Ceramics International 47 (2021) 9125–9131

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Influence of flash sintering on phase transformation and conductivity

of hydroxyapatite
Isabela Reis Lavagnini a, c, *, João Vitor Campos a, c, Ana Gabriela Storion a,
Anderson Oliveira Lobo b, Rishi Raj c, Eliria Maria de Jesus Agnolon Pallone a
a
Department of Biosystem Engineering, Faculty of Animal Science and Food Engineering (FZEA), University of São Paulo (USP), 13635-900, Pirassununga, SP, Brazil
b
Interdisciplinary Laboratory for Advanced Materials (LIMAV), BioMatLab, Department of Materials Engineering, Federal University of Piauí (UFPI), 64049-550,
Teresina, PI, Brazil
c
Department of Mechanical Engineering, University of Colorado at Boulder, 80309-0427, Boulder, CO, USA

A R T I C L E I N F O A B S T R A C T

Keywords: We report on the influence of current density limits on phase transformation, density, and microstructure of
Hydroxyapatite Hydroxyapatite (HAp) subjected to flash sintering experiments. Arrhenius plots of the electrical conductivity
Flash sintering during the constant heating rate experiments showed changes in the ionic conductivity mechanisms during the
Electric field assisted sintering
incubation time, contrasting behavior from other materials presented so far. Flash sintering also suppressed the
Electrical properties
Conduction mechanisms
formation of β-tricalcium phosphate, which occurs during conventional sintering. We report herein that low
current density limits were able to successfully sinter dense HAp with minimal phase transformations under
lower furnace temperature and significantly shorter time processing.

1. Introduction applied to several materials [14–19]. However, papers on flash sintering

of calcium phosphates are relatively rare. Frasnelli and Sglavo (2018)
Hydroxyapatite (HAp) [Ca10(PO4)6(OH)2] is the calcium phosphate were able to produce dense β-tricalcium phosphate (β-TCP) [Ca3(PO4)2]
that is the principal inorganic component of bone and teeth. Therefore it using flash sintering [20]. As a result, they could avoid the typical β-to
is widely used in biomedical applications, e.g., in drug-delivery systems α-TCP phase transformation, very common in conventional sintering
[1], bone implants [2], and bioactive coating [3,4]. However, conven­ [20–22]. In a further study, Frasnelli et al. (2019) flash sintered
tional sintering of HAp requires several hours at 900–1300 ◦ C [5]. Mg-doped β-TCP, also avoiding the undesirable phase transformation
Furthermore, HAp is not stable at high temperatures, which can lead to [23]. In a preliminary study, Bajpai et al. (2016) [24] flash sintered HAp
the formation of (undesirable) secondary phases of calcium phosphates and reported a decrease in the furnace temperature and in the processing
during the sintering process [5–7]. time, but phase transformations on flash sintered samples were not
Since phase transformation in calcium phosphates is affected by investigated.
sintering parameters, such as temperature, heating rate, and holding The current density limit is a critical parameter in the flash sintering
time, we decided to explore if flash sintering could avoid phase trans­ process. While the onset of flash is related to the combination of the
formations. This sintering technique is known to drastically reduce the electrical field and furnace temperature, the extent of sintering is linked
furnace temperature and shorten the sintering time to a few seconds [8]. to the current density limit placed at the power supply [25]. In the
Besides that, flash sintering is also known for its rapid heating rate, present experiments, we report on the influence of the current density
resulting in an accelerated diffusion that may inhibit phase trans­ limit on phase transformation, density, and microstructure. We also
formation, prevent grain growth, and suppress volatilization, which is show that the conduction mechanisms of the HAp change during the
difficult to control during conventional sintering [8–13]. incubation time of the flash sintering process.
Since the original work [8], the flash sintering process has been

* Corresponding author. Department of Biosystem Engineering, Faculty of Animal Science and Food Engineering (FZEA), University of São Paulo (USP), 13635-
900, Pirassununga, SP, Brazil.
E-mail addresses: isabela.lavagnini@usp.br (I. Reis Lavagnini), joao2.campos@usp.br (J.V. Campos), anagstorion@usp.br (A.G. Storion), lobo@ufpi.edu.br
(A.O. Lobo), rishi.raj@colorado.edu (R. Raj), eliria@usp.br (E. Maria de Jesus Agnolon Pallone).

https://doi.org/10.1016/j.ceramint.2020.12.036
Received 19 November 2020; Received in revised form 3 December 2020; Accepted 5 December 2020
Available online 6 December 2020
0272-8842/© 2020 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
I. Reis Lavagnini et al. Ceramics International 47 (2021) 9125–9131

details about this setup were reported in previous work [27].

The samples were flash sintered under a DC electric field of 1300
V⋅cm− 1. The current density limits were: 3, 6, 12, and 24 mA⋅mm− 2. The
experiment was carried out by applying the field and heating the furnace
at a constant heating rate of 15 ◦ C⋅min− 1. At the onset of flash, the power
supply was switched to current control, and the specimen was held in
the state of flash for 10 s before the experiment was completed. For
comparison, samples were conventionally sintered (without applying
electric field) at 1200 ◦ C with 2 h of holding time, using a heating rate of
15 ◦ C⋅min− 1. All experiments were performed in air.
Thermogravimetry (TG) and Differential Scanning Calorimetry
(DSC) were performed under a dynamic dry air atmosphere with a flow
rate of 25 mL⋅min− 1, and a heating rate of 10 ◦ C⋅min− 1.
The samples temperatures during the steady-state of flash sintering
(after the current density reached its maximum pre-set value) were
calculated according to the Black Body Radiation (BBR) model [28] with
equation (1).
[ ]1
Pw V 4
T = T04 + (1)
Aσε
In equation (1) PW is the equilibrium power during the flash in
W⋅m− 3, V is the sample volume, A is the surface area in m2, and σ is the
Stefan-Boltzmann constant (5.67 × 10− 8 W⋅m− 2K− 4). The emissivity ε
used in equation (1) was 0.8 [20].
We determined the apparent densities (by Archimedes) of the sam­
ples according to ASTM C373-88. The relative density was calculated
using the theoretical density (%TD) of the majority crystalline phase
(HAp - 3.156 g⋅cm− 3 [29]).
The microstructure of the samples was studied by scanning electron
microscopy (SEM) of the fracture surfaces.
To determine the crystallographic phases of the material (before and
after each sintering condition), x-ray diffraction (XRD) was performed
using Cu-Kα = 0.1542 nm, 40 kV, and 15 mA, in a continuous angular
scan between 20 and 55◦ , with a step of 0.02◦ ⋅min− 1.

3. Results and discussion

Fig. 1 presents the curves of the electric field, current density, and
power density of the flash sintered HAp samples. We observed that
during the incubation time, the current density curves showed behavior
that is different from those reported in the literature. During the incu­
bation time of flash sintering, usually, the materials’ electrical conduc­
tivity rises with the temperature following an Arrhenius-like behavior
Fig. 1. Plots of (a) electric field (E); (b) current density (J) and (c) power [30]. Some authors already reported this typical behavior for many
density (P) as a function of temperature for HAp flash sintered under different ceramic materials [8,17,31–33]. However, when we plotted HAp elec­
current density limits. trical conductivity and power density following Arrhenius, we observed
an unusual behavior.
2. Material and methods Fig. 2 presents electrical conductivity and power density curves
plotted in Arrhenius format and a schematic demonstration of the HAp
Nano-sized HAp powder was synthesized via the wet chemical conductivity mechanisms divided into three zones. In zone 1, the HAp
method as described in the previous work [26]. The powder was uni­ conductivity rose from room temperature to 450 ◦ C. Then it dropped to
axially pressed (280 MPa) as dog-bone shaped samples with holes at its approximately 600 ◦ C (zone 2). Finally, for temperatures above 600 ◦ C
ends. The samples’ cross-section was 1.6 mm × 3.3 mm, and gauge the observed behavior resembled those reported for other materials, e.g.
length 15 mm. 3 YSZ [8], TiO2 [34], Co2MnO4 [14], and SrTiO3 [35], characterized by
The platinum paste was applied to the holes on the edges of the dog- a constant rising of the conductivity during the heating up process (zone
bone to improve the contact between the sample and the platinum wires 3). At approximately 1000 ◦ C the flash event took place, and the sample
that were connected to the power supply. The samples were hung inside started to glow intensively. We believe that each zone is driven by
the tubular furnace with these two platinum wires. A multimeter was different electrical conduction mechanisms, which are briefly explained
connected to the circuit to measure the current. The voltage was below.
measured by the power supply. A CCD (charge-coupled device) camera In zone 1, the electrical conductivity of HAp is a result of the protonic
placed at the bottom of the furnace recorded images at 60 fps. More conductivity [36,37]. Fig. 3 presents TG and DSC curves of HAp,

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Fig. 2. Arrhenius plot of (a) conductivity (σ) and (b) power density (P); (c) conductivity mechanisms of HAp flash sintered under different current density limits;
zone 1 represents flipping and hoping of H+; zone 2 represents the lack of H+ decreasing the protonic conductivity; zone 3 represents the O− conduction.

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conductivity of HAp increases. According to some authors [36,39,40],

this protonic conductivity of HAp happens by the flipping and hoping
mechanism of the H+, which happens at the remained OH groups, as
illustrated in Fig. 2 (c).
In zone 2, the increase in the mobility of H+ is compensated by the
lack of these ions. For each OH− vacancy created, one H+ (charge car­
rier) is used to form the water molecule, and then the electrical con­
ductivity of HAp starts to decrease [36,39,40].
In zone 3, the conductivity of the material starts to behave similarly
to other oxides [30]. We speculate that the lack of H+ is enough to
change the conductivity mechanism, and then the oxygen ions work as
charge carriers, hopping between vacancies throughout the c-axis [20].
In this zone, the conductivity increases with the temperature due to the
increased mobility of charge carriers. The conductivity increases as an
Arrhenius-like behavior until a second critical temperature (flash onset
temperature), at which the flash event occurs.
Vendrell and West (2019) and Jo and Raj (2020) [41,42] reported a
transition from ionic to mixed ionic and electronic conductivity during
the flash event of YSZ. Such a rapid rise in the conductivity may be
explained by this transition for hydroxyapatite as well. Although further
analysis of the electric characteristics of HAp is needed to confirm this
assumption.
The ions removal from HAp structure during flash sintering could
enhance some characteristics, such as polarization, ferroelectricity, and
ion exchange. Thus, it becomes interesting to study the final properties
of flash sintered HAp regarding some of its applications, e.g., heavy
metal removal filters [43–45] and electrets [40,46,47].
The first power peak (transition between zone 1 and zone 2 pre­
sented in Fig. 2 (c)) shows a similar area for the different conditions
Fig. 3. (a)Thermogravimetry (TG) and (b) Differential Scanning Calorimetry studied. The power supply is operating under voltage control during
(DSC) curves followed by their derivatives. zone 1 and zone 2. In this way, at this point, the current density is
controlled accordingly to the material resistance, which is expected to
be equal for all the samples. As previously discussed, the decrease in this
Table 1 first power peak is related to water loss resulting in a decrease in the
Temperature, sintering time, and the relative density followed by standard de­ material conductivity [36,39,40], as a future experiment, combining
viations of the HAp conventionally and flash sintered samples under different flash sintering with a water vapor atmosphere could be of interest. Some
current density limits.
works discuss that the use of a water vapored atmosphere during the
Condition Temperature estimated by Sintering Final relative heat treatment of HAp could affect the dehydroxylation process
BBR (◦ C) Time (s) densities (%) [48–50]. The water vapor atmosphere may facilitate the thermal
Conventional 1200a 7200 94.6 ± 0.4 runaway ignition, and in that way, lowering the flash onset temperature.
3 mA⋅mm-2 1160 ± 5 10 91.5 ± 0.1 For instance, in the case of zinc oxide, Nie et al. (2018) reported an
6 mA⋅mm-2 1196 ± 4 10 90.6 ± 0.3
increase in the conductivity of the specimen that was enough to trigger
12 mA⋅mm-2 1213 ± 2 10 89.3 ± 0.1
24 mA⋅mm-2 1254 ± 6 10 88.5 ± 0.2 the flash event at room temperature [51].
a
Table 1 presents the samples temperatures calculated from equation
This temperature stands for the value measured by the thermocouple.
(1). The data for conventional sintering are included. Table 1 also pre­
sents the relative density values of the HAp conventionally and flash
followed by their derivatives. The figure shows for the same temperature sintered samples under different current densities.
range in zone 1 a mass loss in HAp TG results. According to Sofronia The specimen temperature increases with the current density limit.
et al. (2014) [38], this mass loss refers to the dehydroxylation with an Still, the specimen temperature remains below the conventional sinter­
endothermic effect, which is in agreement with the DSC results. ing temperature for the case of 3 and 6 mA⋅mm− 2. For the case of 12 and
Considering that HAp can be heated up to 1200 ◦ C without changing 24 mA⋅mm− 2, the specimen temperature was a few degrees higher than
its apatite structure, this dehydroxylation affects the electrical conduc­ the conventional sintering temperature. Table 1 also shows that the
tivity characteristics of the material [39,40]. The HAp exhibits a hex­ relative densities decreased with the increase in the current density.
agonal crystalline structure in which OH− groups are lying on the c-axis. The micrographs from flash sintered samples were compared to
During the heating up, HAp dehydration happens when some of the OH conventionally sintered one. As shown in Fig. 4, the nature of fracture in
groups react with each other forming water, following equation (2) [36, the conventionally sintered sample is transgranular while it is inter­
39,40]: granular for samples submitted to flash sintering with a current density
Ca10 (PO4 )6 (OH)2 →Ca10 (PO4 )6 (OH)2− (2) limit of 3 mA⋅mm− 2. The 24 mA⋅mm− 2 specimen has pores in its
2x Ox [ ]x +x H2 O
microstructure, which is consistent with its lower relative density. Note
Where [ ]x are the vacancies for OH− . As equation (2) happens, for every also that the grain size increased with the current density limit.
two OH− released, an H+ vacancy and an OH− vacancy are created. Due Fig. 5 shows the X-ray diffractograms for the powder, convention­
to the appearance of these vacancies, the mobility of H+, and the proton ally, and flash sintered specimens. The synthesized powder perfectly

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Fig. 4. SEM micrographs of the HAp fracture surfaces conventionally sintered and flash sintered under different current density limits.

matches the HAp structural model (PDF card #9–432). The amount of efficiency in densifying HAp without the undesired formation of sec­
other calcium phosphate phases is much lower in the flash sintered ondary phases in larger quantities, coupled with lower grain growth and
samples than in conventionally sintering. Note that the amount of drastically shorter sintering time.
extraneous calcium phosphates phases, with peaks within 29.5◦ < 2θ <
31.5◦ , varied with the current density limit. Higher current density 4. Conclusions
increased the presence of other calcium phosphate phases. The specimen
temperature increases with the current density limit, which may explain We observed that the conductivity of HAp during the incubation time
the increased presence of these phases. behaves differently from other oxides already reported in flash sintering.
Different athermal effects of flash sintering [13] have been reported: The electrical conduction mechanisms change with increasing temper­
sometimes phase transformation is favored [52–54], and sometimes it is ature due to the loss of ions during the dehydroxylation of this material.
avoided [10,20]. In this paper, the HAp to β-TCP transformation was The current density limit influenced the material’s microstructure in
successfully avoided by the application of flash sintering. The conven­ grain size, type of fracture, and porosity also affect the maximum tem­
tionally sintered sample shows β-TCP (PDF card #09–169) as a sec­ perature (BBR model) reached by HAp. The rapid heating rate of flash
ondary phase, which has no assignment for the flash sintered specimens. sintering, provided by Joule heating, may be responsible for the
In temperatures above 1125 ◦ C, β-TCP transforms to α-TCP [20,21,55], avoidance of phase transformations in HAp. Flash sintered samples did
which reverts to the β-TCP phase when the specimen is cooled down not present the formation of β-TCP, as observed in the conventionally
from conventional sintering temperature [55]. The absence of the β-TCP sintered samples. So, low current density limits were able to successfully
phase in flash sintering may be explained by the rapid quenching when sinter dense HAp with minimal phase transformations under a lower
the power supply is turned off. Samples sintered under higher current furnace temperature and significantly shorter time processing.
densities, although avoiding the formation of β-TCP, presented trans­
formations to other phases of calcium phosphates in small quantities.
Therefore, the intermediate current density values showed better

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Fig. 5. X-ray diffractograms of the HAp powder, conventionally and flash sintered samples under different current density limits.

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