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A review of two-step sintering for ceramics

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 Ceramics International 42 (2016) 12556–12572

Contents lists available at ScienceDirect

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

Review article

A review of two-step sintering for ceramics

N.J. Lóh a,b, L. Simão a,b, C.A. Faller a, A. De Noni Jra,b, O.R.K. Montedo a,b,n
a
Grupo de Pesquisa em Cerâmica Técnica (CERTEC), Universidade do Extremo Sul Catarinense (UNESC), Av. Universitária, 1105 - P.O. Box 3167, 88806-000
Criciúma (SC), Brazil
b
Programa de Pós-Graduação em Ciência e Engenharia de Materiais (PPGCEM), Universidade do Extremo Sul Catarinense (UNESC), Av. Universitária,
1105 - P.O. Box 3167, 88806-000 Criciúma (SC), Brazil

art ic l e i nf o a b s t r a c t

Article history: The development of high-density ceramic materials with fine-grained microstructures has been studied
Received 27 January 2016 to considerably improve their properties for high-performance applications. Many alternatives have been
Received in revised form searched to refine their microstructure by changing their composition and/or processing. Among such
30 March 2016
alternatives, the densification of ceramic materials by sintering curve control is an effective, simple and
Accepted 10 May 2016
Available online 11 May 2016
economical microstructure refinement method. Thus, different thermal treatment techniques such as
spark plasma sintering and microstructural forms of control such as the control of sintering conditions
Keywords: have been used to obtain nanostructured materials. One of the techniques widely used in recent years is
Ceramic materials two-step sintering. Two-step sintering (TSS) is a promising method used to obtain high-density bodies
Two-step sintering
and smaller grain sizes. Two TSS methodologies are known: sintering with thermal pretreatment at a low
Suppression of grain growth
sintering temperature, followed by a second stage at elevated temperature, and the more recent ap-
Final microstructure
Properties proach presented by Chen and Wang, which has been the most widely used. In addition to the sintering
conditions (temperature, heating rate and sintering holding times) that must be suitable for each
composition type, the starting materials, particle size and processing method may influence the obtained
microstructure, especially the reduced grain size and increased densification. The current review of two-
step sintering presents the effect of this technique on the grain density and sizes of different ceramic
materials. The influence of the addition of doping agents and its effect on the mechanical properties in
different systems is also presented in the current study.
& 2016 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12557
2. Historical context. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12557
3. Two-step sintering method by Chu . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12557
4. Two-step sintering method by Chen and Wang. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12559
4.1. Yttrium oxide (Y2O3) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12559
4.2. Zinc oxide (ZnO) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12560
4.3. Aluminum oxide (Al2O3) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12560
4.4. Yttria (Y2O3)-stabilized zirconia (ZrO2). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12561
4.5. Titanium dioxide (TiO2). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12563
4.6. Barium titanate (BaTiO3, BTO). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12564
4.7. Carbides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12564
4.8. Corundum abrasive . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12565
4.9. Piezoelectric ceramics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12566
4.10. Bioceramics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12566
5. Miscellaneous . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12567

n
Corresponding author at: Grupo de Pesquisa em Cerâmica Técnica (CERTEC), Universidade do Extremo Sul Catarinense (UNESC), Av. Universitária, 1105 - P.O. Box 3167,
88806-000 Criciúma (SC), Brazil.
E-mail addresses: nayadie@gmail.com (N.J. Lóh), lisandrosimao@gmail.com (L. Simão), cristian.faller@hotmail.com (C.A. Faller), agenordenoni@gmail.com (A. De Noni Jr),
oscar.rkm@gmail.com (O.R.K. Montedo).

http://dx.doi.org/10.1016/j.ceramint.2016.05.065
0272-8842/& 2016 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
 N.J. Lóh et al. / Ceramics International 42 (2016) 12556–12572
6. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12570
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12571
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12571
1. Introduction
The properties of polycrystalline ceramics are controlled by the
microstructure. The density, grain size and presence of hetero-
geneities in the microstructure are carefully controlled to improve
the properties and reliability of ceramics [1]. Highly dense cera-
mics with nanometric or submicrometric grain size are difficult to
obtain through conventional sintering.
However, there are some manufacturing routes available for
the production of these ceramics, including colloidal powder
processing with controlled distribution of particle sizes [2,3], the
use of sintering additives [4], pressure-assisted sintering [5,6],
spark plasma sintering (SPS) [7] and pulsed electric current sin-
tering (PECS) [8]. These sintering methods may not be cost-ef-
fective for any materials because the devices are more complex,
expensive and difficult to implement.
Solid-phase sintering requires relatively high temperatures to
facilitate diffusion and, through different mechanisms, promote
material densification. However, diffusion is the matter transport
mechanism, which promotes not only densification but also grain
growth. Therefore, sintering conditions that allow densification to
occur without simultaneously stimulating grain growth are sui-
table for microstructural refinement. This dissociation between
densification and grain growth is what allows highly dense cera-
mics and nanometric grains to be produced [9].
An outstanding technique used to manipulate the micro-
structure during the sintering stage is known as rate-controlled
sintering (RCS), which was first reported in 1965 [18]. There are
several studies about this issue; however, the equipment advance
and the improvement in the theoretical and empirical models
related to the microstructure development and densification al-
lowed the advancement in the RCS technique.
In the 1990s, Chu et al. [10] introduced the two-step sintering
(TSS) technique, which is described in the current study as TSS-C.
According to this technique, the first stage (pretreatment) was
performed at a relatively low temperature and was followed by a
higher-temperature stage and subsequent cooling. The process
allows refinement of the microstructure and, thus, improvement
of the material properties.
Later, Chen and Wang [11] suggested a modification in the two-
step sintering technique. This modification, which is identified in
the current study as TSS-CW, has become widely used. This tech-
nique consists of suppressing the accelerated grain growth, which
usually occurs in the final sintering stage. High-temperature
heating is performed and is followed by structural freezing. Fast
cooling at a constant rate suppresses grain growth but allows
densification to occur [11,12]. The technique may be successfully
applied to many ceramic materials, thus enabling high-density
microstructure refinement and improving several properties of the
materials.
The aim of the current review is to present the state of the art
of two-step sintering applied to ceramic materials. Thus, the study
is divided into three main topics. First, a brief history of the two-
step sintering technique (TSS) evolution will be presented, fol-
lowed by a presentation of papers that used the methodology
suggested by Chu (TSS-C) and, finally, studies that addressed the
two-step sintering technique suggested by Chen and Wang (TSS-
CW). This section shows the effect of the addition of doping agents
and that of the processing characteristics on the grain density and
12557
size in each ceramic material type identified in the literature and
compares it to conventional sintering (CS). It also presents a CS
contribution to the improvement of mechanical properties.
2. Historical context
Studies about controlled sintering methodology date back to
the mid-1960s, which was when the first studies on the RCS
method emerged [13–24]. This term was first introduced by Pal-
mour and Johnson in 1965 [18]; the methodology consists of mi-
crostructure refinement by sintering curve manipulation, and it
features advantages such as simplicity and economy. The proce-
dure consists of determining the relationship between the densi-
fication rate and the grain growth rate, thus suggesting tempera-
ture and sintering time values for material densification [20,21].
Therefore, ultrafine nickel powders were sintered at controlled
rates, and high-density materials (
99% relative density) with a
grain size smaller than 100 nm were obtained.
Thus, controlled-rate sintering is an effective methodology in the
obtainment of dense bodies with a nanocrystalline structure [21].
In 1991, Chu et al. [10] conducted a study about the sintering
process of conventional alumina (Al2O3) and magnesium oxide
(MgO) powders. Conventional isothermal sintering and pre-coar-
sening at a low temperature were comparatively evaluated before
the use of conventional isothermal sintering. The two-step sin-
tering technique suggested by Chu (TSS-C) was favorable for sys-
tems with wide-particle-size-distribution conventional powders,
and it produced uniform ceramic bodies in a simple way [10].
However, in 2000, Chen and Wang [11] suggested a new
methodology for the two-step sintering (TSS-CW) technique, ac-
cording to which the ceramic body is rapidly subjected to a high
temperature and is subsequently cooled and kept at a lower tem-
perature (sintering holding time). The authors report that densifi-
cation occurs with no grain growth in a certain temperature range
called the "kinetic window". Residual porosity is eliminated at this
temperature level during sintering with no grain growth, which
occurs at the final stage [11,12]. The grain growth suppression, but
not its densification, is determined by a network of grain bound-
aries anchored by joints in the triple points, which have higher
activation energy for migration than the grain boundaries. However,
the critical density must be achieved in the first stage so that there
are sufficient triple joints throughout the body [12].
A sufficiently high relative density (70% or higher) is re-
commended in this first stage [11,25]. The sintering temperature
decreases to a critical level, leading the triple joints to interrupt
the grain growth, whereas densification is not affected. The sam-
ples must then be exposed to prolonged heating at a low tem-
perature in the second isothermal stage [11]. Fig. 1 schematically
depicts the comparison between the TSS-C and TSS-CW sintering
curves.
3. Two-step sintering method by Chu
The two-step sintering suggested by Chu (TSS-C) was applied to
different ceramic materials. Huang et al. [26] evaluated the ob-
tainment of silicon nitride (Si3N4) through this method and found
increased material densification, although the grain size growth
12558 N.J. Lóh et al. / Ceramics International 42 (2016) 12556–12572

Fig. 1. Illustrative representation of the TSS-C and TSS-CW sintering plots.

occurred at a higher temperature in the second stage. This growth
was related to the great structural disarray.
The use of high-purity Al2O3, both with and without MgO ad-
dition, was evaluated by applying thermal pretreatments. The use
of low temperatures (800 °C) and long periods (50 h) improved
the material densification and the microstructure [27]. The effect
of thermal pretreatment performed in a high-quality alumina was
also evaluated [1]. The delay in the initial densification stage was
observed at low temperature levels owing to the elimination of the
finer particles. Therefore, the elimination of these particles in the
first level reduced the differential densification and the formation
of denser regions in the initial densification stages. Thus, the
density variations in the ceramic body were reduced, leading to a
more homogeneous final microstructure. Fig. 2 shows the sche-
matic representation of the TSS technique.
Sato and Carry [28] determined the effect of pretreatments on
two types of ultrafine aluminas (submicron-sized particles with
median volume diameters of 0.2 mm and 0.4 mm). Before the sin-
tering, pretreatments were executed at 820 or 920 °C for 50 h. They
concluded that the use of pretreatment delays the onset of abnor-
mal grain growth, resulting in a more uniform microstructure be-
fore densification.

Fig. 2. Schematic diagram illustrating the microstructural refinement produced by the TSS technique [1].
 N.J. Lóh et al. / Ceramics International 42 (2016) 12556–12572 12559

ceramics with 3-mm-mean-size uniform grains were obtained

following the pretreatment.

4. Two-step sintering method by Chen and Wang

The two-step sintering technique suggested by Chen and Wang

(TSS-CW) has been widely used because it is a methodology used
to obtain ceramic bodies with a controlled microstructure.
The effects of the addition of doping agents and the processing
characteristics on grain density and size are detailed in this section
for each type of ceramic material identified in the literature, and
their contributions to the improvement of mechanical properties
are discussed.

4.1. Yttrium oxide (Y2O3)

As previously mentioned, Chen and Wang [11] suggested a new

Fig. 3. Grain size of Y2O3 in TSS and CS [11].
method for sintering in two stages. Yttrium oxide powders with
sizes ranging from 10 to 100 nm were evaluated. High densifica-
tion was achieved without grain growth in pure Y2O3. The first
Kim and Kishi [29] studied the effect of pretreatments on the stage of temperature (T1) was 1310 °C, and that of the second
resistance and the subcritical crack growth in alumina. The alu- stage (T2) was 1150 °C for 20 h. Smaller grain size was achieved by
minas sintered by the hot-pressing technique had flexural strength using a lower value for T1 (1250 °C). Fig. 3 shows the relationship
values of 400–500 MPa, whereas the pretreated ones (1000– between the relative density and the grain size of pure Y2O3 ob-
1200 °C for 10 h) increased their resistance to 750 MPa. The au- tained through conventional and two-stage sintering processes.
thors concluded that the pretreatment increases the fracture High-density samples (approximately 100%) with grain size
toughness of the grain boundary, reducing the subcritical growth smaller than 200 nm were obtained through TSS, and they were
rate of sintering flaws and resulting in strengthening. The result much smaller than those obtained through CS (
400 nm).
led to increased material resistance. The bodies reached relative The effect of magnesium and niobium additions was also
density exceeding 90% in SrBi2(VxNb1  x)2O9 ferroelectric ceramics evaluated. The addition of 1 wt% Nb2O5 shifted the kinetic window
(x between 0 and 0.3) [30]. to a higher temperature. However, the addition of 1 wt% MgO had
A study was conducted on pure alumina and on alumina doped the opposite effect. According to the authors, the use of doping
with 140, 500 and 2500 ppm of MgO, vacuum sintered at 1700 °C, agents is even more satisfactory when the difference in the ki-
with and without thermal sintering pretreatment at 800 °C for netics between grain-boundary diffusion and grain-boundary mi-
50 h in air [31]. The thermal pretreatment and the greater MgO gration is exploited to achieve densification without growth at
addition led to decreased grain growth, resulting in a more lower temperatures. A fully dense microstructure with a smaller
homogeneous structure. The grain size in the samples was reduced grain size in the range of 60 nm was obtained using Y2O3 doped
from 16 mm to less than 10 mm owing to the addition of 500 ppm with 1 wt% MgO, as shown in Fig. 4. The sintering process occurred
MgO. The grain size was reduced to 8 mm with 2500 ppm MgO. at T1 1080 °C, with 76% initial relative density. The material was
Porosity was also reduced. However, the addition of dopant agents, then kept at 1000 °C for 20 h (T2).
although low, reduced the density of the samples. The combina- Wang et al. [12] also evaluated yttria powders with different
tion of MgO and Al2O3 and the thermal pretreatment technique particle sizes ranging from 10 to 60 nm. Two dopant agents, i.e.,
proved to be helpful in preventing abnormal grain growth.
Han et al. [32] obtained uniform hexagonal grains of yttria-
stabilized zirconia. Three different conformation methods were
applied: tape casting (TCS), tape calendaring (TCL) and gel casting
(GC). Grain sizes of 3–5 mm and between 8 and 15 mm were ob-
tained for TCS and GC samples, respectively, in the conventional
treatment (1450 °C for 2–4 h). Samples with 1–4 mm grain sizes
were produced using the TSS-C process (T1 at 1000 °C, holding
time of 2 h, and T2 at 1400–1450 °C for 2 h) and the TCL con-
formation process.
ZnO was doped with aluminum (Al) and initially subjected to
thermal treatment at a low temperature and to external pressure
by using the same methodology. The specimen was heated to 800–
1000 °C at a 5 °C min  1 heating rate under external pressure (0,
1 or 2 MPa) for 10 min Subsequently, the pressed specimens were
sintered without pressure at 1250, 1300, and 1350 °C for 2 h in air
using a separate furnace. Effective TSS-C implementation reduces
the final sintering temperature to obtain similar density to dif-
ferent dopant contents. It was also reported that the cohesion
between the particles during the initial thermal treatment must be
established and that the high specific area should be preserved for
successful application of TSS-C [33]. Liu et al. [34] studied
KSr2Nb5O15 (KSN) ceramics manufactured through TSS-C. Dense Fig. 4. Microstructure of fully dense Y2O3 doped with 1 wt% MgO [11].
12560 N.J. Lóh et al. / Ceramics International 42 (2016) 12556–12572
magnesium (Mg2 þ ) and niobium (Nb5 þ ), were used in addition to
pure yttria, and they replaced yttria at 1 wt%. The samples were
sintered through CS and TSS-CW. The heating rate in CS was
10 °C min  1 to 1600 °C (no holding time) with natural cooling.
Regarding TSS-CW, the heating rate was 10 °C min  1 to T1, in
which it cooled at the rate of 50 °C min  1 to T2 and remained
there for 6–30 h. By comparing the results found by Wang et al.
[12] to the study by Chen and Wang [11], it appears that both
yielded pure Y2O3 through TSS-CW with grain sizes smaller than
200 nm. Relative density of 99% and a grain size of 123 nm were
obtained using 1250 and 1100 °C as T1 and T2, respectively. The
same evidence was verified regarding the influence of doping
agents. Finally, Wang et al. [12] concluded that the Y2O3 TSS-CW,
with or without doping agents, develops by grain boundary dif-
fusion. The grain growth suppression may be attributed to triple-
point immobility, which is facilitated by pre-firing high-tempera-
ture single-step sintering.
4.2. Zinc oxide (ZnO)
Mazaheri et al. [35] evaluated the effect of temperature on the
grain density and size of high-purity ZnO compacts (99.7%) with a
mean particle size of 31 nm. Three different sintering regimes
were used, i.e., 850–750, 800–700 and 800–750 °C, respectively,
for T1 and T2. Specimens with density and grain size similar to
those of the CS method (approximately 4 mm) were obtained using
the temperatures of 850 and 750 °C. The samples were dense, but
there was no grain growth suppression. Grain growth and 86%
densification were observed using lower temperatures such as 800
and 700 °C (T1 and T2, respectively). The best condition was ob-
tained at the temperatures of 800 and 750 °C. Submicrometric
grains (
680 nm) were obtained with 98% relative density. It was
concluded that the temperatures of both sintering stages play a
significant role in densification and grain growth.
Wu [36] conducted a study on pure ZnO with mean particle
size of 400 nm and sintered in four different sintering plans. The
temperature ranged from 1000 to 1300 °C in the first stage and
from 950 to 1250 °C in the second stage, with a 12-h holding time.
The best condition was obtained at 1100 and 1050 °C, wherein the
relative density was 95.1% and the grain size was 3.9 mm. Com-
pared with the study by Mazaheri et al. [35], the TSS-CW method
is inefficient for ZnO in regard to larger particle sizes and higher
sintering temperatures. Wu [36] explained this inefficiency based
on the studies by Maca et al. [37,,38]. According to these authors,
the TSS-CW efficiency depends more on the crystalline structure
than on other factors such as particle size, and the cubic structure
may be more easily densified by TSS-CW than the hexagonal and
tetragonal structures.
ZnO with 2 wt% Al2O3 was also evaluated [36]. Five temperature
plans (1400–1350, 1450–1400, 1500–1250, 1500–1350 and 1500–
1450 °C) were used, and the density and grain size were evaluated.
Samples with 99.8% relative density and 3.6 mm grain size were
obtained at temperatures of 1500 and 1350 °C. The authors report
that the doping changed the TSS-CW kinetic window and helped
densify the material. The Al2O3 reacted with ZnO to form ZnAl2O4
(spinel), and these precipitates contributed to the higher density
and prevented grain growth. A relative density improvement from
97.4% to 99.8% was observed compared with CS (1500 °C for 12 h).
The grain size was reduced from 9.1 to 3.6 mm [36].
Duran et al. [39,40] evaluated ZnO varistors doped with Bi2O3,
Sb2O3, CoO, and MnO. Two sintering profiles (900–825 and 940–
825 °C) were evaluated by varying the holding time in T2 between
10 and 6 h, respectively. The grain size for the first profile was
500 nm. Regarding the second profile and the shorter holding time
in T2 (6 h), the grain size increased to 700 nm. The presence of
dopant agents enabled the liquid phase formation in the first stage
at temperatures up to 900 °C. The amount of liquid phase de-
creased in the second stage because of cooling at 825 °C, and the
ZnO-ZnO direct contact was improved by suppressing the grain
boundary migration and maintaining the active grain boundary
diffusion to obtain densification. Thus, full densification was
achieved in the second stage (10-h holding time) without grain
growth.
Another study using ZnO varistors [41] found that the molar
composition of the varistor was 95.01% ZnO and 4.99% other oxi-
des (4.99% Bi2O3, Sb2O3, Mn3O4, Co3O4, NiO, Cr2O3 and
Al(NO3)3  9 h2O). Other sintering systems have been tested with
T1 ranging from 1000 to 950 °C and T2 ranging from 875 to 825 °C.
The decrease in the temperature of the first stage reduced the
density and grain size at the beginning of the second stage. Thus,
more time was required in the second stage to achieve an almost
fully densified microstructure. A smaller grain size (750 nm) was
obtained with sintering temperatures at 950 and 825 °C in the first
and second stages, respectively, and a 10-h holding time in the
second stage.
By comparing this study with those conducted by Durán et al.
[39,40], it appears that despite the different compositions (in re-
lation to the used dopant agents), the decrease in T1 and T2, even
with longer T2, allowed material with higher density and smaller
grain size to be obtained.
Among the studies presented herein, it is concluded that the
addition of dopant agents to ZnO in conjunction with TSS-CW
helped suppress grain growth.
4.3. Aluminum oxide (Al2O3)
Alumina is the most studied ceramic. The initial alumina con-
ditions (pre-sintering), such as the smaller particle size, the chosen
conformation method and the reduced pore size in the green body,
affect the success of TSS-CW and the ceramic crystal symmetry.
Adding dopant agents to the alumina also hinders grain growth.
Li and Ye [42] applied the TSS-CW method to manufacture
alumina-based nanoceramics. Alumina with a mean particle size of
10 nm was synthesized using the doped Al2O3 seed poly-
acrylamide gel method. Two sintering plans were used in their
study, both of which used alumina conformed at 1120 MPa. The
samples were first heated at 1450 °C for 1 h in the first plan and
then at 1350 °C for 34 h in the second sintering stage. The relative
density of the samples was 96%, and the mean grain size was
approximately 90 nm, as estimated from the peak broadening of
X-ray diffraction. The second sintering plan occurred at 1380 °C for
1 h. Subsequently, the samples were cooled at 1330 °C with a 50-h
holding time. Despite the reduced temperature and the longer
holding time in the second stage, the relative density was 95%, and
the obtained grain size was slightly smaller than 70 nm.
Bodišová et al. [43] assessed the application of TSS-CW to
submicrometric alumina powders. The material had a mean par-
ticle size of 150–200 nm. The samples were sintered at 1330–
1450 °C in the first stage and at 1100–1160 °C in the second stage,
with 3- and 24-h holding times, respectively. According to the
authors, the minimum density to be achieved in the first sintering
stage should correspond to 92% relative density. They compared
this value to the density obtained in the study by Li and Ye [42],
which was 82% in the first stage, and attributed the densification
increase to the smaller particle size and the smaller pore size in
the green body. The sintering plan that yielded the best results
was T1 at 1400–1450 °C and T2 at 1150 °C. The obtained relative
density was 98.8% with a 0.9 mm grain size. Regarding an ap-
proximate relative density value, the grain size was 1.6 mm com-
pared with CS (temperature at 1350 °C with a 1-h holding time).
Hesabi et al. [44] applied TSS-CW to 150 nm submicrometric
alumina. Five sintering plans were used in the TSS-CW to sinter
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the material. T1 ranged from 1200 to 1300 °C, whereas T2 ranged
from 1100 to 1200 °C. Holding times of 15, 50 and 64 h were
evaluated for T2. Two compaction types were tested–namely,
uniaxial pressing and cold isostatic pressing. The authors con-
cluded that, unlike the study by Bodišová et al. [43], the initial 75%
density of the samples conformed by cold isostatic pressing is
sufficient to remove pores in the second stage. In addition, the
difference between the relative density values in the first stage
may be attributed to the green compact conformation method.
The best results were achieved by using 1250 °C in T1 and 1150 °C
in T2. By comparing their results to those obtained by Bodišová
et al. [43], it was possible to see that T1 was significantly lower
(1250 °C), although T2 (1150 °C) remained the same and that the
final grain size was 0.5 mm. It was also concluded that the size and
distribution of the pores after the first sintering stage determined
the critical density, which ensured the success of two-step sin-
tering [44]. The mechanical properties of the alumina samples
were evaluated. Samples with the best relative density (98%) and
smaller grain size (0.5 mm) had a hardness value of 18.2 GPa, ex-
ceeding the 15.01 GPa value of a sample with larger grain size
(0.85 mm). The fracture toughness value between 4.24 and
4.29 MPa m1/2 was similar in both samples and is in the range of
values reported in the literature.
A zirconia-doped alumina (5 wt%) with submicrometric grains
and high density was evaluated [45]. The alumina particle size was
150 nm. Two tests were initially performed. The first test was
performed to determine the first sintering stage. The samples were
heated at 10 °C min  1 to 1525 °C. The second test consisted of
isothermal sintering in the range of 1250–1450 °C at the rate of
10 °C min  1 for 0–8 h. TSS-CW was performed after the pre-
liminary tests. T1 and T2 ranged from 1400 to 1450 °C and from
1300 to 1400 °C, respectively. The holding time in the second stage
was evaluated for each sintering plan at 4, 8, 12 and 24 h. The
authors concluded that 1450 °C is the best temperature for the
first sintering stage because lower final density was obtained using
lower temperatures, regardless of the holding time in the second
stage. Regarding the second sintering stage, 1350–1400 °C was
found to be the best temperature range because there was good
material densification, without the apparent surface diffusion ef-
fect on grain growth. The authors also evaluated the presence of
zirconia. Compared with the study by Bodišová et al. [43], the
elevated temperature in the second stage was explained by the
presence of zirconia, which increases the activation energy to
densify the alumina. Another observation was related to the grain
growth inhibition caused by zirconia, which induced a change in
the kinetic window to a higher temperature and changed the re-
lationship between grain size and density, compared with pure
alumina. The final ceramics obtained by the introduction of zir-
conia had relative density exceeding 99% and grain size of 0.62–
0.88 mm. By comparing the study by Hesabi et al. [44] and that by
Bodišová et al. [43], who both worked with uniaxial pressing, it
was possible to see that the effect of zirconia was decisive in grain
growth inhibition. However, Hesabi et al. [44] obtained a smaller
grain size (0.5 mm).
Galusek et al. [46] evaluated the influence of doping agents on
alumina, such as MgO, which is known to increase densification
and grain growth, and Y2O3 and ZrO2, which are known as grain
growth and densification inhibitors. These oxides were added
(500 ppm) to an alumina with a 150 nm particle size and sintered
through TSS-CW. The temperature in the first stage was de-
termined by heating the samples at a temperature range between
1300 and 1475 °C and immediately cooling them to room tem-
perature. Regarding the dopant-free compositions with MgO ad-
dition, the temperature in the first stage was 1360–1400 °C. In
contrast, the temperature was higher (1450–1475 °C) in the com-
positions with Y2O3 and ZrO2. The presence of defects due to
12561
limitations in the compaction process is usually the reason why
the ceramics are not fully densified. Therefore, all compositions
were sintered for 1 h at 1450 °C, which is the condition required
for the complete densification of non-doped powders (1 h at
1300–1350 °C). The maximum relative density did not exceed 99%,
which was considered to be the limit for samples compacted by
uniaxial pressing and by cold isostatic pressing. To minimize grain
growth, the temperature in the second stage was determined
based on the lowest temperature at which the relative density of
99% was achieved in less than 24 h of holding time. The tem-
peratures in the second stage were 1150 °C for pure alumina,
1200 °C for MgO-doped alumina, and 1300 °C for
Y2O3-and-ZrO2-doped alumina. Regarding the non-doped alumi-
na, coarsening was found in the microstructure at the final sin-
tering stage, and a final grain size of 650 nm was obtained. The
doping using MgO, Y2O3 and ZrO2 resulted in grain growth sup-
pression at the final sintering stage. The doped samples were
sintered up to the relative density near 100%, and the mean grain
size was 500 nm. The MgO-based doping was considered to be
more advantageous because of the lower sintering temperature
required to achieve high final density. The grain size obtained by
adding dopant agents to the alumina (500 nm) was the same value
found by Hesabi et al. [44] in a study conducted on pure alumina.
Two types of hexagonal α-alumina with particle sizes of
100 nm (TAI) and 240 nm (REY), one 60 nm tetragonal zirconia
(Z3Y) and one 140 nm cubic zirconia (Z8Y) were investigated. The
thermal treatment was performed at heating rates of 10 °C min  1
to 800 °C and 5 °C min  1 to T1 (it varied according to each ma-
terial). Subsequently, the samples were kept at T2 for 0, 5, 10, 15
and 20 h using a cooling rate of 60 °C min  1. By comparing the
results, the authors found little success in the alumina sintered
through TSS-CW. The grain size values were lower, but they
showed little difference: 0.66 mm TAI for CS, 0.51 mm for TSS-CW
and a decrease from 0.93 to 0.82 mm for REY alumina. The zirconia
samples showed Z8Y improvement and no change in Z3Y. The Z8Y
relative density was 99.54%, and the grain size was 3.58 mm in CS.
Regarding the TSS-CW, T1 was 1440 °C and T2 was 1340 °C for
10 h, reaching 99.54% relative density and 1.71 mm grain size. A
smaller microstructural refinement was found in the hexagonal
alumina, and no effect was found in the tetragonal zirconia. The
authors suggested that the efficiency of two-step sintering in-
creases because of the ceramic crystal symmetry, which is more
influential than the particle size and the microstructure of the
green body [38].
4.4. Yttria (Y2O3)-stabilized zirconia (ZrO2)
The TSS-CW application to yttria-stabilized zirconia has sa-
tisfactorily reduced grain growth compared with the conventional
method (CS); however, a certain limitation was observed in tech-
niques such as SPS (sparking plasma sintering) and microwave
sintering. The good homogeneity of the green samples proved to
be an important condition for TSS-CW applicability.
Lee [47] evaluated 3 mol% Y2O3-stabilized zirconia (Z3Y pow-
der) and organic polymers of polyvinyl butanol (PVB) and dibu-
tylphthalate (DBP) in solvent ethanol. The mean particle size was
0.27 mm. The conformation stage was carried out on an injector
with 680-bar pressure at 140 °C, and the samples were thermally
treated through CS and TSS-CW. The CS technique used a heating
rate of 10 °C min  1 to 1500 °C with a 30-min holding time. Re-
garding the sintering through TSS-CW, the same heating rate was
used to T1 at 1500 °C for 5 min; the second stage was carried out
at 1300 °C (T2) for 10 h. The TSS-CW technique obtained samples
with a 0.59 mm grain size, whereas the CS samples had a 1.05 mm
grain size. The flexural strength of the samples obtained through
the TSS-CW technique was approximately four times greater than
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that of the samples obtained though CS, i.e., 1078 and 295 MPa,
respectively.
Mazaheri et al. [48] studied ZrO2 with 3 mol% yttria, with a
mean particle size of 75 nm. The powder was compacted in a cy-
lindrical die at 150 MPa to produce green compacts. The samples
were sintered in a single stage at a heating rate of 5 °C min  1 and
a temperature range from 1100 to 1500 °C with 50 °C intervals
between the temperatures. The holding time ranged from 1 to 8 h.
The TSS-CW specimens were heated at 5 °C min  1 to T1 (1300 and
1350 °C), kept at T1 for 1 min, and cooled at 50 °C min  1 to T2
(1050 and 1250 °C), with holding times between 2 and 30 h. The
CS technique obtained compacts with a grain size of 275 nm;
however, the use of CW-TSS showed that the grain growth rate
might be further reduced. The sintering program that showed the
best results used T1 at 1300 °C for 1 min The critical density ob-
tained in the first stage was 83% of the theoretical density, and the
second stage was processed at 1150 °C for 30 h. Samples with
maximal densification and a 110 nm mean grain size were ob-
tained. By comparing the study by Mazaheri et al. [48] to the study
by Lee [47], it is observed that the difference in the powder par-
ticle size (0.27 mm and 75 nm) and the conformation processing
(injection and pressing process) affected the final grain size of the
samples. Mazaheri et al. [48] obtained bodies with a smaller grain
size; however, the TSS-CW technique proved to be satisfactory
when compared with the CS technique in both studies.
By using 3 mol% Y2O3-doped tetragonal ZrO2 powder with a mean
particle size of 65 nm, Suárez et al. [49] investigated the effects of the
bead-milling treatment on colloidal processing. A comparison be-
tween two processes, i.e., colloidal processing and bead-milling
processing, was performed. Aqueous ceramic suspensions with
30 vol% of solid loading were prepared in the colloidal processing by
dispersing the ZrO2 powder in distilled water using different
amounts of polyelectrolyte. The aqueous ceramic suspensions were
dispersed in an ultrasonic stirrer for 15 min The slip-cast samples
were dried slowly to avoid cracking and were cold isostatically
pressed at 392 MPa. The bead-milling processing uses bead-milling
equipment comprising ZrO2 beads with a 50 mm diameter at
4000 rpm. The suspension obtained after 60 min of treatment was
evacuated, slip-cast and cold isostatically pressed at 392 MPa for
comparison with the cast samples without bead milling. The tem-
perature in the first TSS-CW sintering stage was 1300 °C, without
holding time, and the temperature in the second stage was 1200 °C
for 15 h. The temperature of 1250 °C for 3 h was used in CS. By using
the bead-milling equipment and the TSS-CW, it was possible to see
better sinterability in the samples, with relative density near 100%
and smaller grain size (155 nm for CS and 125 nm for TSS-CW, re-
spectively). The samples without milling showed 99% densification,
with grain sizes of 160 nm for CS and 150 nm for TSS-CW.
Suárez et al. [50] evaluated the effect of starting powders on
sintering. The used starting materials were high-purity monoclinic
zirconia (TZ0, particle size of 74.8 nm), commercial Y2O3 powder
and 3 mol% Y2O3-stabilized tetragonal ZrO2 (3YTZ, 65 nm particle
size). Suspensions were prepared through colloidal processing and
bead-milling processing [49], and the thermal treatment was
carried out through three different methodologies: CS, TSS-CW
and SPS. Regarding CS, a heating rate of 3 °C min  1 to 1250 °C was
used, with a 5-h holding time. By comparing TZ0 and 3YTZ, the
authors found that the relative densities were the same (greater
than 99.5%) at this temperature, whereas the grain sizes were 113
and 175 nm, respectively. The TSS-CW temperatures were defined
as T1 at 1300 °C without holding time and T2 at 1200 °C for 15 h.
However, because the initial compositions were different, there
was a decrease in grain size in TZ0 compared with 3YTZ, i.e., 95
and 125 nm, respectively. The SPS method was carried out at
1150 °C, with a heating rate of 300 °C min  1, pressure of 150 MPa
and 30-min holding time. There was a reduction in the grain size
in TZ0 (90 nm) compared with 3YTZ (115 nm). By comparing the
used sintering processes, it was found that the TSS-CW produced
samples with a smaller grain size than those found in the CS.
However, between both techniques, SPS yielded samples with
smaller grain sizes [50].
Xiong et al. [51] evaluated 3 mol% yttria-doped zirconia. The
powders were spherical granules ranging from 60 to 120 mm by
thermal spraying. Two different methods were evaluated for the
first stage of the thermal treatment. One of them was pressureless
sintering, which was carried out in a self-made air furnace. First,
samples were conformed by uniaxial pressing and then compacted
by cold isostatic pressing. The other method was the high-pressure
spark plasma sintering (referred to as HPSPS) technique. The CS
technique used a heating rate of 10 °C min  1 to 1250–1350 °C,
with a 1-h holding time. Regarding the TSS-CW, the heating rate
was 10 °C min  1 to T1 at 1250–1300 °C, with a 1-min holding
time. The temperatures of the second stage were 1150 and 1175 °C
with 30- and 20-h holding times, respectively. The second method
was carried out with the initial pressure of 100 MPa up to 600 °C
with a 3-min holding time. The pressure was then increased to
300 MPa, where it remained until the end of the cycle with a
temperature of 1000 °C for 5 min The temperature in the second
stage was 1100–1175 °C, with a 30-h holding time. By comparing
the sintering methods, it was found that the TSS-CW (T1 at
1300 °C and T2 at 1175 °C for 20 h) achieved 99.2% relative density,
with a small grain size (184 nm). The TSS treatment through
HPSPS (T2 at 1175 °C for 30 h) resulted in a smaller grain size
(173 nm); however, the density was lower (97.46%). Finally, the
high relative density of 99.92% was achieved in CS (1350 °C);
however, the grain size reached 221 nm [51].
Ghosh et al. [52] studied zirconia containing 8 mol% yttria in
nanocrystalline form synthesized by the co-precipitation method.
The formation of an easily filterable hydroxide was facilitated by
the addition of ammonium sulfate and polyethylene glycol during
precipitation. The precipitate was then calcined to produce na-
nocrystalline powder. CS was carried out between 1000 and
1400 °C. The heating rate was 5 °C min  1 to 1000 °C, followed by
decreasing at 1 °C min  1 to the desired temperature (3-h holding
time). The TSS-CW used a heating rate of 5 °C min  1 to 1000 °C,
which decreased to 1 °C min  1 until it reached 1125 °C (3-h
holding time). T2 was 1090 °C (20-h holding time). The powder
enabled the obtainment of relative density exceeding 95% at a low
temperature (1150 °C) in CS. By comparing the grain sizes between
the two sintering processes, CS and TSS-CW, little difference (150–
180 and 185–220 nm grain sizes, respectively) was found. Re-
garding the mechanical evaluation, the hardness range was 9–
11 GPa, and the fracture toughness was 5.3 MPa m1/2 for the two
evaluated thermal treatments.
Lourenço [53] studied two commercial yttria-stabilized zirco-
nia powders synthesized by co-precipitation. One powder had a
tetragonal phase partially stabilized with 3 mol% yttria (Z3Y), and
the other had a cubic phase stabilized with 8 mol% yttria (Z8Y).
The mean particle size ranged from 25 to 70 nm. The TSS-CW
sintering process enabled grain growth inhibition through the Z3Y
powder and produced dense microstructures with a grain size of
approximately 100 nm. The sintering program used T1 at 1320 °C
and T2 at 1250–1270 °C for 12 h. The mean grain size of the single-
step sintered bodies (1500 °C for 2 h) was approximately 200 nm.
The grain growth was also inhibited in the Z8Y composition, and a
mean grain size of 450–460 nm was obtained under the conditions
of T1 at 1320–1340 °C and T2 at 1270 °C (12-h holding time). The
grain size of the samples was 1 and 2 mm in the Cs cycle. The Z8Y
grain size found by Lourenço [53] was higher (450–460 nm) than
that obtained by Ghosh et al. [52]. The difference in the results
obtained in these two studies may be explained by the different
used starting powders and by the TSS-CW sintering programs.
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Lourenço et al. [54] considered the experimental data by
Lourenço [53] and evaluated the TSS-CW method using predic-
tions of sintering kinetics based on shrinkage data with Taguchi
fractional experimental plans. The authors concluded that T1 may
be defined as the temperature at which 75% of the relative density
is achieved in Z3Y. The temperature range with typical Arrhenius
dependence was taken as a guideline to determine T2 and its re-
spective holding time. The data found from the sintering kinetics
predictions were similar to the results of the experiments planned
according to the Taguchi method. However, the methodology was
not considered suitable for Z8Y because the temperature range
required to attain unstable microstructures already yielded an
increase in the grain size by nearly one order of magnitude.
Nanocrystalline 8 mol% yittria-stabilized zirconia was synthe-
sized using modified glycine-nitrate [55]. The TSS-CW used T1 at
1250 °C and a heating rate of 5 °C min  1 and T2 at 950 and
1050 °C, with a cooling rate of 50 °C min  1 and a 20-h holding
time. Single-step sintering was performed using the same heating
rate at 1500 °C, without holding time, and it was compared with
the TSS-CW. The variation in T2 allowed the authors to observe
that the highest temperature (1050 °C) showed the best result
with respect to the grain growth and densification process. When
a lower temperature (950 °C) was used, no densification was ob-
served even after prolonged soaking treatment. However, there
was significant reduction in the grain size values: 2.15 mm for the
samples sintered through CS and 295 nm for those sintered
through TSS-CW. Hardness and fracture toughness were also ob-
served: 12.87 GPa and 1.61 MPa m1/2 for CS; and 13.51 GPa and
3.16 MPa m1/2 for TSS-CW, respectively.
Mazaheri et al. [56] conducted a comparative analysis of three
sintering techniques using nanocrystalline 8 mol% yittria-stabi-
lized zirconia synthesized using a glycine-nitrate process. Micro-
wave sintering was evaluated in addition to the two treatments
(CS and TSS-CW) used in the study by Mazaheri et al. [55]. A
temperature of 1500 °C was used in the microwave sintering at
two different heating rates: 5 °C min  1 (lower-rate microwave
sintering, LMS) and 50 °C min  1 (higher-rate microwave sintering,
HMS). After the samples reached the maximum temperature, they
were cooled to room temperature. The relative density value in all
sintering methods was 97%. The grain size was 2.14 mm for CS,
2.35 mm for LMS, 0.9 mm for HMS, and 0.29 mm for TSS-CW. A
comparison was also performed between the fracture toughness
values. The samples treated through HMS (3.17 MPa m0.5) and TSS-
CW (3.16 MPa m0.5) had higher values than did those that were
conventionally treated (1.61 MPa m0.5) and those treated through
LMS (1.9 MPa m0.5). Despite the larger grain size in the HMS
sample, the fracture toughness value was similar to that of TSS-
CW. According to the authors, this was due to the higher micro-
structural homogeneity caused by HMS. It was also reported that
despite the known ability of the TSS technique to inhibit ac-
celerated grain growth, factors such as the lack of microstructural
homogeneity and the long total sintering time (4 20 h), compared
with that of HMS (29 min), show that there are restrictions on the
application of the TSS-CW method [56].
The influence of two conformation methods, uniaxial dry
pressing (DP) and slip casting (SC) [57], was evaluated for nano-
crystalline 8 mol% yttria-stabilized zirconia powder processed
through the glycine-nitrate combustion method [55]. Several
pressures were tested in the first method (DP), and 600 MPa was
chosen because it achieved 48% relative density. Regarding SC,
suspensions were prepared with 42–67 wt% solids, and 65 wt%
was used with 60% relative density. The same thermal treatments
of the previous study [56] were used: CS, TSS-CW and microwave
sintering. By comparing the two conformation methods sintered
by CS, the SC method yielded better results. The improved green
properties resulted in a lower sintering temperature and smaller
12563
grain size compared with those of DP. The DP grain size was
2.15 mm, whereas the SC grain size was 1.3 mm. DP specimens were
sintered through microwave sintering and TSS-CW to evaluate the
sintering process effect. A smaller grain size (0.295 mm) was ob-
tained through TSS-CW. By using the same conformation techni-
que and microwave sintering, the grain size was 0.9 mm. According
to the authors, pinning the grain boundaries through immobile
triple junctions in the two-step sintering method ensured grain
growth inhibition [57].
Schwarz and Guillon [58] evaluated zirconia with 8 mol% yttria
and a mean particle size of 58 77 nm. Two methods were applied
in the conformation of the specimens: pressure filtration and dry
pressing. A suspension was prepared and filtered under pressure
in the pressure filtration process. It was then pressed in a me-
chanical testing machine with a maximum pressure of 50 MPa,
which was kept for 15 min Dry pressing was the other compaction
performed at 50 MPa in the graphite tool. The thermal treatment
was carried out through the field-assisted sintering technique,
which is known as spark plasma sintering (SPS). The heating rate
was 200 °C min  1 to T1 at 1150 °C (kept for 20 s) at an initial
pressure of 10 MPa, which was increased to 50 MPa when the
temperature was 200 °C from T1. T2 was 1050 °C, with 2- and 5-h
holding times. The samples were heterogeneous in the dry pres-
sure conformation, and a micrometric grain size was reached
(1.67 mm), despite the TSS-CW and the incomplete densification
(93.6% relative density). The samples conformed by pressure fil-
tration showed lower grain growth (190 nm) even for a high
density (99.8% relative density). According to the authors, the
homogeneous densely packed green body plays an important role
in the grain growth control for the success of the TSS-CW meth-
odology and the pressure-assisted sintering method.
4.5. Titanium dioxide (TiO2)
Mazaheri et al. [59] used TiO2 nanopowders with particle size
in the range of 11–27 nm and containing 77% anatase and 23%
rutile. The powder was uniaxially pressed at 100 MPa and ther-
mally treated though CS and TSS-CW. The CS treatment used a
heating rate of 5 °C min  1 to temperatures in the range of 500 and
1000 °C for 1 h. The TSS-CW treatment used a heating rate of
5 °C min  1 to T1, which was held for 1 h, and a cooling rate of
50 °C min  1 to T2 (700 °C), with a holding time of up to 30 h. Two
temperatures were used as T1 to reveal the structural change
between the anatase and rutile phases: 800 °C with a 25-h holding
time in T2 (TSS1) and 750 °C with a 30-h holding time in T2 (TSS2).
Grain sizes between 1 and 2 mm were obtained in CS for sintering
at 1000 °C for 1 h. By comparing the TSS-CW results, it is possible
to see that the TSS1 process reached a grain size of approximately
250 nm with a relative density higher than 98% using an amount
of rutile near 100% at the beginning of T2. TSS2 reached a grain
size of approximately 100 nm and a relative density greater than
98% using an initial amount of 88% rutile and 12% anatase at the
beginning of T2. The use of TSS-CW along with the phase trans-
formation evaluated at the TSS2 process allowed a more refined
structure to be obtained (100 nm).
Mazaheri et al. [60] compared CS and TSS-CW to the SPS pro-
cess evaluated by Lee et al. [61] to evaluate the TSS-CW process
applicability to TiO2 nanostructures. The CS heating rate of
5 °C min  1 was used to temperatures in the range of 500–1000 °C
for 1 h. The TSS-CW consisted of a heating rate of 5 °C min  1 to
800 °C (T1), which was held for 1 h, and cooled at the rate of
50 °C min  1 to 700 °C (T2), which was held for 25 h. By comparing
the obtained data to the study by Lee et al. [61], it was possible to
see that the SPS method used to sinter the TiO2 resulted in grain
size and relative density similar to those found in the TSS-CW
method. The grain size in the SPS treatment was 200–300 nm, and
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the relative density was 98%, whereas the grain size in the TSS-CW
was 250 nm and the relative density was 98%. Considering the SPS
process, the authors state that the TSS-CW method is a simple and
feasible process in the obtainment of TiO2 nanostructures.
Li et al. [62] used TiO2 with a mean particle size between 30 and
40 nm and performed a two-step sintering thermal treatment using
the spark plasma sintering (SPS) parameters assisted by TSS. A low
pressure of up to 30 Pa was used in the beginning of the (SPS)
process to reach the maximum temperature. The heating rate was
100 °C min  1, and the holding time ranged from 1 to 60 min A
temperature of 850 °C with a 1-min holding time was used in T1. T2
featured a temperature range between 810 and 840 °C with high
densification and invariable grain size. The best relative density and
grain size values, 97.7% and 40 nm, respectively, were found using
T1 at 850 °C and T2 at 830 °C. By comparing the TSS-CW, SPS and
TSS-assisted SPS processes through the D/Do ratio value (found
grain size/initial grain size), values near 10 were found for TSS-CW,
between 3 and 6 for SPS, and near 1 for TSS-assisted SPS. The TSS-
assisted SPS value showed virtually no grain growth. These results
demonstrate that the combination of the SPS and TSS techniques
may suppress the growth of grains more effectively than when the
two techniques are used separately.
It is clear that the TSS-CW method applied to TiO2 favors grain
growth reduction, with values similar to those of the expensive
SPS process. In addition, lower T2 combined with a longer holding
time allowed smaller grains to be obtained, as observed in other
materials.
4.6. Barium titanate (BaTiO3, BTO)
The BaTiO3-related literature shows that lower sintering tem-
peratures are necessary in both TSS-CW process stages to obtain a
smaller grain size. The initial particle size of BaTiO3 and the ad-
dition of dopant agents also help obtain a smaller final grain size.
Kim and Han [63] evaluated a BaTiO3 nanometric composition
with a particle size of approximately 17 nm and a BaTiO3-doped
mixture of 1 mol% dysprosium (Dy), whose samples were pressed
at 300 MPa. The TSS-CW treatment used T1 at 1300 °C and T2 at
1100 °C for 0–20 h. The CS temperature was 1200 °C, for 1–5 h. The
density achieved in the CS treatment with a 5-h holding time was
5.6 g cm  3, corresponding to more than 93% of the theoretical
density and grain size in the range of 5–6 mm. Regarding the TSS-
CW treatment, the best result was found using a 20-h holding
time, in which the relative density was 5.7 g cm  3 (approximately
95% relative density) with a grain size near 1 mm. The use of
1 mol% BaTiO3-doped Dy led to approximately 93% relative density
with a smaller grain size (between 200 and 400 nm).
Wang et al. [64] evaluated high-purity BaTiO3 powders with a
particle size between 10 and 30 nm and a nanocrystalline ferrite
composed of Ni0.2Cu0.2Zn0.6Fe2O4 with a 10 nm particle size. The
conformation was performed by isostatic pressing at 200 MPa.
Different sintering programs were analyzed for TSS-CW. The
heating rate was 10 °C min  1 to T1 at 950–1250 °C for BTO and at
850–930 °C for ferrite. The cooling rate for T2 was 30 °C min  1,
and T2 varied from 1150 to 850 °C for BTO (holding time between
2 and 20 h) and from 750 to 870 °C for ferrite (holding time be-
tween 4 and 12 h). Samples with more than 96% relative density
were obtained for all sintering runs by applying TSS-CW. Up to
100% relative density was achieved in a ferrite sample. The sample
sintered at 950 °C in T1 and at 900 °C in T2 for 2 h showed the best
result for BTO, in which the obtained grain size was 35 nm
(starting particle size of 10 nm). A grain size of 1.2 mm was
achieved in CS (starting particle size of 30 nm) at 1200 °C for 2 h.
The ferrite sintered at 850 °C in T1 and at 800 °C for 6 h in T2
exhibited the smallest grain size (200 nm) among the tested
samples. Samples with a grain size of 2 mm were obtained at
900 °C for 4 h in CS. By comparing these results with those found
by Kim and Han [63], who obtained Dy-doped BTO samples with a
200–400 nm grain size, it is possible to see that Wang et al. [64]
obtained samples with a smaller grain size (35 nm). The con-
formation method, the lower T1 and T2 temperatures, and the
shorter holding time in the second stage were the main differ-
ences observed.
Karaki et al. [65] evaluated hydrothermally synthesized BaTiO3
with a 100 nm particle size. The specimens were compacted at
200 MPa. During the sintering stage, the samples were heated at
10 °C min  1 to T1 (1230–1340 °C) and held for 1 min Next, they
were cooled to T2 (1150 and 1200 °C) at 30 °C min  1 and held for
2, 4, 15 and 20 h. The sintering program with T1 at 1320 °C, T2 at
1150 °C and a 15-h holding time showed the best result. The mean
grain size was 1.6 mm with relative density of 98.3%. The study also
evaluated the piezoelectric material properties, and the authors
stated that the grain size and density strongly influenced the final
properties and noted the advantage that BaTiO3 was manufactured
using a low-cost process.
Isostatic pressing was performed at 200 MPa using high-purity
BTO with a mean particle size ranging from 10 to 30 nm [66]. The
applied TSS-CW used a heating rate of 10 °C min  1 to T1 (920–
1250 °C), which was immediately cooled at 30 °C min  1 to T2
(1150–850 °C) with holding times in the range of 4–20 h. CS was
performed at a heating rate of 10 °C min  1 to 1200 °C for 2 h, and
it led to 97% relative density and a 1.2 mm grain size. Regarding
TSS-CW, the relative density also reached 97% using T1 at 980 °C
and T2 at 900 °C with a 4-h holding time; however, the grain size
was reduced to 70 nm. Powder with a particle size smaller than
10 nm was cold pressed at 200 MPa and treated at 920 °C in T1 and
at 850 °C for 20 h in T2, reaching 99.6% relative density and a
smaller grain size between 8 and 10 nm. According to the authors,
it was the first study that obtained a dense BTO nanocrystalline
structure with such a reduced grain size using pressure-free
sintering.
Huan et al. [67,68] used TSS-CW to prepare BTO with an initial
particle size of 100 nm and different final grain sizes. The com-
pacts were isostatically pressed at 200 MPa. The samples were
heated at 10 °C min  1 to T1, and they were then cooled at
20 °C min  1 to T2. Different sintering conditions were applied. The
T1 temperatures were 1250, 1280, 1310, and 1340 °C, and the T2
temperatures were 800, 850, 900, 950, 1000, 1050 and 1100 °C. The
holding time in the second stage was 24 h in all evaluated con-
ditions. A number of BTO ceramics with high density (greater than
95%) and different grain sizes (from 0.29 to 8.61 mm) were suc-
cessfully produced through TSS-CW. In addition, it was observed
that the piezoelectric coefficient is strongly influenced by grain
size, enabling the obtainment of high-performance BTO ceramics
through TSS-CW.
4.7. Carbides
SiC (silicon carbide) nanostructured ceramics were obtained
through TSS-CW. According to the literature, TSS-CW allows the
sintering temperature to be reduced by 50–200 °C compared with
SC, with the same relative density. Thus, the particle size obtained
through CS is approximately 2–3 times greater than that obtained
through TSS-CW, with significant influence on the mechanical
properties.
Lee et al. [69] evaluated the two-step sintering process used to
obtain SiC (silicon carbide) nanostructured ceramics in the pre-
sence of the liquid phase. The SiC composition containing 7 wt%
Al2O3, 2 wt% Y2O3 and 1 wt% CaO and a mean particle size of
20 nm was processed by milling in a vibratory mill. The compacts
were sintered at 20 MPa using three different sintering programs.
The CS specimens were sintered at 1500 and 1550 °C for 8 h and at
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1750 °C for 5 and 30 min The second sintering program—the so-
called "zero-time sintering"—had no holding time at 1700, 1750,
1800 and 1850 °C. Finally, the TSS-CW was performed with T1
ranging from 1650 to 1750 °C and with T2 at 1500 °C or 1550 °C,
with an 8-h holding time. Among the evaluated sintering pro-
grams, TSS-CW with T1 at 1750 °C and T2 at 1550 °C for 8 h
showed the best results. Specimens with 99% relative density and
a 43 nm grain size were obtained. According to the authors, the
size and density of the pores obtained after the first sintering stage
are critical to obtain high density in the second sintering stage.
Relative densities exceeding 85% in the first stage were required in
this study. Lee et al. [69] concluded that TSS-CW might be applied
to sintering in the presence of the liquid phase.
Lee et al. [70] investigated the TSS-CW process parameters
using the same material: SiC with the addition of Al2O3, Y2O3 and
CaO. Twelve experimental runs were conducted by varying T1
(between 1550 and 1750 °C), T2 (1550 and 1600 °C) and the
holding time in the second stage (0, 1, 4 and 8 h). After analyzing
the results, the authors suggested that SiC nanostructures might
be manufactured using T1 of 1700–1750 °C and T2 of 1550–1600 °C
for 8 h. The smaller grain size obtained in their study was near
40 nm, approximately two times the initial particle size. The au-
thors suggested the existence of a processing window for nanos-
tructured microstructures, i.e., a "quasi-frozen region". In this
window, there is a separation of grain growth densification during
the liquid-phase sintering in other liquid-phase sintered systems.
Magnani et al. [71] used α-SiC with sintering aids, boron (B) and
carbon (C), as the starting powder to manufacture SiC ceramics by
pressureless sintering using the TSS-CW method. The specimens
were obtained by uniaxial pressing at 60 MPa, followed by cold
isostatic pressing at 200 MPa. The sintering stage was carried out
using an argon stream at 1 atm. CS used the temperature of 2200 °C
for 1 h, whereas SST-CW used T1 at 2100 °C and T2 at 2050 °C, with
a 7-h holding time. There was sharp grain growth (more than
100 mm) in CS, whereas the grain size was approximately 30 mm in
TSS-CW. These values were obtained for virtually the same relative
density, 97% and 97.7%, respectively. The authors concluded that the
TSS-CW carried out at a temperature lower than that of CS (2050 °C
instead of 2200 °C) leads to the same densification with grain
growth suppression. With respect to the evaluated mechanical
properties, it was observed that the flexural strength was most in-
fluenced by grain size reduction. The CS value was 341 MPa,
whereas the SST-CW value increased to 556 MPa. The hardness and
fracture toughness values were the same for both processes.
Magnani et al. [72] used the same starting material, commercial
SiC powder containing boron carbide and carbon as sintering aids,
to manufacture specimens through uniaxial pressing at 100 MPa,
followed by cold isostatic pressing at 200 MPa, by changing the
sintering temperatures. The CS treatment was carried out at 2130 °C
for 1 h, whereas TSS-CW was conducted with T1 at 2030 °C and T2
at 1980 °C for 7 h. By reducing the temperature of the second stage
from 2050 to 1980 °C, specimens were obtained with a refined
microstructure comprising equiaxed grains and some elongated
grains with a 10-mm grain size (the grain size is approximately
100 mm in CS). Despite the microstructural differences, samples
subjected to CS and TSS-CW exhibited very close relative densities
of 98.6% and 98.4%, respectively. Better results were found using a
lower sintering temperature for SiC consolidation. The flexural
strength values were higher (530710 MPa) than those of the CS-
sintered samples (480712 MPa). In addition, the high flexural
strength value was similar to the values found in more complex and
expensive sintering techniques such as hot pressing and spark
plasma sintering.
An investigation with tungsten carbide and magnesium oxide
nanocomposite (WC-4.3 wt% MgO) [73] was performed through
two-step hot-pressing sintering and compared with conventional
12565
hot-pressing sintering. Regarding conventional hot-pressing sin-
tering, the bodies were hot-pressed at 1450–1900 °C, with 0.13 Pa
vacuum, a temperature range of 50 °C and a heating rate of
10 °C min  1. The specimens were held at the highest temperature
for 3 min under a pressure of 39.6 MPa to obtain a uniform tem-
perature in the entire sample. Regarding TSS-CW, the samples
were heated under the same CS conditions, with T1 at 1750 °C. The
applied cooling rate was 60 °C min  1, and T2 was evaluated at
1450, 1550 and 1650 °C for 2, 4 and 8 h under a pressure of
39.6 MPa. A temperature of 1550 °C in the second stage resulted in
99% densification and a 2.58 mm grain size. At 1650 °C, the relative
density was also near 99%, but the grains grew to 2.99 mm. The
temperature of 1550 °C provided a more homogeneous and more
consolidated structure than that of CS. The mechanical properties
of the nanocomposite were improved; the hardness improved
from 16.7 to 18.4 GPa, whereas the flexural strength increased
from 976.6 to 1283.7 MPa. The fracture toughness, which was
10.2 MPa m0.5 in CS, increased to 12.95 MPa m0.5 in TSS-CW.
Qu and Zhu [74] evaluated the two step hot-pressing sintering
in WC-Al2O3 composites (WC–40 vol% Al2O3). To perform the hot-
pressing sintering, pressure of 39.6 MPa was used in 0.13 Pa va-
cuum, with heating rate of 10 °C min  1. The temperature range
used in CS was 1450 b750 °C for 90 min, with temperature inter-
vals of 50 °C. Regarding the two step hot-pressing sintering, the
samples were heated at 1650 and 1600 °C (T1), kept for 3 min, and
then cooled down to T2 (1500, 1450 and 1400 °C), with holding
times of 2, 4 and 6 h. The sintering regime with T1 at 1600 °C and
T2 at 1450 °C inhibited the accelerated growth of grain size, which
was 2.38 mm (2.79 mm for CS) with 99% relative density. The im-
provements in the samples due to microstructure refinement re-
flected in the mechanical properties. The hardness of the CS-
treated samples increased from 18.65 to 19.71 GPa. The fracture
toughness and flexural strength increased from 10.43 MPa m0.5
and 756 MPa m0.5 to 12 MPa m0.5 and 1285 MPa m0.5, respectively.
4.8. Corundum abrasive
Few studies related to corundum abrasive sintering through
TSS-CW have been identified. However, the obtained results de-
monstrate that this method is effective in grain growth inhibition
and allows better mechanical properties to be obtained compared
with CS. By considering the same maximum sintering temperature
and the same holding time, the grain size is 5–10 times greater in
CS, thus significantly affecting hardness, fracture toughness and
wear resistance.
Li et al. [75] evaluated corundum abrasive prepared by the sol-
gel process with sintering additives (MgO-CaO-SiO2). Two sinter-
ing programs were applied: CS and TSS-CW. CS was carried out at
1250 and 1300 °C (T1) at the rate of 4 °C min  1, without holding
time, followed by cooling to room temperature (25 °C). Next, the
samples were heated again to 1150 °C (T2) and held for 5 h. Al-
though the authors named this sintering plan CS, Li et al. [76]
renamed it as a third sintering method called CTS. The same
temperatures were used in TSS-CW, i.e., T1 at 1250 and 1300 °C
and T2 at 1150 °C for 5 h. Materials with relative density greater
than 99.2% were obtained in both TSS-CW cycles. The grain size of
the samples was smaller than 100 nm, whereas the grain size in CS
ranged from 480 to 610 nm. The liquid phase formation sintering-
aid oxides (MgO-CaO-SiO2) contributed to grain growth suppres-
sion and to nearly full densification owing to the formation of a
continuous amorphous silicate film in the material. The wear re-
sistance was also evaluated in the tested processes and, according
to the authors, the TSS-CW-sintered samples were considered to
exhibit excellent results. The wear rate of samples sintered via CS
was found to be 5–4  10  7 mm3 N  1 m  1, whereas TSS-CW
routes showed values o2  10  7 mm3 N  1 m  1.
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Li et al. [76] applied three different sintering methods to nano-
crystalline corundum abrasive: TSS-CW and CTS, based on the study
by Li et al. [75], and CS (temperatures of 1250 and 1300 °C and a 5-h
holding time). The smallest grain size was found in TSS-CW, be-
tween 65 and 85 nm, whereas the CS grain size ranged from 680 to
800 nm and that of CTS ranged from 400 to 560 nm. Regarding the
investigated mechanical properties, the higher hardness and frac-
ture toughness values were found for the TSS-CW technique
(22.5470.21 GPa and 3.3770.06 MPa m0.5), CTS (20.8270.22 GPa
and 2.9370.09 MPa m0.5) and CS (19.5570.43 GPa and
2.8670.08 MPa m0.5), respectively. The TSS-CW-sintered samples
also exhibited excellent compressive strength (over 39.2 N) and
wear resistance less than 1.8670.45  10  7 mm3 N  1 m  1 com-
pared with the other methods (CS and CTS).
4.9. Piezoelectric ceramics
The TSS-CW technique has also been successfully applied to
piezoelectric ceramics.
Fang et al. [77] investigated a typical Li- and Ta/Sb-modified
KNN composition, 0.9625(Na0.5K0.5NbO3)-0.0375Li(Ta0.4Sb0.6)O3.
The samples were treated by CS, with temperatures ranging from
1075 to 1120 °C and a 4-h holding time. The TSS-CW was per-
formed with T1 ranging from 1100 to 1160 °C without holding
time and T2 ranging from 1000 to 1075 °C with holding times of
12, 24 and 36 h. With respect to CS, the temperature increase in-
itially led to microstructure densification, which was followed by
the formation of a porous microstructure, with abnormal grain
growth. However, TSS-CW resulted in dense microstructures with
a bimodal grain size distribution. According to the authors, the
increased holding time in the second sintering stage allows the
pores to be eliminated, thus improving densification. The authors
concluded that TSS-CW sintering is an effective way to broaden
the sintering temperature range of KNN-based ceramics.
Li et al. [78] evaluated piezoelectric ceramics composed of
0.95(Na0.52K0.44Li0.04)(Nb0.88Sb0.08Ta0.04)O3-0.05KNbO3. The TSS-
CW sintering process was carried out with a heating rate of
10 °C min  1 to T1 (1130 and 1150 °C) and a 1-min holding time.
Next, the specimens were cooled to T2 (which ranged from 900 to
1040 °C) and held for 7 h. The condition with T1 at 1130 °C and T2
at 950 °C provided higher relative density (96.5%) and a better
piezoelectric property. The authors also concluded that the driving
force of the solution–precipitation process of the crystal particles
for liquid-phase sintering was improved by the increase in T2. This
mechanism accelerated the process of liquid phase formation and
left nano-sized spots [78].
KNN-based ceramics ((K0.4425Na0.52Li0.0375)(Nb0.8925Sb0.07Ta0.0375)O3)
were prepared by the conventional mixed-oxide method [79]. The
powders were compacted by uniaxial pressing at 300 MPa. The TSS-
CW was set with T1 at 900 °C (10-min holding time) and a heating rate
of 10 °C min  1. The specimens were then rapidly cooled to T2 (be-
tween 980 and 1040 °C) and held for 5, 10, 15 and 20 h. The micro-
structures were dense in all TSS-CW-sintered samples, and the ap-
propriate holding time increase in the second sintering stage allowed
elimination of the pores and improvement of the density. According to
the authors, T1 at 1130 °C, T2 at 1020 °C and a 15-h holding time al-
lowed the samples to exhibit excellent temperature stability over a
wide temperature range, which is useful in the application of KNN-
based ceramics.
With respect to piezoelectric ceramics (KxNa1  x)0.94Li0.06NbO3
(abbreviated as KxNLN, x ¼0.34–0.61) [80], the TSS-CW sintering
process was used with T1 at 900 °C (heating rate of 10 °C min  1
and 10-min holding time) and T2 at 1100 and 1050 °C with a 12-h
holding time. The CS temperature was held at 1080 °C for 2 h. The
evaluation of the micrographs showed that the microstructure
obtained by CS was not homogeneous and that a minority of the
grains showed a size of 10 mm, most of which were smaller than
3 mm. The TSS-CW treatment resulted in significantly different and
denser microstructures presenting a bimodal grain size distribu-
tion, and no distinct pores could be found. The TSS-CW-processed
samples had 98% relative density, whereas the CS-processed
samples had 95% relative density.
Bafandeh et al. [81] investigated KNNLT powders synthesized
by the conventional solid-state reaction method using Na2CO3,
K2CO3, Li2CO3, Nb2O5, Ta2O5, SrO and TiO2 with more than 99%
purity as raw materials. Three different sintering methods were
applied: CS, TSS-CW and microwave sintering (MWS). The CS
samples were sintered between 1060 and 1150 °C for 2 h. TSS-CW
used T1 at 1060 and 1140 °C (for 10 min) and T2 at 1000 and
1040 °C for 6 and 10 h. Regarding MWS, the specimens were sin-
tered between 950 and 1050 °C (T1) for 10 min and between 850
and 950 °C (T2) with 30- and 120-min holding times. By com-
paring the grain size results, it was found that TSS-CW effectively
inhibited grain growth compared with the conventional process.
The grain size in CS was 1.8–2.2 mm, whereas TSS-CW obtained a
grain size of 1.0–1.2 mm. However, the samples had a smaller grain
size (0.6–0.8 mm) in the MWS treatment. According to the authors,
the high heating rate during MWS affected the sintering behavior
and slowed the grain growth.
Bafandeh et al. [82] investigated CS and TSS-CW sintering using
the same material (KNN ceramics). The material was compacted at
50 MPa and sintered by TSS-CW using T1 between 1090 and
1140 °C (10-min holding time) and T2 between 1000 and 1040 °C
(holding times of 6, 8 and 10 h). The authors observed that the
grain growth rate (ratio between the grain size of the sintered
material and the particle size of the calcined powder) was ap-
proximately 8 for CS and 3 for TSS-CW. According to the authors,
there is evidence of the ability of the TSS-CW method to inhibit
grain growth. The ceramics also showed better dielectric and
piezoelectric properties compared with CS.
Regarding the use of the TSS-CW technique in piezoelectric
ceramics, it is concluded that the method mainly helps form
denser microstructures. In most of the evaluated cases, the longer
holding time in the second stage resulted in reduced pores and
increased relative density. In addition, according to Hao et al. [80],
TSS-CW further improved the piezoelectric properties of KxNLN
ceramics by
10%, thus proving to be a promising technique used
in the production of such materials.
4.10. Bioceramics
Fathi and Kharaziha [83] investigated high-purity forsterite
nanopowders. The samples were formed by uniaxial pressing at
550 MPa. TSS-CW was performed with T1 ranging from 1100 to
1300 °C and a 6-min holding time and with T2 at 750 and 850 °C
for 2–15 h. The heating rate was 10 °C min  1, and the cooling rate
between T1 and T2 was 50 °C min  1. The best results were ob-
tained with T1 at 1300 °C, T2 at 750 °C, and a 15-h holding time.
Bodies with relative density of approximately 98.5% and a grain
size of 60–75 nm were obtained. The use of the TSS-CW technique
to prepare dense forsterite ceramics showed the possibility of
obtaining good mechanical properties. Compared with the hy-
droxyapatite ceramics (HAp), which shows fracture toughness
between 0.75 and 1.2 MPa m0.5 and hardness of 700 Hv, the results
suggested that the forsterite might be significantly improved in
terms of fracture toughness and hardness, which were
3.61 MPa m0.5 and 940 Hv, respectively.
Forsterite suspensions were prepared in ethyl alcohol powder,
and sponge samples were placed in the slurry and stirred. These
samples were removed from the slurry and sintered at different
TSS-CW thermal regimes. T1 ranged from 1300 to 1600 °C, and a
holding time of 5 or 60 min was used. The second stage used a
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cooling rate of 50 °C min  1, T2 at 800 °C and holding times of 300
and 900 min A microstructure with a grain size in the range of 16–
38 nm and a 25 nm mean grain size was obtained with T1 at
1500 °C with a 60-min holding time and T2 at 800 °C for 300 min
This method provided several scaffolds with different compressive
strengths. Compressive strength values were 0.03–24.16 MPa, and
porosity was 58–88%. The authors concluded that the synthesized
scaffolds showed a nanostructure, which is crucially important to
the bioactivity and degradability of forsterite ceramics used in
biomedical applications [84].
Another study [85] used the same procedure to prepare the
samples, and the material was processed through TSS-CW. Two
lower temperatures were tested in the first stage: 1300 and
1500 °C with a 5- or 60-min holding time and T2 at 800 °C for 300
and 900 min Other properties such as bioactivity and biodegrad-
ability were analyzed in this investigation to apply this material to
tissue engineering. By processing T1 at 1500 °C for 60 min and T2
at 800 °C with a 900-min holding time, the authors obtained
samples with a grain size in the range of 18–78 nm and a mean
size of 33 nm. The results demonstrated that nanostructure scaf-
folds with a mean crystallite size of approximately 33 nm showed
suitable bioactivity.
Samples conformed by pressing at 200 MPa were prepared in
high-purity HAp materials (Ca10(PO4)6(OH)2) [86] with a mean size
of 93 nm. The samples were sintered through CS and TSS-CW. CS
used a temperature of 1100 °C for 60 s TSS-CW used T1 at 900 °C
for 60 s and T2 at 800 °C with a 20-h holding time. The same re-
lative density (98.3%) was obtained in both processes. However,
the grain size was 190 nm in TSS-CW and 1.7 mm in CS. The frac-
ture toughness increased by 95% in the TSS method, i.e., from 0.98
to 1.92 MPa m0.5, and hardness increased from 7.1 to 7.8 GPa.
Lukić et al. [87] evaluated HAp bioceramics compacted at
175 MPa and thermally treated through TSS-CW. Different sinter-
ing procedures were performed, wherein T1 ranged from 850 to
1150 °C with a 5-min holding time and T2 ranged from 800 to
1050 °C with a 20-h holding time. The specimens were sintered in
CS at 900 and 1200 °C for 1 and 20 h. The influence of the heating
rate (2, 10 and 20 °C min  1) on the non-isothermal sintering be-
havior was also evaluated. It was found that the higher heating
rate delays the densification. The difference in density became
evident at 800 °C, ranging from 2.1 g cm  3 for 2 °C min  1 to
1.9 g cm  3 for 20 °C min  1. The best results were obtained in the
TSS treatment with a heating rate of 2 °C min  1, T1 at 900 °C (5-
min holding time), T2 at 850 °C and a 20-h holding time. Samples
with 99.2% relative density and a uniform microstructure were
obtained without uncontrolled grain growth and with few pores in
the grain boundaries. The mean grain size of the samples was
approximately 75 nm. High relative density (99.5%) was obtained
in CS at 1200 °C with a 20-h holding time; however, the final grain
size was 2.25 mm. It was possible to manufacture fully dense na-
nostructured bioceramics by pressureless sintering at low sinter-
ing temperatures. Marković et al. [88] used this same TSS-CW
sintering condition to consolidate nanostructured calcium phos-
phate functionally graded materials (FGMs). The mean grain size of
the FGMs was smaller than 100 nm, and according to the authors,
the functionally graded chemical and physical properties could be
obtained through powder processing and reaction in two-step
sintering.
The consolidation of fluoridated hydroxyapatite (FHA) pow-
ders, which had a chemical composition of Ca10(PO4)6(OH)2  xFx
(wherein the x values were 0.0, 0.5, 1.0, 1.5 and 2.0) was evaluated
[89]. Uniaxial compaction was used at different pressures, from
100 to 500 MPa. CS was held in the range of 900–1150 °C in air. T1
at 975, 1000 and 1025 °C for 1, 5 and 10 min, and T2 at 850, 900
and 950 °C for 20, 22 and 24 h were investigated in TSS-CW. FHA
nanostructures were prepared using T1 at 1000 °C, T2 at 900 °C,
12567
holding times of 10 min (T1) and 24 h (T2), and compaction
pressure of 200 MPa. The best density values of 92.4 and 91.1 and
grain sizes of approximately 136 and 162 nm were obtained for
compositions with x ¼0.0 and 2.0, respectively. They also showed
the best microhardness values: 6.76 and 7.25 GPa. The authors
concluded that material density decreased because of the in-
creased fluoride in the composition; however, it increased because
of the longer holding time in the second sintering stage.
The TSS-CW technique was applied to biphasic calcium phos-
phate (BCP) bioceramics [90]. The samples were compacted at
400 MPa. CS was performed at a temperature of 1200 °C for 1 h. T1
at 1100 °C (1- to 30-min holding times) and T2 at 1000 and
1050 °C for 20 h were used in TSS-CW. The heating rate was
5 °C min  1 to T1 and 50 °C min  1 between T1 and T2. A dense
structure with non-uniform grains and a grain size of 1.4 mm was
observed in CS. The sample grain growth was suppressed by the
TSS-CW sintering using T1 at 1100 °C (30-min holding time) and
T2 at 1050 °C and a 20-h holding time. A grain size of 375 nm was
obtained with high density. The authors concluded that another
advantage of the TSS-CW technique was the lowest sintering
temperature, which enabled the material in question to obtain
benefits pertaining to biological and mechanical behavior. Re-
garding the mechanical properties, the fracture toughness was
1.11 MPa m0.5, and the hardness was 4.9 GPa; these values are
consistent with those obtained in the application of more so-
phisticated sintering techniques, with slightly higher values for
fracture toughness.
The TSS-CW technique was also applied to a calcium magne-
sium silicate bioceramic called merwinite (Ca3MgSi2O8) [91]. The
mean particle size of the material was approximately 90 nm. CS
was performed at a temperature of 1400 °C, heating rate of
5 °C min  1 and a 20-h holding time. TSS-CW used T1 at 1250 and
1300 °C, a heating rate of 10 °C min  1 and a 5-min holding time.
The cooling rate was 60 °C min  1 to 1250, 1200 or 1150 °C in T2,
with holding times of 5, 10 and 20 h. Samples with a mean grain
size of 633 nm and 98% relative density were obtained in TSS-CW
using T1 at 1300 °C and T2 at 1250 °C, with a 20-h holding time in
T2. A significant increase in fracture toughness from 1.77 to
2.68 MPa m0.5 occurred in the CS specimens compared with the
TSS-CW specimens.
Zhou et al. [92] prepared porous nano-CaP ceramics through
TSS-CW. Biphasic calcium phosphate (BCP) powder was manu-
factured by the H2O2 foaming method. The sintering stage con-
sisted of heating at 10 °C min  1 to T1 (950 °C), a cooling rate of
30 °C min  1 and T2 at 850 °C. The holding time in T2 was 0.5 h.
The grain size of the nano-CaP ceramics ranged from 50 to 100 nm,
whereas CS processed at 1100 °C with an 8-h holding time ob-
tained grain sizes between 1 and 2 mm. Porous CaP ceramics with
nanometric grains were manufactured at the lowest sintering
temperatures.
Based on the studies reported herein, it is concluded that the
mechanical properties of TSS-CW-processed bioceramics im-
proved even when compared with more sophisticated sintering
techniques.
5. Miscellaneous
The two-step sintering technique has also been applied to other
ceramic oxides in combination with other sintering techniques
(such as microwave and spark plasma sintering) or by changing a
process condition. These different studies are presented in this
section.
TSS was carried out in BaTiO3 under controlled atmosphere by
using a combination of processes, including rapid-rate sintering
and RCS [93]. BaTiO3 nanopowders were compacted by cold
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isostatic pressing at 300 MPa. The sintering process was carried
out in a precise RCS, high-temperature dilatometer equipped with
computer-aided design and a gas control system. The partial
oxygen pressure during sintering was adjusted to a H2/N2/H2O
ratio in a blowing gas mixture. Initially, the non-isothermal sin-
tering was evaluated up to 1300 °C, with a heating rate ranging
from 200 to 3000 °C h  1 under partial oxygen pressures ranging
from 10  1 to 10  19 atm. The purpose was to define the best
heating system. Temperatures of 1000–1200 °C with 0.5- to 20-h
holding times were then used in the second sintering stage, and
the partial oxygen pressure remained unchanged. Samples with
grain sizes of 108 711 nm and 99.7% relative density were ob-
tained using T1 at 1300 °C and oxygen pressure at 10  19 atm and
T2 at 1100 °C with a 7-h holding time. By combining these sin-
tering techniques, the authors stated that the process simplified
control of the grains and the morphology of the pores.
Chang et al. [94] investigated TSS-CW in (Ba, Ca)(Ti, Zr)O3
(BCTZ). The thermal treatment used a heating rate of 10 °C min  1
in T1 (from 1250 to 1300 °C) and T2 ranging from 1150 to 1200 °C.
The cooling rate in T2 was 30 °C min  1, with an 8- to 15-h holding
time. The morphological analysis of the samples showed that the
sintering conditions, i.e., T1 at 1250 °C for 1 min, T2 at 1200 °C for
8 h; and T1 at 1300 °C for 1 min, T2 at 1200 °C for 8 h, resulted in a
microstructure with grains smaller than 0.5 mm and high relative
density (higher than 95%). The grain size obtained in the CS
samples was 5 mm.
Balaya et al. [95] investigated dense nanocrystalline strontium
titanate (SrTiO3). They avoided significant grain growth by apply-
ing TSS using hot pressing. Isostatic pressing was applied at
300 MPa for 5 min in addition to uniaxial hot pressing. TSS was
applied to the pressed samples (300 MPa), with T1 at 1220 °C and
a heating rate of 15 °C min  1 under nitrogen atmosphere and T2
at 1000 °C with a 20-h holding time. The obtained grain size was
150 nm. T1 at 1060 °C was used in high-pressure TSS and in hot
pressing with a heating rate of 150 °C min  1 under nitrogen at-
mosphere subjected to a uniaxial pressure of 125 MPa for 1 min
The temperature of the second stage was 1020 °C with a 3-min
holding time. Samples with a smaller grain size (80 nm) and 93%
relative density were obtained.
A comparative study [37] used three different oxides to com-
pare the TSS and SPS thermal treatments: Al2O3, 3 mol%
Y2O3-stabilized ZrO2, and SrTiO3, with particle sizes of 240 nm,
60 nm and 50 nm, respectively. The evaluation was carried out by
considering samples compacted at 300 MPa with a 5-min holding
time. Heating rates of 10 °C min  1 to 800 °C and 5 °C min  1 to T1,
decreasing by 60 °C min  1 to T2, were used in TSS, and T1 and T2
were in the range of 1000–1400 °C with holding times of 0, 5, 10,
15 and 20 h. The SPS samples were prepared under vacuum with a
uniaxial pressure of 200 MPa. The use of TSS did not cause sig-
nificant changes in the alumina and zirconia microstructures when
the grain density and size data were compared to those of CS.
Significant changes were observed in SrTiO3, wherein T1 was
1220 °C and T2 was 1000 °C for 15 h in TSS, and the grain size was
0.35 mm. CS used a temperature of 1250 °C for 30 min and ob-
tained a grain size of 0.56 mm, i.e., a grain size reduction of ap-
proximately 40%. The relative density was 95% in both processes.
However, the best result was achieved by the SPS method, with a
temperature of 875 °C for 5 min under a pressure of 200 MPa. The
SrTiO3 grain size was 80 nm, and the relative density was 98%.
The use of high-purity cobalt oxide (chromium) and iron oxide
(Fe2O3) resulted in a cobalt ferrite composition (CoFe2O4), which
was processed based on TSS. The specimens were heated at
1 °C min  1 to 550 °C, at 5 °C min  1 to 950 °C, and at 1 °C min  1 to
T1 at 1310 °C, where they remained for 1–3 h. The specimens were
then cooled at 20 °C min  1 to 1500 °C (T2) with a holding time
ranging from 30 min to 3 h. Finally, the material was cooled at
5 °C min  1 to room temperature. The thermal treatment in this
study was characterized by the control of heating rates rather than
by the conventional TSS process, in which the cooling process
freezes the structure. Cobalt ferrite discs with 96% relative density
were obtained by applying the sintering profile [96].
Nanopowders of yttrium aluminum garnet (YAG) synthesized
by a modified co-precipitation method were obtained through the
TSS method. Powders with a 50 nm particle size were cold pressed
at 10 MPa and isostatically cold pressed at 200 MPa to 40–45%
relative density. Sintering occurred between 1500 and 1800 °C
under vacuum (10  3 Pa). The temperatures of the first stage were
1700, 1750 and 1800 °C without holding time, and those of the
second stage were 1500, 1550 and 1600 °C with a 10-h holding
time. CS was performed at the same temperatures used in the first
and second TSS stages to compare the obtained results. After the
sample reached the desired temperature in T1, it was cooled and
held at T2 for 10 h. The results of relative density and grain size for
CS (corresponding to the range from 1700 to 1800 °C) were 90.0–
98.1% and 2.11–5.33 mm, respectively. Regarding CS at 1500–
1600 °C, the relative density (76.8–97.2%) and the grain size (0.65–
1.33 mm) were reduced. Regarding TSS, the densities were higher
than 99%, with a grain size ranging from 2.62 to 8.36 mm. T1 at
1800 °C and T2 at 1550 °C reached 99.9% relative density with a
6.04 mm grain size [97].
Y3Al5O12-YAG nanopowders were sintered by the co-pre-
cipitation method using ammonium hydrogen carbonate as the
precipitant [98]. The samples were pressed at 10 MPa, followed by
isostatic pressing at 200 MPa. The TSS treatment was performed at
1800 °C (T1) without holding time, with immediate cooling to T2
at 1600 °C, and held for 8 h. The process occurred under vacuum
(10  3 Pa). After sintering, the samples were annealed at 1450 °C
for 6 h. CS was used at temperatures T1 and T2 for comparison.
After T1 (1800 °C) was reached, the sample was cooled. T2
(1600 °C) was held for 8 h. The samples treated in a single stage
showed density values of 98.2% and 97.1% for T1 and T2, respec-
tively. TSS obtained 99.9% relative density and a 4 mm grain size,
which was lower than that obtained in the study by Chen et al.
[97].
Ultrafine alumina powders with a mean particle size of 0.2 mm
were also evaluated by TSS. The TSS suggested by Chu was com-
pared with the method developed by Chen and Wang (TSS-CW).
Temperatures from 1000 to 1050 °C with holding times of 3, 6 and
9 h were used regarding the methodology suggested by Chu. The
temperature was set at 1300 °C with a 3-h holding time in the
second stage. Regarding the process developed by Chen and Wang,
T1 was 1400 °C with a 5-min holding time. Two different tem-
peratures (1260 and 1300 °C) with holding times of 3, 6 and 9 h
were evaluated in T2. Both TSS methods were effective in con-
trolling the alumina microstructure compared with CS. The TSS-
CW method, which used T1 at 1400 °C and T2 at 1300 °C with a
9-h holding time, showed the best relative density and grain size
results, 96.58% and 460.7 nm, respectively. The holding time was
significantly important to grain growth in both techniques, and it
most influenced the TSS-CW technique [99].
Chinelatto et al. [100] evaluated the TSS processes performed
according to the methodology by Chu and the technique by Chen
and Wang. The used material was 5 vol% of nanometric zirconia
inclusions in alumina matrix. TSS-CW used T1 at 1450 °C (for
5 min) and T2 at 1400 °C with an 8-h holding time. Samples with a
grain size of approximately 538 nm and 98.5% relative density
were obtained. The Chu-based TSS used T1 at 1100 °C with a 2-h
holding time and T2 at 1400 °C for 2 h, and it obtained a smaller
grain size (472 nm) but with lower relative density (97.1%). CS was
performed at 1500 °C for 2 h and showed a larger grain size with
less density, 960 nm and 96.7%, respectively. The authors stated
that the TSS-CW technique allowed more effective densification
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and grain size suppression to be obtained, in addition to an in-
creased microhardness value (18.10 GPa).
The effect of the two-step sintering process (TSS-CW) on the
optical transmittance and on the mechanical strength of poly-
crystalline alumina ceramics was evaluated [101]. Injection-based
molding was used in a vacuum atmosphere at a high temperature
along with the implementation of the TSS-CW method. The first
stage was held at 1780 °C, and the second stage was held at 1300
and 1600 °C with different holding times, to prevent surface dif-
fusion and the formation of secondary phases. The increased sin-
tering temperature and holding time in the second stage promoted
a significant increase in grain size. The optical transmittance va-
lues significantly increased because of grain growth. The condition
with low temperature in the second sintering stage and a shorter
holding time showed the highest flexural strength (191 MPa) and
the lowest optical transmittance (12.5%). The relative density and
grain size values in this condition (1780–1300 °C for 1 h) were
99.39% and 7.2 mm, respectively. However, grain sizes larger than
those previously obtained were observed.
Pouchly et al. [102] changed the concept from the master sin-
tering curve (MSC) to the master two-step sintering curve using
four different ceramics appropriate to represent the TSS-CW pro-
cess. Thus, a tetragonal zirconia with 3 mol% Y2O3, two cubic zir-
conia with 8 mol% Y2O3, and one alumina were used. Different
heating rates (2, 5, 10 and 20 °C min  1) and CS at a temperature of
1500 °C were used in all materials. With respect to TSS, T1 (1440–
1328 °C), T2 (1340–1228 °C) and the holding time (10 or 15 h) var-
ied for each material under study. The application of MSC to the
TSS-CW-sintered samples demonstrated the need to divide the
curves (plots) into two parts: one with low density and with the
same activation energy calculated for the single-step sintering ex-
periments and the other with high density and low activation en-
ergy. An increase in TSS-CW efficiency was also observed because of
the reduction in the activation energy at the final sintering stage.
The calculated activation energy values were 770 kJ mol  1 for
Al2O3, 1270 kJ mol  1 for ZrO2 with 3 mol% Y2O3, 620 kJ mol  1 and
750 kJ mol  1 for ZrO2 with 8 mol% Y2O3 ceramics.
Lee and Kim [103] studied aluminum nitride (ALN) with cal-
cium zirconate (CaZrO3) and Y2O3 added. The specimens were
treated through TSS, with temperatures between 1450 and
1700 °C. The process occurred under nitrogen atmosphere in a
graphite furnace. The heating rate was 10 °C min  1 to T1 (3-h
holding time), and the cooling rate was 25 °C min  1 to T2 for 2 h.
Limited grain growth was verified owing to the use of the two-step
process. The highest thermal conductivity was achieved by the
two-step sintering, and the ceramics showed moderate flexural
strength (560 MPa).
Hejazi et al. [104] applied TSS-CW to prepare Mg-substituted
fluorapatite and MFA/alumina composites using different amounts
of alumina. T1 at 1050 or 1200 °C (1-min holding time) and T2 at
950 or 1100 °C (12- and 20-h holding times) were used. A com-
posite with a fine particle size was obtained using the TSS-CW
process. However, an increase in particle size from 175 nm to
590 nm was observed after alumina was introduced into the
composite, and it improved the mechanical properties.
Khosroshahi et al. [105] used a modified TSS process for cation
(Si4 þ , Er3 þ , Yb3 þ , Al3 þ or Ti4 þ )-doped yttria and molar dopant:
yttria ratio of 0.01. The samples were compacted by uniaxial
pressing at 5.3 MPa, followed by cold isostatic pressing at 350 MPa
for 3 min The SST was performed at a heating rate of 10 °C min  1
to T1 at 1490 °C, when it was cooled to room temperature. Next,
the specimens were reheated at a rate of 20 °C min  1 to T2 at
1350 °C with a 20-h holding time. Regarding Ti-doped Y2O3, Ti
showed the best results in terms of densification and mechanical
properties; thus, an optimized TSS with holding times of 0, 1 and
5 min was used in the first stage. With respect to the Ti-doped
12569
Y2O3 samples sintered in a single stage at a rate of 10 °C min  1 to
1490 °C with a 4-h holding time, a grain size reduction from 3.8 to
0.76 mm was observed, and the Vickers hardness increased from
686 to 867 Hv and flexural strength increased from 103.5 to
158.5 MPa compared with TSS without holding time in T1. Owing
to the use of a holding time (5 min) in the first sintering stage, Ti-
doped Y2O3 showed the best mechanical properties among the
tested samples: Vickers hardness of 874 Hv and flexural strength
of 307.0 MPa with densification of 99.4%. The flexural strength
increased by approximately two times more than the values re-
ported in the literature.
Wang et al. [106] extensively investigated barium-doped cerate
ceramics with a nominal composition of BaZr0.1Ce0.7Y0.1Yb0.1O3  δ
(BZCYYb), owing to their high proton conductivity at intermediate
temperatures, which can be applied to proton-conducting solid
oxide fuel cells (SOFCs). The powder with a mean particle size of
30 nm was uniaxially pressed at 600 MPa. The material was sin-
tered by TSS-CW at 5 °C min  1 up to T1 at 1450 °C for 1 min and
cooled to T2 at 1300 °C with a cooling rate of 15 °C min  1 and a
20-h holding time. Regarding CS, the specimens were heated at
5 °C min  1 to 1450 °C (5-h holding time). By controlling the sin-
tering curve through TSS-CW, a material with a grain size of
184 nm was obtained, whereas CS obtained a grain size of 445 nm.
In addition, the TSS-CW-sintered samples showed less impurity
and higher electrical conductivity compared with the CS samples.
Zhang et al. [107] evaluated BS-PT ceramics
(0.37BiScO3-0.63PbTiO3, initial particle size of 10 nm) by combin-
ing the SPS and TSS-CW techniques. The SPS heating rate ranged
between 150 and 175 °C min  1 to Ts (sintering temperature) with
a 3-min holding time. The specimen was cooled to room tem-
perature under vacuum and pressed at 50 MPa for 3 min after
reaching Ts. Subsequently, the samples were treated through TSS
at a heating rate of 5 °C min  1 to T1, cooled at 50 °C min  1 to T2,
and held for 6 h. The treatment at 650 °C (Ts) and a heating rate of
150 °C min  1, followed by T1 at 800 °C and T2 at 750 °C, produced
samples with a 70 nm grain size and 94.7% relative density. Ts at
700 °C and a heating rate of 175 °C min  1, followed by T1 at
800 °C and T2 at 750 °C, obtained a grain size of 33 nm and re-
lative density of 96.6%. With respect to the sample treated with Ts
at 600 °C, a heating rate of 150 °C min  1, T1 at 900 °C and T2 at
750 °C, the grain size and relative density were lower at 23 nm and
95.7%, respectively. The authors concluded that the grain size in-
creased with increasing Ts, and it decreased according to the
heating rate in the SPS process.
Commercial powders of Al2O3, Y2O3 and Nd2O3 (99% purity)
were used to obtain Nd-doped YAG ceramics produced by a solid-
state reaction [108]. Compaction was performed by uniaxial
pressing at 10 MPa and cold isostatic pressing at 200 MPa. The
powders were thermally treated in TSS with T1 at 1800 °C and a
heating rate of 10 °C min  1. T2 ranged between 1550 and 1750 °C
(1- to 8-h holding time) in a vacuum graphite tube furnace under
10  3 Pa during the holding process. Samples sintered at 1680 °C
(8-h holding time) showed a dense structure, pore-free micro-
structure and excellent optical properties.
The TSS process was applied to yttrium and gadolinium-doped
ceria-based electrolytes (20 at% dopant cation) (YCO and GCO)
with and without small Ga2O3- additions (0.5 mol%). The treat-
ment used T1 of 1250–1300 °C and T2 at 1150 °C with a holding
time of 0 or 10 h. The GCO samples reached 93.4% relative density,
using T1 at 1300 °C and T2 at 1150 °C with a 10-h holding time.
YCO using T1 at 1300 °C and T2 at 1150 °C with a 10-h holding
time reached slightly higher relative density (94.3%). Compacts
with a submicrometric grain size ranging from 150 to 250 nm
were produced [109].
The 0.89Bi0.5Na0.5TiO3-0.06BaTiO3-0.05 K0.5Na0.5NbO3 ternary
system ceramics derived from Bi2O3, Na2CO3, K2CO3, BaCO3, TiO2
12570 N.J. Lóh et al. / Ceramics International 42 (2016) 12556–12572
and Nb2O5 with more than 99% purity were treated through TSS-
CW and CS. The samples were compacted by pressing at 40 MPa.
The temperature in CS was 1140 °C with a 3-h holding time. TSS-
CW used T1 at 1140 °C (no holding time) and T2 at 1000 °C with a
5-h holding time. The cooling rate was 20 °C min  1. The TSS-CW-
sintered samples showed a homogeneous microstructure without
abnormal grain growth and with mean size of 1 mm. The grain
sizes were abnormal and ranged from 1.5 to 3.0 mm in CS [110].
Zhou et al. [111] evaluated nano-sized Nd3 þ :Lu2O3 powders
with an initial particle size of 40 nm. The thermal treatment was
performed through TSS-CW, and it used T1 at 1720 °C and T2 at
1620 °C with a 10-h holding time. H2 atmosphere was used during
the process. The grain size was approximately 400 nm, which was
approximately 150 times smaller than that obtained by CS [112].
Khakpour et al. [113] investigated samarium-doped CeO2 (SDC)
compounds. Two different compositions were prepared: ceria
doped with 20 (2SDC) and 30 (3SDC) mol% Sm. The powder was
compacted at 500 MPa and thermally treated through TSS-CW and
CS. TSS-CW used T1 at 1450 °C and a heating rate of 10 °C min  1.
The cooling rate for T2 was 50 °C min  1 to 1300 °C, at which it was
held for 20 h. CS used temperatures of 1400 °C (2SDC) and 1450 °C
(3SDC) with a heating rate of 2 °C min  1. The holding times were
5 h for 3SDC and 8 h for 2SDC. A grain size and relative density of
1.7 mm and 95%, respectively, were obtained for the 2SDC sample
processed through CS, whereas the TSS-CW grain size and relative
density values were 1.15 mm and 99.6%, and they were significantly
better. The 3SDC composition obtained a grain size and relative
density of 4.5 mm and 97%, respectively, through CS. However, TSS-
CW achieved a grain size reduction to 2.13 mm (with 98% relative
density). Again, the effectiveness of the TSS-CW technique in
suppressing grain growth was demonstrated.
The TSS technique may also be useful to control the pore size.
The pore size and porosity of porous ceramics depend on the par-
ticle size and the green body porosity. Therefore, the sintering plan
is an important factor that should be considered in the preparation
of porous ceramics. Isobe et al. [114] used 30 vol% α-Al2O3 with
70 vol% distilled water and 0.62 wt% poly (ammonium acrylate) to
prepare suspensions and shaped them through slip-casting. The CS
thermal treatment used temperatures of 1000–1400 °C for 2 h with
a heating rate of 1.5 °C min  1. The TSS-CW used a heating rate of
100 °C min  1 to T1 (1000–1300 °C) and T2 at 850–1150 °C with
holding times between 2 and 12 h. The cooling rates were
15 °C min  1 from T1 to T2 and 1.5 °C min  1 from T2 to room
temperature. One of the results showed that when T1 is sufficiently
high, the pore size and porosity do not change. The pores showed a
mean size of 61–76 nm for T1 at 1150 °C and T2 at 1000 °C.
Li et al. [115] investigated the behavior of a MgO microstructure
with 99.9% purity and a 50 nm particle size. The powder was
compacted at 6 MPa for 3–4 min The sintering process was carried
out in tube furnace using the TSS-CW and CS processes. CS was
performed between 1000 and 1600 °C, with heating and cooling
rates of 5 °C min  1. Two holding times were used, 5 min and 2 h,
and the samples were designated as C1 and C2, respectively. TSS-
CW used a heating rate of 5 °C min  1 to T1 (5-min holding time).
The cooling rate was 8 °C min  1 to T2, which was held for 20 h.
Based on the results obtained for the C1 and C2 samples, the TSS-
CW temperatures were determined to optimize the results. T1 was
chosen as 1550 °C and T2 as 1400 °C owing to high grain growth at
temperatures above 1410 °C. The use of TSS-CW produced samples
with high relative density (98%), a 21 mm grain size, and a mean
hardness of 6.1 GPa. Regarding CS, a lower relative density (96.2%)
was achieved for a grain size of 23 mm. Thus, MgO ceramics with
greater densification were obtained through TSS-CW without
using additives in the sintering.
Eoh et al. [116] used the TSS-CW process to investigate the
microstructural features of Zn1.8SiO3.8 ceramics. The powders were
isostatically pressed at 1500 kg cm  2. A CS heating rate of
3 °C min  1 was applied to reach the sintering temperature of
1300–1400 °C (4-h holding time). The same heating rate was used
in the TSS-CW process up to T1 at 1300–1400 °C (5-min holding
time). The cooling rate was 25 °C min  1 to 1250 °C (T2) with
holding times of 4, 8 and 12 h. The TSS-CW-sintered samples (T1
at 1350/1400 °C and T2 at 1250 °C for 4 h) showed increased mi-
crostructural homogeneity and higher relative densities (higher
than 96%) compared with the CS samples.
Hosseini et al. [117] evaluated nanostructured forsterite coat-
ing. The TSS-CW sintering process was used in argon atmosphere
with T1 at 1100 °C and a 30-min holding time and with T2 at
900 °C for 120 min The heating and cooling rates were 5 °C min  1.
The novel nanostructured forsterite coating was successfully de-
posited onto the 316 L stainless steel substrate by the electro-
phoretic deposition (EPD) method, followed by TSS.
6. Conclusions
The sintering of ceramic materials by sintering curve control is
an effective, simple and economical microstructure refinement
method. Thus, two-step sintering (TSS) is a promising method
used to obtain high-density bodies and smaller grain sizes. Two
TSS methodologies are known: the sintering with thermal pre-
treatment at a low sintering temperature, followed by a second
stage at an elevated temperature, and the more recent approach
presented by Chen and Wang, which has been most widely used.
Among the studies identified in the literature, the vast majority
have employed the technique developed by Chen and Wang by
adjusting the parameters to each study system.
The sintering specifications, including the temperatures, heat-
ing/cooling rates, sintering holding times and atmosphere types,
were determined for each study to obtain the best features for
each material. Most studies reported the obtainment of higher
relative density through the two-step sintering technique than
that obtained through conventional sintering, thus inhibiting the
accelerated grain growth. Nanometric structures were obtained in
some studies. Some general conclusions should be highlighted in
the current study:
1. specific particularities were observed in each material owing to
the addition of dopant agents and the effects of the two-step
sintering technique. Regarding the yttrium, zinc, barium tita-
nate and alumina oxides, it was possible to see that dopant
agents inhibit grain growth;
2. the initial powder features, such as particle size, molding pro-
cessing, microstructural homogeneity, and amount of green
body pores are factors that significantly influence the success of
two-step sintering, in addition to alumina and yttria-stabilized
zirconia;
3. specifically regarding the two-step sintering developed by Chen
and Wang (TSS-CW), the temperature reduction of the first
stage (T1) and the second stage (T2), despite the longer holding
time in T2, allows smaller grain sizes to be obtained for the
same relative density compared with conventional sintering;
4. the grain size reduction for the same densification allows ma-
terials with improved properties to be obtained, especially in
terms of mechanical properties. Two-step sintering indirectly
improves these properties;
5. the TSS method is an effective microstructure control method
compared with more expensive processes, such as spark plasma
sintering (SPS). However, techniques such as SPS and micro-
wave sintering are more effective for some materials, such as
yttria-stabilized zirconia. The cost/benefit ratio of the material
under study must be evaluated.
 N.J. Lóh et al. / Ceramics International 42 (2016) 12556–12572
Acknowledgements
The authors are very grateful to Coordenação de Aperfeiçoa-
mento de Pessoal de Nível Superior (CAPES/Brazil, Edital PRÓ-
DEFESA n. 031/2013, Auxílio n. 031/2013) for funding the current
study.
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