of Ti were made at
200 W to create 30 vol % porosity, which can achieve stable long-term xation due to bone cell in-growth through
interconnected porosity [16]. The transition layers were
made at 300 W to achieve fully dense transition/top layers.
In the transition zone, the powder feed rate for TiO2
increased from 0 to 23.7 g min 1 over the number of transition layers. For Ti it was 17.5 g min 1 to start with and
reduced to zero over the same number of layers. These
compositionally graded structures with gradient porosity
having open porosity on one side of the structure can
improve cellmaterial interactions [16,17] and hard, lowfriction coating on the other side can decreases the wear
of UHMWPE liner. All samples were fabricated in a glove
box containing argon atmosphere with O2 content less than
10 ppm to limit oxidation of alloys during processing.
Cross-sectional microstructures of the samples were
examined using both optical and scanning electron microscopy (SEM). Constituent phases in the as-received TiO2
powder and in the top surface of graded coatings were identied using a Siemens D 500 Kristalloex diractometer with
Cu Ka radiation. In order to track the compositional gradient across the deposit, a series of microhardness indentations
were placed from one end of the deposit to the other end with
neighboring indents being separated by 0.2 mm using Vickers microhardness tester (Leco, M-400G3) at 300 g load
applied for 20 s. Top surface hardness was also measured,
and an average of 10 measurements on each sample is
reported.
2.2. Simulated body uid (SBF) study
Bioactivity of compositionally/structurally graded
TiTiO2 structures was evaluated by immersing in SBF
with similar ionic composition as that of human blood
plasma, and compared with that of laser-processed pure
Ti control sample. The SBF solution is prepared by dissolving NaCl, KCl, NaHCO3, MgCl2
6H2O, CaCl2
2H2O,
Na2SO4
10H2O and K2HPO4 into distilled water and buffered at pH 7.35 with tris-hydroxymethyl aminomethane
(TRIS) and 1 (N) HCl at 37 C [18]. The ion concentrations
(mmol L 1) in SBF thus prepared was Na+: 142.0, K+: 5.0,
Ca2+: 2.5, Mg2+: 1.5, HCO3 : 4.2, Cl : 148.5, HPO42 : 1.0
and SO42 : 0.5. Samples were immersed in a glass vial containing 10 ml of SBF solutions and were kept under static
conditions inside a incubator at 37 C for 7 and 14 days.

V.K. Balla et al. / Acta Biomaterialia 5 (2009) 18311837

The SBF solution was changed every 23 days for the duration of the experiment. All experiments were performed in
duplicate, by running two independent glass vials simultaneously. After exposure, samples were washed with distilled water and then dried at 150 C for 24 h. Surface
feature of samples after SBF immersion were studied using
a SEM. SBF-immersed samples were also analyzed by Fourier transform infrared (FTIR) spectroscopy (Nicolet 6700,
Thermo Fischer Scientic) to identify functional groups of
apatite precipitations on the surface.
2.3. Contact angle measurement
All the sample surfaces for contact angle measurements
were ground using series of SiC grinding papers with various sizes up to 1200 grit. Samples were then polished on
velvet cloth using 1 lm Al2O3 suspended in distilled
water. Finally, just before testing, all the samples were
ultrasonically cleaned in alcohol bath. This procedure
ensured identical surface roughness and topography on
all sample surfaces. Contact angles were measured using
the sessile drop method with a face contact angle set-up
equipped with a microscope and a camera. A 0.51.0 ll
droplet of distilled water was suspended from the tip of
the microliter syringe. The sample surface was advanced
toward the syringe tip until the droplets made contact
with the sample surface. Images were collected with the
camera and the contact angle between the drop and the
substrate was measured from the magnied image. All
the measurements were carried out at 21 C with a relative humidity of 21%.
2.4. Cell culture and morphology of osteoblastic precursor
cell line 1 (OPC1)
All samples for cell culture test were sterilized by autoclaving at 121 C for 20 min. In this study, the cells used
were an immortalized, cloned OPC1, which was derived
from human fetal bone tissue [19]. OPC1 cells were seeded
onto the samples placed in 24-well plates. Initial cell density
was 5.0  104 cells/well. One milliliters of McCoys 5A
medium (enriched with 5% fetal bovine serum, 5% bovine
calf serum and supplemented with 4 lg ml 1 of fungizone)
was added to each well. Cultures were maintained at 37 C
under an atmosphere of 5% CO2. Medium was changed
every 23 days for the duration of the experiment. Samples
for testing were removed from culture at 4, 7 and 11 days
of incubation.
All samples for SEM observation were xed with 2%
paraformaldehyde/2% glutaraldehyde in 0.1 M cacodylate
buer overnight at 4 C. Post-xation was performed with
2% osmium tetroxide (OsO4) for 2 h at room temperature.
The xed samples were then dehydrated in an ethanol series (30%, 50%, 70%, 95% and 100% three times), followed
by a hexamethyldisilane (HMDS) drying procedure. After
gold coating, the samples were observed under SEM for
cell morphologies.

1833

3. Results and discussion

3.1. Microstructures and phase analysis
A representative cross-sectional microstructure of
graded TiTiO2 structure is shown in Fig. 1. The TiTiO2
graded structures exhibited good bonding between individual layers without gross porosity, cracks or lack of fusion
defects. This indicates that laser parameters used in the
present work are sucient to ensure complete melting
and uniform mixing of TiO2 and Ti powders. However,
severe cracking was observed in the structures with 100%
TiO2 on the top surface and the cracking was reduced with
decreasing TiO2 concentration. Therefore, further characterization and testing was not performed on the samples
with 100% TiO2 on the top surface. Using optimized
LENSTM processing parameters crack-free structures containing up to 90% TiO2 on the top surface were successfully
fabricated with excellent reproducibility. Interface between
porous Ti and graded TiO2 top surface, shown in Fig. 2,
also indicate complete melting of Ti and TiO2, ensuring
sound interface without cracks or porosity. Also, no
unmelted or partially melted powders were observed
throughout the structures cross-section. This indicates
small temperature uctuations in the liquid metal pool
due to changes in the composition across the sample
cross-section. Large temperature uctuations can result in
non-uniform or inadequate intermixing of powders in the
transition region of such graded structures [17]. In the present work, the small temperature uctuations could be due
to small dierence between melting points of Ti (1668 C)
and TiO2 (1800 C), and their laser absorption coecients.
Top surface microstructural variation as a function of
TiO2 concentration of graded structures is shown in
Fig. 3. The top surface microstructures did not show clear
contrast between Ti and TiO2 phases. However, it can be
seen from Fig. 3a and b that the amount of Ti phase (phase
with clear grain boundaries and grains with b needles)
decreased with increasing TiO2 concentration. Lightly
etched, ne TiO2 grains in the range of 68 lm (measured
using linear intercept method) can be seen from Fig. 3b.
Overall scale of the solidication structure in these graded
coatings is very ne, reecting the extremely high cooling
rates, in the range of 103105 K s 1, associated with
LENSTM process. This is a signicant advantage of LENSTM,
as the slow cooling rates associated with other processing
techniques often result in coarse-grained structures and
results in poor wear resistance. The Ti phase in Fig. 3a is
found to contain some high temperature b phase (needles).
The retention of b phase at room temperature is attributed
to the high cooling rates associated with laser processing.
However, the amount of b phase observed in the present
samples was considerably lower than observed in our earlier study [20] on LENSTM-processed porous Ti, where a
considerable amount of b phase is retained at room temperature. The lower amount of b phase in the present samples is presumably due to stabilization of a phase by the

1834

V.K. Balla et al. / Acta Biomaterialia 5 (2009) 18311837

Fig. 1. Typical cross-sectional microstructures of laser-processed, compositionally graded TiO2 coating on porous on Ti.

Fig. 2. Microstructure showing the interface between porous Ti and

graded TiO2 coating.

oxygen present in top surface with varying concentrations

of TiO2. In addition, the ratio of b phase peak intensity
to the a phase peak intensity found to decrease from
0.252 in the as-received powder to 0.102 in the graded
structure with 50% TiO2 on top surface. This indicates that
the amount of b phase present in the as-received powder
was reduced due to laser processing. The presence of b
phase in the top surface of these samples was also conrmed by XRD study. Fig. 4 presents the XRD results of
as-received powders and laser-processed gradient structures. All the peaks from top surface of gradient structures
correspond to as-received powders of Ti (JCPDS le No.
011197) or TiO2 (JCPDS le No. 881172).
In order to systematically track the compositional gradient across the deposit, a series of microhardness indent
markers were placed from one end of the transition region
to the other end. The hardness gradually increased with the
increase in TiO2 concentration as shown in Fig. 5. Gradual
increase in the hardness from Ti towards the top TiO2 coating validates the potential of LENSTM process in creating
unique microstructural gradients across the compositionally graded surfaces/coatings, which are dicult to process
using traditional manufacturing routes. The hardness of
the top surface increased from 1102 140 Hv to 1122
116 Hv when the TiO2 concentration at the top surface
was increased from 50% to 90% in the coating. This indicates that the concentration of TiO2 above 50% had little

Fig. 3. Top surface microstructures of graded TiO2 coatings with varying

TiO2 concentration on top surface: (a) 50% TiO2, (b) 90% TiO2.

inuence on the top surface hardness. These top surface

hardness values are signicantly higher than the average
hardness of the laser-deposited Ti, which was 192
14 Hv. Gradient coatings with only 50% TiO2 in top surface showed 474% increase in the surface hardness. The
ner grain size, uniform microstructure and high hardness
of this laser-processed gradient coating can potentially provide excellent wear resistance. Moreover, the porosity on
the Ti side, which will be in contact with bone, can improve
cellmaterial interactions [16]. It is anticipated that hard
TiO2 ceramic coating on the other side can decrease the
wear of UHMWPE due to its higher wettability and chemisorbed lubricating lms [1315]. Therefore, these composi-

TiO2(112)

Ti(112)

TiO2(301)

1835

TiO2(301)

TiO2(220)

TiO2(211)

Ti(102)

Ti(110)/TiO2 (002)

Ti(101)

TiO2(002)
TiO2(310)

TiO2(210

Ti-(110)

TiO2(101)

TiO2(110)

TiO2(200
TiO2(111

Ti(100)

Intensity (a.u)

TiO2(201)

TiO2(101)

Ti(100)

V.K. Balla et al. / Acta Biomaterialia 5 (2009) 18311837

20

30

40

50
Two Theta

60

70

80

Fig. 4. XRD pattern of TiO2 powders and top surface of graded TiO2 coatings: (a) TiO2 powder; (b) coating with 90% TiO2 on top surface; (c) coating
with 50% TiO2 on top surface; (d) Ti powder.

1300
50% TiO2 Top (Surface Hardness 1102140 HV)
90% TiO2 Top (Surface Hardness 1121116HV)

Vicker's Hardness, HV

1100

900

700

500

300
increasing TiO2 concentration

Titanium

100

-4

-3.6

-3.2

-2.8

-2.4

-2
-1.6
-1.2
Distance, mm

-0.8

-0.4

0.4

0.8

Fig. 5. Hardness variation across the graded TiO2 coatings.

tionally/structurally graded TiTiO2 structures could provide a favorable articulation surface with low friction coefcient and high wear resistance against UHMWPE
reducing its wear rate.
3.2. SBF study
For comparison of bioactivity in terms of apatite-forming ability, laser-processed graded structures and Ti samples were immersed in SBF for 7 and 14 days. Fig. 6
shows surface micrographs of these samples after 14 days
of immersion in SBF. It can be seen from Fig. 6a that
laser-processed pure Ti control sample surface has low apatite-forming ability than graded surfaces with various concentrations of TiO2 on top. Also, signicant amount of
apatite precipitation was noticed after 7 days on these compositionally graded surfaces. The FTIR results of these pre-

cipitates, shown in Fig. 7, indicate the presence of HPO42 ,

PO43 , OH and CO32 groups. The enhanced apatiteforming ability of TiO2 containing surface can be explained
on the basis of several reported models for apatite deposition on the TiO2 surface [21,22]. The TiOH groups formed
on the TiO2 lm, upon immersion in aqueous solutions, act
as preferential nucleation sites for apatite crystals and
favor deposition/precipitation on the surface. Therefore,
the TiO2 in the graded structures surface enhances apatite
formation.
3.3. Contact angle
While TiO2 in the surface of graded structures greatly
improved the apatite precipitation, it can also signicantly
alter surface properties like wettability and surface energy,
which has strong inuence not only on cellmaterial inter-

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V.K. Balla et al. / Acta Biomaterialia 5 (2009) 18311837

Fig. 6. Apatite precipitates after 14 days of immersion in SBF: (a) Ti control; (b) 50% TiO2 on top; (c) 90% TiO2 on top surface.

90% TiO 2 on top

-1

-1

669 cm
495 cm -1

1066 cm

1652 cm -1
1558 cm -1

Transmittance (a.u.)

50% TiO 2 on top

-- OH CO 3 2 -- PO 4 33500

3000

2500

2000

1500

1000

500

Wavenumbers (cm-1)
Fig. 7. FTIR spectra of graded TiO2 surfaces after immersion into SBF
for 14 days.

actions but also on the ability to form chemisorbed lubricating lms. The contact angle between water and the Ti
surface decreased from 62 3 to 41 4 due to TiO2 in
the surface of graded structures indicating that the Ti surface is more hydrophilic in nature. Lower contact angle
also suggests higher surface energy of graded surfaces with
varying TiO2 concentrations. The higher hydrophilicity
and surface energy of these surfaces improved the apatite-forming ability in SBF. Besides, the higher wettability
of surfaces with TiO2 can enhance their ability to form
chemisorbed lubricating lms thus lowering friction coecient against UHMWPE. Similar observations on the
increase of wettability and surface energy due to surface
oxide layers have already been reported [23,24].
3.4. Cellmaterial interactions
Cellmaterial testing is focused on cytotoxicity analysis
of these LENS-processed structures to conrm that LENS

processing does not have any toxic inuence to these structures. The higher wettability of TiO2 containing surfaces
found to inuence the OPC1 cell attachment. Fig. 8 shows
the morphology of OPC1 cells on graded TiTiO2 structure
surfaces after 7 days of culture. Flattened cells with little lopodia extensions were observed on laser-processed pure
Ti samples. In contrast, the cells had numerous lopodia
extensions on TiO2 containing surfaces. Identical cell morphology was observed on the surface with varying concentrations of TiO2 on the top surface, which spread and grew
well on these sample surfaces. Enhanced osteoblast cell
attachment and spreading on TiO2 containing surfaces is
attributed to the higher bioactivity and wettability of these
surfaces compared to that of pure Ti surfaces. These
in vitro results conrm that these compositionally and
structurally graded samples are non-toxic and biocompatible even after LENS processing.
Graded structures fabricated in this work have the
potential to replace conventional multi-piece hip implants
by introducing monoblock structures. With these structures, acetabular shells can be designed with porosity in
one side for bone tissue in-growth and the hard ceramic
coating on the other side to reduce liner wear. This conguration can reduce the standard two-piece acetabular cup
into a one-piece design. With further modication, the
UHMWPE liner part can also be removed, making it a
direct ceramic-on-ceramic implant. Such monoblock
designs reduce the possibilities of osteolysis from polymeric
debris and also make the surgical procedure easier.
4. Conclusions
Novel, unitized structures with porous Ti on one side
and compositionally graded, hard TiO2 surface on the
other side have been fabricated using LENSTM process.
Gradient structures with 50% TiO2 in top surface showed
a hardness of 1102 140 Hv, which is approximately four
times higher than the hardness of laser-processed Ti. Moreover, these gradient coatings decreased the contact angle by
34% indicating their enhanced wettability, cellmaterial
interactions and lubrication ability. Our results indicate

V.K. Balla et al. / Acta Biomaterialia 5 (2009) 18311837

1837

Fig. 8. SEM micrographs of OPC1 cells after 7 days of culture: (a) Ti control; (b) 50% TiO2 on top; (c) 90% TiO2 on top surface.

that compositionally/structurally graded TiTiO2 structures with 50% TiO2 on top can provide a favorable articulation surface with low friction coecient against
UHMWPE reducing its wear rate.
Acknowledgments
The authors would like to acknowledge the nancial
support from the W. M. Keck Foundation to establish a
Biomedical Materials Research Lab at WSU; also the Ofce of Naval Research for nancial support under Grant
No. N00014-1-05-0583. Authors would also like to
acknowledge the nancial support from the National Science Foundation under the grant number CMMI 0728348.
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