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To cite this article: Dheepa Srinivasan , Anubhav Singh , Anigani Sudarshan Reddy & Kaushik
Chatterjee (2020): Microstructural study and mechanical characterisation of heat-treated
direct metal laser sintered Ti6Al4V for biomedical applications, Materials Technology, DOI:
10.1080/10667857.2020.1830566
Article views: 21
a
INTECH DMLS, Pvt. Ltd., Peenya Industrial Area, Bangalore, India; bPratt and Whitney R &D centre, Bangalore, India; cDepartment of
Materials Engineering, Indian Institute of Science, C.V. Raman Avenue, Bangalore, India
CONTACT Kaushik Chatterjee kchatterjee@iisc.ac.in Department of Materials Engineering, Indian Institute of Science, C.V. Raman Avenue,
Bangalore, India 560012
*Current address: Pratt and Whitney R &D centre, Bangalore, India
© 2020 Informa UK Limited, trading as Taylor & Francis Group
2 D. SRINIVASAN ET AL.
Powder characterisation
Heat treatment
Pre-alloyed Ti6Al4V powder sourced from EOS,
GmbH of a nominal composition 90.0% Ti, 5.5% Both the coupons and the implant were subjected
Al, 4.08% V, 0.05% Fe, 0.13% O, 00.07% H and to heat treatments in air (ambient pressure using
0.01% N (all wt%) and mean size of ~ 38 μm (d a Nabertherm box furnace) or in vacuum (10−5
(10):25, d(50):38 and d(90):59), was used to prepare mbar pressure, using a Delta power controls tube
test samples and a cranial implant. The morphol furnace) at 800°C, 4 h. The furnace heating rate
ogy and chemical composition of the as-received was 5°C/min in air and 10°C/min in vacuum, with
powder were characterised by scanning electron furnace cooling at a rate between 5 and 10°C/min.
microscopy (SEM, Zeiss Ultra55, field emission In order to understand the evolution of the β-phase
SEM with an Oxford Link system for the energy and establish the stability of the DMLS Ti6Al4V
dispersive spectroscopy (EDS). implant, the coupon and implant were both
Figure 1. Photograph of as-printed (a) test coupons and (b) model implant.
MATERIALS TECHNOLOGY 3
subjected to a heat treatment at 1100°C, in air and The samples were tested in the as-printed condition
in vacuum, using the same conditions as used for and after heat treatment at 800°C in air and in
the 800°C heat treatment. The samples were ana vacuum. The sample orientation was such that the
lysed for their surface and bulk microstructures tensile axis was placed along the longitudinal build
after heat treatment. direction. Room temperature tensile tests were carried
out using a Zwick Roell instrument at a crosshead
speed of 0.006 mm/sec.
Microstructural characterisation
The model cranial implant was further subjected to an
anodising surface treatment after hand polishing the Results and discussion
surface. Porosity in the coupons and implant were Powder characteristics
quantified using a Zeiss Axiocam optical microscope
with a Clemex image analysis system. The samples The starting Ti6Al4V powders showed a unimodal
were polished following standard metallographic tech distribution of spherical particles, as shown in Figure
niques and electrolytically etched using Kroll’s reagent 2(a,b). The powder composition conformed to the
(92 ml distilled water, 6 ml HNO3, 2 ml HF). The nominal Ti6Al4V composition, as shown in the repre
microstructural analysis of the samples was done on sentative EDAX spectrum (inset in Figure 2(c)).
an inverted optical microscope (CarlZeiss MAT 200 Elemental distributions taken from the EDS spectra
Motorised Axio Vision 4.7.2 Version) using ImageJ show a uniform distribution of Al and V in the Ti
software. SEM along with EDS was carried out on the powders (Figure 2(d–f)).
implant and the coupons, before and after heat treat
ment. Phase identification was carried with X-ray dif
fraction (XRD, Panalytical X’Pert Pro, operated at 40 Microstructure of as-printed and heat-treated
kV, 30 mA, Cu-Kα (1.54 Å). A normal θ-2θ scan with coupons
step size of 0.033° and a scan speed of 0.014°/s was The as-built coupon and implant measured a surface
used for the samples before and after heat treatment. roughness of 5 to 6 μm Ra, which reduced to half the
Electron back-scattered diffraction (EBSD) was per value after grit blasting (2 to 3 μm Ra). The surface
formed using FEI Helios G4 Dual Beam operated at roughness was marginally higher (by 10%) in the long
25 kV. itudinal direction as compared to the transverse direc
tion. The microstructures in the longitudinal and
transverse planes of the as-printed coupon built with
Hardness measurement and tensile testing
a 30 µm layer thickness are shown in Figure 3. The
Vickers microhardness measurements were made porosity in the as-printed coupon was less than 0.5%
using a Future-Tech, FM-810 hardness tester, with (> 99.5% relative density) as quantified by analysis of
200 gf load and 10 s dwell time. Micro-tensile speci the micrographs in Figure 3(a,b) and consistent with
mens of 21 mm (length), 6 mm (gauge length) and earlier work involving similarly prepared samples [31].
0.5 mm (thickness) were drawn out of the cuboid The prior β grain size varied between 100 and 300 µm
blocks, before and after heat treatment, along both and the microstructure within the grains consisted of
the longitudinal and the transverse directions [30]. metastable α′ martensite formed due to the high
Figure 2. SEM micrographs of Ti6Al4V powders showing (a–b) spherical morphology of powders at different magnifications, (c)
EDS spectra and (d–f) EDS maps of distribution of Al and V in the powder particles.
4 D. SRINIVASAN ET AL.
Figure 3. Optical micrograph of the as-printed coupon with 30 µm layer thickness in (a, c) longitudinal and (b, d) transverse planes.
Porosity and α′ microstructure are seen in (a, b) and (c, d), respectively.
cooling rates in the SLM process, as reported by sev micrographs of the longitudinal plane are presented
eral groups for Ti6Al4V prepared by DMLS [26,31– in all the figures hereafter.
33]. Note that this microstructure is markedly differ The microstructure of the as-printed coupon after
ent from that of the wrought alloy that typically con heat treatment in air at 800°C for 4 h, as shown in
sists of equiaxed grains of α [33]. A change in the layer Figure 5, revealed α′ martensitic laths transformed
thickness from 30 to 50 µm did not produce any into α + β phases. The β phase was present in between
significant change in the microstructure, with porosity the α laths and appeared with a brighter topographi
of less than 0.5% and α′ martensite, the predominant cal contrast as shown in the secondary electron
phase, in the as-printed condition. A magnified view micrographs. The two-phase α + β microstructure
of the α′ phase can be seen in representative SEM was similar at the surface and in the bulk of the
micrographs taken from the coupon along the long coupon. This result suggests that heat treatment in
itudinal plane fabricated with a 50 µm layer thickness, air at 800°C for 4 h did not significantly influence the
as illustrated in Figure 4. The microstructure along the microstructural evolution at the surface. More
surface and in the bulk regions of the as-printed cou importantly, the influence of oxygen on microstruc
pon was found to be similar. Since there were no tural evolution seems minimal for this specific heat
discernable difference in the microstructure between treatment.
the two different layer thickness used for DMLS, all the The microstructures after heat treatment in
further studies were done with the higher layer thick vacuum (800°C, 4 h) are shown in Figure 6. Here
ness of 50 μm, in order to enhance the build time and again, the α′ laths also transformed in to an α + β
thereby, productivity. Furthermore, since there was no microstructure and the microstructures resembled
observable difference in the microstructures in the each other with no significant differences between
longitudinal and transverse planes, only the the surface and the bulk. Thus, there was no
Figure 4. SEM micrographs of the as-printed coupon built with 50 µm layer thickness: (a) in the bulk, and (b) at the surface of the
as-printed coupon with 50 µm layer thickness.
MATERIALS TECHNOLOGY 5
Figure 5. SEM micrographs of, (a, b) bulk and (c, d) surface of the as-printed coupon after heat treatment at 800°C for 4 h in air, at
low and high magnifications.
Figure 6. SEM micrographs of (a, b) bulk and (c, d) surface of the as-printed coupon after heat treatment at 800°C for 4 h in
vacuum.
observable difference in the microstructures, exam microscopy are warranted for further characterisation
ined by SEM, after heat treatment in air or vacuum. of these precipitates.
In both heat treatments, at 800°C, the as-printed XRD patterns for the as-printed and 800°C heat-
microstructure appeared to exhibit similar transfor treated (air and vacuum) coupons are compiled in
mation to a two-phase microstructure, primarily com Figure 8. The α′ and α phase both form with HCP
prising α phase and a lean β phase. When examined at structure of similar lattice parameters that makes it
higher magnification, fine aligned precipitates (10 to difficult to discern the two phases by XRD. The XRD
20 nm in length) with fibre-like appearance can be patterns are similar before and after the heat treatment
seen. Figure 7 is a representative micrograph of the and confirm the predominant presence of α′ and α
coupon heat treated in vacuum at 800°C exhibiting phases. The relative intensities of the peaks also did
these fine bright features. More detailed investigations not change markedly suggesting that the crystallo
using high resolution transmission electron graphic texture did not significantly evolve due to the
6 D. SRINIVASAN ET AL.
Figure 7. SEM micrographs of the coupon heat treated in vacuum at 800°C showing the fine precipitates viewed at two different
magnification (a) 25,000 × and (b) 100,000 ×.
Figure 8. XRD patterns of the as-printed coupon and after heat treatment at 800°C in air and vacuum and 1100°C in vacuum.
heat treatment and the α phase likely inherited the The surface of the as-printed coupon was aggres
texture of the parent α′ phase. Note that negligible sively oxidised when heat treatment was done in air at
fraction of β phase is seen. Heat treatment at 800°C a higher temperature of 1100°C and tended to crum
decomposes the α′ into α + β phases during which Al ble, limiting any practical use of this heat treatment
and V are expected to partition between the α and β owing to the apparently much higher diffusivity of
phases, respectively. Figure 9 presents the EBSD oxygen at 1100°C, unlike at 800°C. Figure 7 shows an
inverse pole figure maps of the coupon after the heat XRD pattern taken from the 1100°C (vacuum) heat
treatment are in shown in Figure 9(a) (air) and Figure treatment.
9(b) (vacuum). The α phase is the predominant phase Heat treatment at 1100°C in air was considered
and there is very minimal β phase seen after heat unviable for implant applications due to oxidation and
treatment suggesting that the α phase likely inherited therefore, is not discussed hereafter. The microstructure
the texture of the parent α′ phase. after heat treatment at 1100°C for 4 h in vacuum is
MATERIALS TECHNOLOGY 7
Figure 9. EBSD inverse pole figure maps of the coupon after heat treatment at 800°C in (a) air and (b) vacuum.
Figure 10. SEM micrographs of the coupon after heat treatment at 1100°C for 4 h in vacuum (a) in the bulk and (b) at the surface
(c) composition measured by EDS at different regions of the micrographs.
shown in Figure 10. A markedly different microstruc Mechanical properties of as-printed and
ture evolved after heat treatment at 1100°C compared to heat-treated coupons
that observed at 800°C. The microstructure consists of The effect of heat treatment of the coupon on Vickers
equiaxed grains of primary α. The regions between the microhardness is plotted in Figure 11. The average
primary α grains is occupied by the β and secondary α hardness at the surface and in the bulk of the as-
phases. The secondary α has a lath shaped morphology printed coupon was comparable at 406 HV and 411
in contrast to the equiaxed morphology of the primary HV, respectively, in agreement with the similar micro
α. Figure 10(c) has a detailed elemental distribution structures noted in Figure 4. These values are similar
carried out in this microstructure, taken at high magni to those reported for this alloy prepared by DMLS in
fication. The relative volume fractions of the primary several other studies [32]. The hardness was observed
and secondary α are a function of the temperature-time to be reduced after the heat treatment at 800°C by ≈
profile of the heat treatment. 10% (± 5%) for both surface and bulk regions of the
8 D. SRINIVASAN ET AL.
Figure 11. Vickers microhardness of the as-printed and 800°C heat-treated coupons.
coupon, in both air and vacuum. Minimal difference slightly higher in the vacuum heat-treated coupon
in the values between the surface and bulk hardness is compared to air heat-treated, in agreement with the
further supported by the microstructural evidence in hardness values, this difference was marginal. In
Figure 5 suggests that oxygen diffusion was limited agreement with reported literature, heat treatment
during the heat treatment in air at 800°C for 4 h. reduced the strength and enhanced the elongation of
Oxygen is a strong solid solution strengthener in Ti the alloy [33]. However, the elongation was lower than
that makes hardness very sensitive to the oxygen con that of the wrought material and unique heat treat
centration and so any significant oxygen diffusion ment schedules have been proposed to achieve elonga
would have reflected in a higher surface hardness. tion and toughness comparable to the wrought alloy
The hardness was higher after heat treatment in [31]. This result signifies that heat treatment at 800°C
vacuum than air. Heat transfer can be quite different can be performed in air without any significant loss in
between air and vacuum due to lack of convection in mechanical properties compared to vacuum. Heat
the latter that can lead to different temperature–time treatment in air is simpler, cost-effective, and indust
profiles and consequently, different final hardness in rially, a more attractive process than the use of
the coupons. Moreover, the difference in the heating vacuum furnaces.
rate in the two furnaces (5°C/min in air and 10°C/min
in vacuum) could have contributed to these marginal
Microstructure and mechanical properties of the
differences.
implant
Room temperature tensile properties of the as-
printed and heat-treated coupons measured along Microstructure was characterised across the thin
the longitudinal direction are compared in Table 1. cross-section (≈ 0.8 mm) of the as-printed implant
The ultimate tensile strength (UTS) reduced and elon and the SEM micrographs are presented in Figure
gation increased after heat treatment. The as-printed 12. The microstructure of the implant resembled that
microstructure consisted of fine martensite that com of the as-printed coupon comprising α′ martensite and
bined with its high initial dislocation density led to the was uniform across the cross-section, systematically
high strength. Heat treatment coarsened the as- taken from different regions from the left to the right
printed martensitic microstructure and would have hand side, marked as L1, L2, C, R1 and R2, in Figure
reduced the dislocation density substantially, 12(a).
a combination of which led to reduction in strength Thin strips of the implant were subjected to 800°C,
and improvement in tensile elongation. These obser 4 h heat treatment, in air or vacuum, and the respec
vations are in good agreement with reported literature tive SEM cross-section micrographs are compiled in
suggesting that DMLS alloy is stronger and brittle than Figures 13 and 14. The α′ martensite transformed into
the wrought alloy [31,33]. Although the strength was the α + β microstructure that was similar to the micro
structure of the heat-treated coupons (Figure 5). The
microstructure was also found to be uniform across
Table 1. Summary of tensile properties of as-printed and 800°
C heat treated coupons. the cross-section of the implant heat-treated in air and
Tensile property As-printed 800°C, 4 h (Air) 800°C, 4 h (vacuum) vacuum. Notably, heat treatment of implant in air at
UTS (MPa) 1343 ± 11 1060 ± 16 1191 ± 4 800°C did not influence the microstructure. The heat
% Elongation 10.1 ± 2.0 (1) 12.5 ± 1.0 14.5 ± 0.2 treatment simply achieves the effect of stress relieving
MATERIALS TECHNOLOGY 9
Figure 13. Cross-sectional SEM micrographs of the implant after heat treatment at 800°C for 4 h in air.
Figure 14. Cross-sectional SEM micrographs of the implant after heat treatment at 800°C for 4 h in vacuum.
and eliminating the undesirable effects of deformation contrasts with the similar surface and bulk hardness
of shape and loss of ductility. of the as-printed coupon (Figure 11). The higher
The hardness along the cross-section of the as- surface hardness could be an outcome of the effect
printed and heat-treated implants are plotted in of differing processing parameters of DMLS (such as
Figure 15. The hardness was slightly higher (≈ 8%) scan speed and laser power) that are typically used
along the surface (left and right edges) as compared during the layer by layer processing at the surface of
to the centre of the implant. This observation a part. The parameters of DMLS are varied from
10 D. SRINIVASAN ET AL.
Figure 15. Vickers microhardness across the cross-section of the implant in as-printed and heat treated (800°C, air and vacuum)
conditions.
those used for the bulk. Therefore, all hardness mea validated in a thin cranial implant. Change in layer
surements of the coupons performed are those for the thickness of DMLS from 30 to 50 μm did not result in
alloy prepared under the conditions of the bulk as the a change in porosity or microstructure. The micro
coupons had been prepared from the rectangular structure in the as-printed condition in the coupon as
blocks. In contrast, the measurements on the thin well as the implant consisted of α’ martensitic laths.
section of the cranial implant would have significant Heat treatment of the as-printed coupon at 800°C
contributions from the surface regions prepared resulted in the transformation of α′ into α + β phases.
using altered printing parameters, which likely There were no discernable differences in the micro
resulted in the small differences in the values structure in the bulk or at the surface when the heat
observed here. treatment was done in air or vacuum. The hardness
Nevertheless, there were other similarities between decreased after heat treatment from the as-printed
the coupons and implant. The bulk hardness of the condition but with minimal differences when heat
as-printed implant was comparable to the hardness treated in air or vacuum, which was also reflected in
of the as-printed coupon. Heat treatment of the the UTS values from the tensile tests. The implant
implant in both air and vacuum reduced the hard exhibited similar microstructures and comparable
ness. The relatively higher surface hardness than bulk trends in hardness similar to the coupons in as-
hardness in the as-printed implant was preserved printed condition and after heat treatment in air
even after heat treatment in air and vacuum. This and vacuum. These results suggest that it is feasible
observation suggests that oxygen diffusion in the to do heat treatment of DMLS parts of Ti6Al4V at
implant was limited during heat treatment in air 800°C in air without the need for vacuum furnaces
and therefore, is a viable processing route for the that can help in augmenting productivity and redu
implant. In a slight difference from coupons, heat cing the costs.
treatment of implant in air and vacuum produced
similar hardness, despite the difference in heat trans
fer conditions. Overall, the results of this investiga Acknowledgements
tion show that the 800°C heat treatment of implant in
The authors acknowledge funding from Uchchatar Avishkar
air poses no significant difference with respect to the Yojana program (UAY, Project number IISc_004).
vacuum heat treatment and therefore, a preferred
processing route to enhance productivity and mini
mise cost of production. Disclosure statement
No potential conflict of interest was reported by the authors.
Conclusion
DMLS of Ti6Al4V alloy powder was used to prepare Funding
blocks from which test coupons were prepared to This work was supported by the Uchchatar Avishlkar
optimise heat treatment conditions and further Yojana.
MATERIALS TECHNOLOGY 11
[32] Mezzetta J, Choi JP, Milligan J, et al. Microstructure- [33] Shunmugavel M, Polishetty A, Littlefair G.
properties relationships of Ti-6Al-4V parts fabricated Microstructure and mechanical properties of
by selective laser melting. Int J Precis Eng Manuf - wrought and additive manufactured Ti-6Al-4V
Green Technol. 2018;5:605–612. https://doi.org/10. cylindrical bars. Procedia Technol.
1007/s40684-018-0062-1 2015;20:231–236.