Materials Science & Engineering A 684 (2017) 466–469

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Materials Science & Engineering A

journal homepage: www.elsevier.com/locate/msea

Short communication

Alumina assisted grain refinement and physical performance enhancement MARK

of yttria transparent ceramics by two-step sintering
⁎
Le Zhanga,c, Yue Bena, Jiadong Wua, Hao Yanga, Chingping Wongc, Qitu Zhangb, Hao Chena,
a
Jiangsu Key Laboratory of Advanced Laser Materials and Devices, School of Physics and Electronic Engineering, Jiangsu Normal University, Xuzhou
221116, China
b
College of Materials Science and Engineering, Nanjing Technological University, Nanjing 210009, China
c
School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta 30332, USA

A R T I C L E I N F O A BS T RAC T

Keywords: Submicrometer grain-sized (1.5 µm) yttria ceramics exhibited the remarkable flexural strength enhancement
Transparent ceramics from 28.5 to 165.0 MPa, and equivalent or superior transparency (81.8%, 1064 nm) to that of single crystal
Two-step sintering under the two-step sintering of 1550–1500 °C and Al2O3 additive amount of only 150 ppm.
Nanoparticles
Sintering additives

1. Introduction
Recently, the development of polycrystalline laser material has been
accelerated due to the fabrication technology of transparent ceramic
[1–3]. Cubic yttria (Y2O3) is one of the most promising host materials
for 0.2–8 µm applications owing to its broad transparency, outstanding
absorption efficiency and stimulated emission. It can be potentially
applied as the host material for high-power, ultra-short pulse solid
state lasers, and transparent windows [4].
In order to fabricate high-transparency yttria ceramics, residual
porosity should be eliminated as low as possible. Typically, transparent
Y2O3 ceramics are fabricated by pressure sintering (hot pressing and
hot isostatic pressing (HIP)) or pressure-less sintering [5,6]. The main
driving force of densification is the reduction of surface energy, and
usually accompanied by grain coarsening with average grain sizes
approaching tens to hundreds of micrometers. Large grained ceramics
tend to exhibit a lower mechanical strength than smaller-grained ones.
As a result, they are less desirable in application demanding high
thermal shock resistance such as high-energy solid-state lasers [7].
Therefore, the reduction of grain size is needed to improve the strength
of ceramics.
However, maintaining a fine grain structure while achieving a fully
densified ceramic is a significant challenge because of the rapid grain
growth at the final stage of sintering. Recently, the two-step sintering
technique has been adopted to suppress grain growth at a low
temperature without sacrificing densification [8,9]. The first high-
temperature sintering (T1) for short dwell time can achieve a density
> 75% such that sufficient triple junctions exist throughout ceramics to
pin grain boundaries, while the subsequent low temperature (T2) could
make grain boundary diffusion active but its migration being impeded
[10,11]. Therefore, the densification is decoupled from grain growth by
prolonged isothermal heating at T2.
Furthermore, synthesizing high sintering activity nanopowders is
also an efficient way to yield smaller grains while achieving full
densification [12]. Generally used coprecipitation method, however,
easily results in wide size distribution and some agglomeration.
Because the drop-by-drop feed style produces the big droplets, and
the local concentrations of metal ions or precipitants are relatively
high, leading to the quick nucleation and growth. In addition, the
highly reactive powders would easily lead to abnormal grain growth
during vacuum sintering at higher temperatures, though various
sintering additives, such as LiF, HfO2, ThO2, La2O3 and ZrO2[13,14],
can address these issues to some extent. But, the high sintering
temperature, long dwell time, wide size distribution and the risk of
second phase segregation at grain boundary could not be avoided with
such large amount of sintering additives [15,16]. To date, there are few
reports that high transparency of Y2O3 ceramic with smaller grain size
can be obtained just using the additives at ppm (10−6) level only by
vacuum sintering.
In this letter, a novel spray coprecipitation method was used to
synthesize nanocrystalline Y2O3 powders as the starting materials.
Two-step sintering with the assistance of ppm level of Al2O3 as the
sintering additive was successfully optimized to achieve the refined
grain and improve the optical and mechanical performance.

⁎
Corresponding author.
E-mail address: le.zhang@mse.gatech.edu (H. Chen).

http://dx.doi.org/10.1016/j.msea.2016.12.093
Received 27 November 2016; Received in revised form 19 December 2016; Accepted 20 December 2016
Available online 21 December 2016
0921-5093/ © 2016 Elsevier B.V. All rights reserved.
L. Zhang et al.
2. Experimental
The coprecipitation of Y2O3 powders and forming of green bodies
were almost same as our previous study [5]. The difference was that a
spray device (diameter of atomizer nozzle, 10 µm) was designed to
spray the precipitant into Y(NO3)3 solution (2 ml/min) until the pH of
solution was 8.0. The different proportions of Al(NO3)3 were added
into Y(NO3)3 solution in advance ([Al3+]/[Y3+]=50, 100, 150 and
200 ppm). The precursors were calcined at 1250 °C for 4 h to remove
some organics impurities and SO42- group (as the dispersant) and to
obtain nanocrystalline Y2O3 powders. After being calcined at 850 °C for
5 h, the green bodies were employed two-step sintering in vacuum
furnace. Six different temperature systems were named T1(high) for
5 min- T2(low) for 20 h (1700-1600, 1650-1550, 1600-1500, 1550-
1500, 1550-1450, 1500–1400 °C). Then they were annealed in air at
1300 °C for 10 h. Finally, Y2O3 ceramics were grinded and polished.
Morphology of powders was performed by using FSEM (S4800,
Hitachi, Japan) and TEM (G2 20, Tecnai, USA). The relative densities
of ceramics were measured by the Archimedes method and the thermal
mechanical curve was investigated by a TMA (DIL402E, Netzsch,
Germany). Microstructure was carried out by SEM (JSM-6510,
JEOL, Japan). The in-line transmittance was characterized by UV–
VIS–NIR spectrophotometer (Lambda 950, Perkin-Elmer, Waltham,
MA). A three-point test machine (WDW-100, Hualong, China) with a
span of 30 mm and crosshead speed of 0.5 mm/min was used to
measure the flexural strength of test pieces (35 mm×4.0 mm×3.0 mm).
Single edge notched beam method was used to measure the fracture
toughness of specimens (35 mm×2.5 mm×5.0 mm) with crosshead
speed of 0.1 mm/min and the edge notch was made by laser cutting.
Five samples were tested to get the average value.
3. Results and discussion
Fig. 1 shows FESEM and TEM images of calcined Y2O3 powders. All
powders were fairly uniform. Most particles were composed of
coadjacent grains with a mean diameter of 80–100 nm, which aggre-
gated to be a chain in one-dimensional space. This slight agglomeration
could be easily destroyed and it would have little bad for the sintering
activity. The grains displayed pseudo-spherical shape with rough edges.
These nanocrystalline powders exhibited the better dispersibility and
benefited to high-quality Y2O3 ceramics with fine microstructure [17].
Fig. 2 shows relative densities and grain sizes of Y2O3 ceramics with
(a) different T1 temperatures (Al2O3 150 ppm) and (b) different Al2O3
amounts (1550–1500 °C). The relative density increased rapidly with
increasing T1 and reached the maximum at 1550 °C. Furthermore, at
the same T1, a higher T2 (1500 °C) resulted in a higher density.
However, the average grain size increased slowly with increasing T1
below 1600 °C, but then increased rapidly. The grain growth accom-
Fig. 1. FESEM and TEM images of the as-prepared Y2O3 powders calcined at 1250 °C for 4 h.
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Materials Science & Engineering A 684 (2017) 466–469
panying the rapid migration of grain boundary resulted in the pore
breakaway from the grain boundary, leading to the decrease of density
above 1600 °C. In Fig. 2(b), the relative density also increased with
increasing Al2O3 amounts and completed the densification (from
96.42–100.0%) at 150 ppm and occurred a drop off at 200 ppm. The
grain size occurred a rapid and obvious decrease from ~82.0 µm to
~5.0 µm at the appearance of Al2O3 and it decreased slowly when more
than 100 ppm. Al2O3 exhibited an obvious advantage in controlling the
microstructure and accelerating the densification in the case of 1550–
1500 °C two-step sintering. This temperature range was corresponding
to the maximal linear shrinkage rate at 1490 °C in Fig. 2(c), which
defined the second temperature T2. In this stage, the continuous pore
channels located along the grain edges and suppressed grain growth
with the assistance of Al2O3.
The above microstructure control could be obviously displayed in
Fig. 3. With A2O3 addition of 150 ppm, nearly pore-free and homo-
geneous microstructures under different T1-T2 sintering systems were
observed without abnormal grain growth except for a slight increase
from 1.21 to 1.50 µm when T1 increased from 1500 °C (Fig. 3(a)) to
1550 °C (Fig. 3(b)). Under the optimized sintering system of 1550–
1500 °C, A2O3 addition even only 50 ppm resulted in a dramatic
decrease in grain size from ~82.0 µm (Fig. 3(c)) to 5.5 µm (1.50 µm
for 150 ppm) and excess addition (200 ppm) nearly unchanged grain
size (1.47 µm) in Fig. 3(d). A small grain size is important to remove
the residue pores completely and Al2O3 effectively controlled the
microstructure of ceramics.
The in-line optical transparency of Y2O3 ceramics showed the same
change trend like the density in Fig. 2(d). It reached the maximum of
81.8% (1064 nm) under the sintering of 1550–1500 °C with 150 ppm
Al2O3, which was equivalent or superior to that of single crystal
(computed from refractive index [18]) above 900 nm and an optically
transparent yttria ceramic was obtained in Fig. 4. In addition, it was
lower in the visible-light range due to few residual pores with small size
as light scattering centers, which would be completely removed by the
combination of vacuum sintering and HIP and further needed
systematical studies in future. The mechanical performance of Y2O3
ceramics is shown in Fig. 5. Y2O3 ceramic without Al2O3 possessed the
worst mechanical properties. The flexural strength and fracture tough-
ness significantly increased from 28.5 MPa and 0.45 MPa·m1/2 (with-
out Al2O3) to 165.0 MPa and 1.90 MPa·m1/2 (150 ppm Al2O3), respec-
tively. As known, finer grain size with larger area of grain boundary,
higher density with lower porosity and more uniform microstructure
are together served to inhibit crack propagation and enhance the
mechanical strength of ceramics [19]. In the comparison of Fig. 2(b)
and Fig. 5, the flexural strength showed an almost same trend with the
density change, and almost opposite with grain size. In this letter, in
the case of two-step sintering, Al2O3 additive exhibited an obvious
advantage in accelerating the densification and refining the grain size
L. Zhang et al. Materials Science & Engineering A 684 (2017) 466–469

Fig. 2. Relative densities and grain sizes of Y2O3 ceramics with (a) different T1 temperatures, and (b) different Al2O3 amounts, (c) thermal mechanical curves of green compact and (d)
in-line transmittance of Y2O3 ceramics.

Fig. 3. SEM images of thermal etching surface of Y2O3 ceramics with different two-step sintering temperatures (a) 1500–1400 °C, (b) 1550–1500 °C, and different A2O3 amounts (c) 0,
(d) 200 ppm.

468
L. Zhang et al.
Fig. 4. In-line transmittance and photograph of prepared Y2O3 ceramics (1 mm
thickness).
Fig. 5. Mechanical performance of prepared Y2O3 ceramics with different A2O3
amounts.
to get more uniform microstructure (Fig. 3). When without Al2O3,
highest porosity and the abnormal grain growth lead to the lowest
strength. For ceramics with only 150 ppm Al2O3, the flexural strength
increased to 165.0 MPa with the increase of density (near 100%),
decrease of grain size (1.5 µm) with uniform distribution. To the best
our knowledge, this is the highest mechanical strength in all previously
fabricated Y2O3 ceramics. This remarkable enhancement would accel-
erate its high-power laser application, in which high thermal shock
resistance is required.
4. Conclusions
In this paper, the novel spray coprecipitated nanocrystalline
powders was used to fabricate the grain refined and physical perfor-
mance enhanced yttria ceramics by the combined optimization of two-
step sintering temperature (1550–1500 °C) and sintering additive
amount of Al2O3 (150 ppm), for the first time to our knowledge. The
resulting 1.5 µm grain-sized transparent yttria ceramic, exhibiting
remarkable mechanical performance (flexural strength of 165.0 MPa)
and equivalent or superior transparency (81.8%, 1064 nm) to that of
single crystal beyond 900 nm, represented an important advance. The
combination of two-step sintering and ppm-level Al2O3 additive makes
it feasible to control the densification and grain growth for potential
application in high-power laser systems, which demand high thermal
shock resistance and optical quality.
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Materials Science & Engineering A 684 (2017) 466–469
Prime novelty statement
1. The first-time combination of two-step sintering and Al2O3 additive
in ceramic fabrication, effectively accelerated the densification and
suppressed the grain growth and resulted in the enhancement of
physical performance.
2. The flexural strength and fracture toughness significantly increased
from 28.5 MPa and 0.45 MPa m1/2 to 165.0 MPa and 1.90 MPa m1/
2
, respectively, to the best our knowledge, was the highest in all
previously fabricated Y2O3 ceramics.
3. Optical transparency of 81.8% at 1064 nm of fabricated Y2O3
ceramics was equivalent or superior to that of single crystal.
4. Low-agglomerated and narrow size distributed Y2O3 powders were
synthesized by a spray coprecipitation method, which provided high
sinterability nanocrystalline powders for ceramic sintering.
5. Such low-level of Al2O3 addition (150 ppm) resulted in big achieve-
ment of physical properties but would not influence the laser
performance, which required the amount of sintering additives as
low as possible.
Acknowledgements
Priority Academic Program Development of Jiangsu Higher
Education Institutions (PAPD) and National Natural Science
Foundation of China (51402133, 51202111).
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