Journal of Materials Science & Technology 36 (2020) 84–90

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Journal of Materials Science & Technology

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Research Article

Synthesis of W-Y2 O3 alloys by freeze-drying and subsequent low

temperature sintering: Microstructure refinement and second phase
particles regulation
Weiqiang Hu, Zhi Dong, Liming Yu, Zongqing Ma ∗ , Yongchang Liu
State Key Lab of Hydraulic Engineering Simulation and Safety, School of Materials Science and Engineering, Tianjin University, Tianjin 300072, China

a r t i c l e i n f o a b s t r a c t

Article history: In this work, W-Y2 O3 alloys are prepared by freeze-drying and subsequent low temperature sintering. The
Received 28 May 2019 average size of reduced W-Y2 O3 composite powders prepared by freeze-drying method is only 18.1 nm.
Accepted 16 June 2019 After low temperature sintering of these composite nanopowders, the formed W-Y2 O3 alloys possess a
Available online 9 August 2019
smaller grain size of 510 nm while maintaining a comparatively higher density of 97.8%. Besides a few
submicron Y2 O3 particles (about 100–300 nm) with a W-Y-O phase diffusion layer on their surface dis-
Keywords:
tribute at W grain boundaries, lots of nano Y2 WO6 particles (<20 nm) exist in W matrix. Moreover, many
W-Y2 O3 alloys
Y6 WO12 (<10 nm) particles exist within submicron Y2 O3 particles. The formation of these ternary phases
Freeze-drying
Low temperature sintering
indicates that some oxygen impurities in the W matrix can be adsorbed by ternary phases, resulting in the
Ultrafine grains purification of W matrix and the strengthening of phase boundaries. The combined action of the above
factors makes the hardness of the sintered W-Y2 O3 alloys in our work as high as 656.6 ± 39.0 HV0.2 . Our
work indicates that freeze-drying and subsequent low temperature sintering is a promising method for
preparing high performance W-Y2 O3 alloys.
© 2019 Published by Elsevier Ltd on behalf of The editorial office of Journal of Materials Science &
Technology.

1. Introduction
Tungsten-based alloys, due to their excellent physical properties
such as high melting point, good thermal conductivity, corrosion
and wear resistance, are widely used in the field of cemented
carbides and superalloys [1–4]. In the field of superalloys, tungsten-
based alloys are mainly used as aerospace materials and nuclear
materials [5,6]. However, embrittlement, high ductile-brittle tran-
sition temperature (DBTT) and low density limit their applications
[7–9].
In order to solve these problems to obtain tungsten-based mate-
rials with high performance, the microstructures and properties
of conventional tungsten materials need to be improved and opti-
mized. Current studies mainly focus on second-phase dispersion
strengthening and fine-grained strengthening [7,10,11]. On the one
hand, second phase particles with high thermal stability includes
carbides (such as TiC and ZrC) [9,12] and oxides (such as Y2 O3 , La2 O3
and Ce2 O3 ) [13–15]. Rare-earth oxide particles can effectively pin
the movement of W grain boundaries, refining and stabilizing W
∗ Corresponding author.
E-mail address: mzq0320@163.com (Z. Ma).
grain. At the same time, it can improve low temperature brittle-
ness and low recrystallization temperature. Moreover, nanosized
oxide dispersed strengthened (ODS) tungsten materials also have
good creep resistance and radiation resistance at high temperature
[16–18]. Among rare earth oxides, Yttrium oxide (Y2 O3 ) is the best
dispersion strengthening phase [19], so W-Y2 O3 alloys has gained
extensive attention.
On the other hand, according to the principle of fine grain
strengthening, alloys with small grain size have good plasticity and
toughness while maintaining high strength and hardness [5,20].
Moreover, the smaller the grain size, the more grain boundaries.
More grain boundaries can reduce the concentration of impu-
rities at grain boundaries and optimize their distribution [17].
Because of the high melting point of tungsten-based alloys, they
are mainly obtained by powder metallurgy. Fine-grained tungsten-
based alloys can be obtained by low temperature sintering of
ultrafine nano powders with high sintering activity [10].
Former researchers mainly employed tungstic acid co-
precipitation method [21,22] or ball milling method [23–26] to
prepare ultrafine W-Y2 O3 composite powders. However, many
impurities like nickel, iron, and soon are introduced in the process
of ball milling meanwhile the agglomeration is serious [27–29]. In
addition, the refinement of powders is not obvious in the later stage

https://doi.org/10.1016/j.jmst.2019.08.010
1005-0302/© 2019 Published by Elsevier Ltd on behalf of The editorial office of Journal of Materials Science & Technology.
 W. Hu et al. / Journal of Materials Science & Technology 36 (2020) 84–90
of ball milling, which wastes a lot of energy [24,30]. Although the
powders obtained by tungstic acid co-precipitation achieve uni-
form doping at atomic level, there is a phenomenon of bimodal
distribution of their tungsten grain size, which has a negative
impact on subsequent sintering [2,22].
The smaller and more dispersed the second phase particles in
W-Y2 O3 alloys are, the better the dispersion strengthening is. Y2 O3
particles at grain boundaries can refine W grains [27,31]. Because
the interfacial strength of W-W is greater than that of W-Y2 O3
[16,17], large Y2 O3 particles at the grain boundaries are prone to
stress concentration and cracking. In the related papers on ball
milling, even if powders are very fine, the second phase parti-
cles grow up to submicron size after sintering, and almost all of
them are distributed at grain boundaries [23–26]. In addition, apart
from focusing on the size and distribution of second phase par-
ticles, few literatures focus on the composition of second phase
particles. Except for the second phase Y2 O3 particles in W-Y2 O3
alloys [2,14,31–34], few researchers mentioned that the composi-
tion of second phase particles are Y2 WO6 or Y6 WO12 [5,35] and they
did not investigate these W-Y-O ternary phases in depth. The sec-
ond phase composition has an important influence on the interface
structure and strength, so it is necessary to systematically explore
the second phase composition.
In order to solve the W-Y2 O3 alloys problems mentioned above
(including powder preparation, the distribution and composition
of second phase particles, oxygen content), W-Y2 O3 alloys were
innovatively prepared by freeze-drying and subsequent low tem-
perature sintering in this work. Freeze-drying is a physical method
that can mix at atomic level without introducing additives or los-
ing solutes. It has been used to prepare ultrafine powders such
as Al2 O3 , WC-Co, Co2 AlO4 and superconducting powders [36–39].
Hereby W-Y2 O3 composite powders precursor were prepared by
freeze-drying method. The grain size of the powder prepared by
freeze-drying is only 18.1 nm, and the corresponding grain size dis-
tribution is excellently narrow. After subsequent low temperature
sintering, the sintered W-Y2 O3 alloys have a smaller grain size of
510 nm while maintaining a comparatively high density of 97.8%.
Lots of small Y2 WO6 particles (< 20 nm) were found in W matrix
while a few large Y2 O3 particles distribute at W grain boundaries.
Combining with the purification of grain boundary, the distribution
and composition of second phase particles are studied. In addition,
the Vickers microhardness of sintered W-Y2 O3 alloys also reaches
656.6 ± 39.0 HV0.2 .
2. Experimental procedure
2.1. Preparation of powders
Ammonium metatungstate (NH4 )6 H2 W12 O40 ·xH2 O (AMT) and
yttrium nitrate hexahydrate (Y(NO3 )3 •6H2 O) were used as raw
materials to prepare W-2 wt% Y2 O3 composite powders. At first,
20.00 g of ammonium metatungstate and 1.03 g of yttrium nitrate
hexahydrate were dissolved in 200 mL deionized water while ultra-
sonic treatment was introduced to dissolve solutes more fully.
Then, the solution was pre-frozen for 12 h in a constant temper-
ature freezer at −40 ◦ C. Next, after the freeze dryer temperature
decreased and stabilized, the pre-frozen solution is put into freeze
dryer to lyophilize for 48 h. After that, porous precursor powders
were calcined in argon atmosphere at 500 ◦ C for 30 min. The reduc-
tion in pure hydrogen atmosphere was carried out in two steps, that
is, the first step at 600 ◦ C for 2 h and the second step at 800 ◦ C for
2 h. Finally, ultrafine W-Y2 O3 composite powders were obtained by
cooling slowly in hydrogen atmosphere to room temperature.
At the same time, W-2 wt% Y2 O3 composite powders were pre-
pared by ball milling method for comparison. Commercial pure
85
Fig. 1. XRD patterns of the W-Y2 O3 composite powders fabricated by freeze-drying
method and ball milling method.
W powders (99.9% purity, 0.6–1 ␮m in size) and Y2 O3 powders
(99.99% purity, 20–50 nm in size) were used as raw materials. W-
Y2 O3 composite powders were obtained by using planetary ball
mill at a speed of 300 r/min for 20 h.
2.2. Low temperature sintering process
W-Y2 O3 composite powders were placed in a mold having a
diameter of 25 mm, and then the pressure of 20 MPa was applied
to the die and kept for 10 min to obtain preformed samples. The
pre-formed samples were then placed in a furnace with hydrogen
atmosphere, holding for 2 h at 800 ◦ C, then heating to 1600 ◦ C and
holding for 4 h. The sample of W-Y2 O3 alloys sintered by ball milling
powders was named as BM sample, and the sample of W-Y2 O3
alloys sintered by freeze-drying powders was named FD sample.
2.3. Characterizations
The phase, microstructure and second phase particles distri-
bution of composite powders and alloys were measured by X-ray
diffraction (XRD, D/MAX-2500) with CuK˛ radiation, scanning elec-
tron microscopy (SEM, Hitachi Model No. S4800) equipped with
EDX detector and transmission electron microscopy (TEM, JEM-
2100) equipped with EDX detector. The density of sintered W-Y2 O3
samples was measured by Archimedes method. Oxygen content
was detected by inert gas pulse infrared thermal conductivity.
The Vickers microhardness of sintered samples was tested for 20 s
under 200 gf load and each sample was tested for twenty times to
get an average hardness value.
3. Results and discussion
3.1. Characteristics of prepared W-Y2 O3 composite nanopowders
Fig. 1 shows XRD patterns of the W-Y2 O3 composite powders
fabricated by freeze-drying method and balling milling method.
It can be seen that the peak of Y2 O3 phase are not detected due
to the less addition of Y2 O3 . Freeze-dried powders only have ␣-
W phase, indicating that the reduction of these powders has been
completed. According to the calculation of Scherrer’s formula, the
grain sizes of ball milling powder and freeze-dried powder are 14.1
and 19.1 nm, respectively. Furthermore, the full width at half max-
imum (FWHM) of peaks of freeze-dried powders is narrower than
that of mechanical ball-milling powders, which indicates that the
grain size of mechanical ball-milling powders is smaller.
86 W. Hu et al. / Journal of Materials Science & Technology 36 (2020) 84–90

Fig. 2. (a) SEM image and (b) TEM image of the W-Y2 O3 composite powders prepared by balling milling method, (c) SEM image and (d) TEM image of the W-Y2 O3 composite
powders prepared by freeze-drying method.

SEM and TEM images of freeze-dried powders and mechani-

cal ball-milled powders are shown in Fig. 2. It is observed from
Fig. 2(a) and (b) that the agglomeration of powders prepared by
ball milling is very severe, and crystal grains are in close contact
with each other. During the process of balling milling, the plas-
tic deformation and fracture effect caused by friction and impact
from balls and jar can lead to grain refinement, but also result
in the formation of large irregular particles [25]. Because of the
irregular shape of some large particles, large voids between large
particles are hard to eliminate during sintering, which finally affects
the mechanical properties of W-Y2 O3 alloys. Compared with ball
milled powders, the freeze-dried powders of Fig. 2(c) and (d) are
also fine, and the average grain size is about 18.1 nm, which is con-
sistent with the results calculated by Scherrer’s formula based on
XRD data. Moreover, the dispersion of their grains is extremely high
Fig. 3. HRTEM image of the W-Y2 O3 composite powders prepared by freeze-drying
and almost no agglomeration is observed mean while the distribu-
method.
tion of grain size (10–25 nm) is extremely narrow, which means
that freeze-dried powders has high sintering activity. In previous
studies, some researchers obtained a bimodal distribution of W with high dispersion and fine size have a large surface area, which
grain size in the W-Y2 O3 composite powders with particle sizes leads to a high oxygen content. For ball milling powder, on the
of 250 nm and 50 nm using conventional wet chemical methods one hand, impurities such as nickel, iron, and oxygen are intro-
[22]. The W-Y2 O3 composite powders having a size of 0.1–1 ␮m duced during ball milling [27]. On the other hand, after ball milling,
was obtained by a novel wet chemical method [34]. In addition, the multiple defects and high internal energy make W-Y2 O3 compos-
researchers also obtained W-Y2 O3 composite powders with the size ite powders highly active and easy to be oxidized after contact with
of 160 nm by nano-in-situ composite method [27]. Comparing with air. It is worth noting that the impurity oxygen (excluding oxygen
these previous studies, it can be seen that the size of freeze-dried in Y2 O3 phase) content of these two kinds of powders is even close
W-Y2 O3 composite powders is excellent fine. The HRTEM image of to that in the Y2 O3 addition. If the high oxygen content of these
the W-Y2 O3 composite powders prepared by freeze-drying method powders is not controlled, the mechanical properties of sintered W-
is shown in Fig. 3. It can be observed that Y2 O3 is coated by W. Y2 O3 alloys will deteriorate. Finally, the summary of characteristics
The formation of Y2 O3 within W grains is attributed to the homo- of W-Y2 O3 composite powders prepared by these two methods is
geneous doping of the initial precursor powder atoms. Moreover, summarized in Table 1.
the Y2 O3 particles coated by W does not easily grow up after the
subsequent sintering due to the blocking effect of W. 3.2. Low temperate sintering characteristics of prepared W-Y2 O3
The oxygen content of W-Y2 O3 composite powders prepared by composite nanopowders
balling milling and freeze-drying are 2.32% and 2.26%, respectively.
After excluding the oxygen in Y2 O3 phase, the net oxygen (oxy- In order to control the oxygen content and obtain high per-
gen impurity) content of these two powders is 1.90% and 1.84%, formance W-Y2 O3 alloys, low temperature sintering under the
respectively. Oxygen impurities usually form a thin layer of tung- hydrogen atmosphere was performed to the prepared W-Y2 O3
sten oxide on the surface of W grains [40,41]. Freeze-dried powders composite nanopowders precursor. In order to better illustrate
 W. Hu et al. / Journal of Materials Science & Technology 36 (2020) 84–90 87

Table 1 Fig. 4(a) is 0.5–2 ␮m, and these Y2 O3 particles are distributed at
Characteristics of W-Y2 O3 composite powders prepared by balling milling and
grain boundaries. W-2 wt% Y2 O3 alloys with the Y2 O3 particles size
freeze-drying.
of 300 nm-1 ␮m has been obtained in Ref. [26]. In addition, it can
Powder Phase Average Grain size Oxygen be observed that there are many pores (marked by white arrows),
preparation Composition grain size distribution content
resulting in a decrease in the density of W-Y2 O3 alloys.
process (nm) (nm) (wt%)
It is observed from Fig. 4(c) and (d) that FD sample has smaller
Balling milling ␣-W 14.1 (XRD) – 2.32% grain and narrower grain size distribution than BM sample. The
Freeze-drying ␣-W 18.1 10–25 2.26%
average grain size is only about 510 nm, and the corresponding
grain size mainly distributes between 300 nm and 700 nm. In recent
literatures, Zhao et al. obtained W-Y2 O3 alloys with the grain size
the distribution of phases, the atomic ordinal contrast image is of 2–5 ␮m by wet chemical method and subsequent SPS [34]. The
obtained using backscattered electrons as signals. Fig. 4 represents W-Y2 O3 alloys of 5–10 ␮m was also obtained by sol-gel method
the phase composition of microstructure of BM sample and FD and subsequent traditional consolidation sintering [42]. In addi-
sample in which white region is W-enriched matrix and the gray tion, an improved wet chemical method and subsequent SPS were
region is Y-enriched second phase particles. The average W grain used to synthesize W-Y2 O3 alloys with the grain size of 0.76 ␮m
size of BM sample in Fig. 4(a) is about 5.67 ␮m and its correspond- by Dong et al. [5,40]. Compared to these related papers, the freeze-
ing grain size distribution in Fig. 4(b) is wide. In previous studies drying and subsequent low temperature sintering is advantageous
using the ball milled W-Y2 O3 composite nanopowders as precur- in refining W grain size of W-Y2 O3 alloys. The fine grain struc-
sor, the grain size (3–5 ␮m) was obtained by Zhou et al. [23] for the ture of FD sample is mainly due to the pinning effect of second
W-0.5 wt% Y2 O3 alloys sintered by SPS at 1700 ◦ C while the grain phase particles, which is closely related to the size and distribution
size of 1–2 ␮m was obtained by Li et al. for the W-2 wt% Y2 O3 alloys of second phase particles. Combining the gray points in Fig. 4(c)
sintered by SPS at 1200 ◦ C [25]. This is similar to the grain size of amplified locally by using secondary electrons as signals, it can be
W-Y2 O3 alloys sintered under hydrogen atmosphere in our work. observed that there are not only a few large second phase parti-
However, the oxygen content of BM sample is only 0.51%, indicat- cles (marked by white dotted circular frames) of 100–300 nm at
ing that the oxygen content has been effectively reduced. On the grain boundaries, but also many small particles (marked by black
other hand, the size of Y2 O3 particles (marked by black arrows) in arrows) of about 10 nm at grain boundaries. It is reported that

Fig. 4. (a) BSE image of BM sample and (b) corresponding W grain size distribution, (c) BSE image of FD sample and (d) corresponding W grain size distribution.

Fig. 5. TEM images of the W-Y2 O3 alloys prepared by freeze-drying method and subsequent low temperature sintering in different multiples.
88 W. Hu et al. / Journal of Materials Science & Technology 36 (2020) 84–90
Fig. 6. HRTEM images of (a, b) small particles within Y2 O3 grains, (c, d) W and Y2 O3 interface and (e, f) small particles within W grains.
although the size of Y2 O3 particles within W grains is only 2–10 nm
by the improved wet chemical method, the size of Y2 O3 particles
at the grain boundaries is 100–300 nm [5,20]. In addition, submi-
cron Y2 O3 particles (400–800 nm) obtained by a new wet chemical
method almost distribute at W grain boundaries [32–34]. How-
ever, the large number second phase particles of about 10 nm in
our FD sample still exist at grain boundaries, significantly refining
W grains. In order to better explain the detailed characteristics of
these second phase particles, FD sample are further characterized
by TEM (see Fig. 5).
In Fig. 5(a), white particles (marked by white arrows) are dis-
tributed on the black matrix. Combined with EDS, these white
particles are found to be enriched in Y component, proving to
be second phase particles. It is further found from Fig. 5(b) that
there are also many small particles (marked by white arrows)
within W grains. Moreover, an interesting phenomenon was found
in Fig. 5(c). The large white particle was proved to be Y2 O3 by
EDX in the black box region, but many small particles (about
2–10 nm) were dispersed in it. These second phase particles were
characterized by HRTEM (Fig. 6). As can be seen from the HRTEM
images in Fig. 6(a) and (b), these spherical particles are Y6 WO12
particles. Y6 WO12 particles within Y2 O3 matrix has never been
reported in the previous studies on the W-Y2 O3 alloys. At the
same time, there is also a W-Y-O diffusion layer (about 5–10 nm)
between Y2 O3 and W matrix, as shown in Fig. 6(c) and (d).
Because the lattice in the HRTEM image of diffusion layer is incom-
plete, the specific phase needs to be determined in the following
work. On the other hand, the second phase particles within W
grains are shown in Fig. 6(e) and (f) and proved to be Y2 WO6
particles.
What’s the reason for the formation of Y6 WO12 and Y2 WO6 ? In
the related previous studies, Y6 WO12 or Y2 WO6 are obtained by wet
chemical method and subsequent SPS sintering. Yar et al. consider
that these W-Y-O ternary phase particles may have two formation
stages, i.e. in powder preparation stage or in high temperature sin-
tering stage, but they did not make in-depth analysis [35]. Dong
et al. believe that W atoms can be incorporated in Y2 O3 lattice to
form Y6 WO12 phase at the high temperature sintering stage, and
the formation of W-Y-O phase depends on the Y2 O3 particle size
[5]. Compared with SPS sintering, the FD sample in our work was
sintered at 1600 ◦ C for 4 h in a hydrogen atmosphere, so that the W
atoms had sufficient time to diffuse into the small Y2 O3 particles to
 W. Hu et al. / Journal of Materials Science & Technology 36 (2020) 84–90
Fig. 7. Schematic diagram of freeze-drying and low temperature sintering.
form Y6 WO12 or Y2 WO6 particles. On the other hand, the diffusion
distance of W is limited, so a W-Y-O diffusion layer is formed on
the surface of submicron Y2 O3 particles.
Compared with Y2 O3 particles, the advantages of the formation
of Y6 WO12 and Y2 WO6 particles are illustrated from a new angle.
In the grain boundary strengthening principle of W-ZrC alloys, ZrC
particles at the grain boundaries adsorb oxygen impurities to form
W-ZrC-O phase, which purifies and strengthens grain boundaries
[12,43]. By comparison, the formation of Y2 WO6 (WO3 ·Y2 O3 ) and
Y6 WO12 (3WO3 ·Y2 O3 ) particles [35,44] has similar strengthening
mechanism. On the one hand, Y2 O3 particles can absorb nearby
oxygen impurities in the W matrix to form Y2 WO6 (WO3 ·Y2 O3 )
particles, which purifies and strengthens W grain boundaries and
grain interior. On the other hand, Y6 WO12 (3WO3 ·Y2 O3 ) particles
with high oxygen content mean that more oxygen impurities are
absorbed within Y2 O3 particles interior. This also means that the
oxygen content of W matrix is also relatively reduced. The oxy-
gen content of FD sample is 0.51% and after excluding oxygen in
Y2 O3 phase, its net oxygen content is 0.058%, which is the same as
that of BM sample. However, due to the formation of these W-Y-O
ternary phases, the actual net oxygen content is much lower than
0.058%. It’s also worth noting that because of the formation of W-Y-
O ternary phases, the content of oxide exceeds 1 wt%, so the density
of FD sample should be higher [35]. From the above discussion, it
can be seen that the formation of the Y6 WO12 and Y2 WO6 phases
has many advantages.
Y6 WO12 particles are distributed in Y2 O3 matrix and Y2 WO6
particles are distributed in W matrix. This new phenomenon can
also be explained from oxygen content. Compared with Y2 WO6
(WO3 ·Y2 O3 ), Y6 WO12 (3WO3 ·Y2 O3 ) has more WO3 , which means
more nearby oxygen impurities are adsorbed. Y2 O3 particles hav-
ing high oxygen content can adsorb oxygen impurities nearby [7],
so Y6 WO12 particles are easy to form in Y2 O3 matrix. In contrast,
W matrix has a low oxygen content, which leads to the formation
of Y2 WO6 particles.
89
The formation of submicron Y2 O3 particles in the FD sample is
explained. In addition to the fusion growth of Y2 O3 dispersed at
grain boundaries during sintering, another reason for the forma-
tion of a few submicron Y2 O3 particles may be that the original
precursor powders of Y component are not ideal uniform mixing.
When pre-freezing with a refrigerator, the cooling rate is slower,
resulting in the rate of solute movement is faster than that of water
solidification. A part of deionized water solidifies evenly into ice
crystals first in the solution to separate solutes [45]. When solute
concentration reaches their critical value, they solidify with deion-
ized water and distributes in the gap between ice crystals [46,47].
Because of the different solubility and addition of AMT and YN3 O9 ,
AMT and YN3 O9 cannot reach the critical value at the same time.
However, due to the limitation of surrounding ice crystals [45],
solutes may be segregated in a small region. The precursor pow-
ders enriched in Y component precipitate numerous large Y2 O3
particles and these Y2 O3 particles are easy to aggregate and grow
up to submicron during subsequent low temperature sintering due
to their concentrated distribution. Meanwhile, the W component
within Y2 O3 particles reacts with the surrounding Y2 O3 and oxy-
gen impurities, thus forming Y6 WO12 particles. Through the above
analysis, the reasons for the composition, size and distribution of
second phase particles in FD sample are well explained. Finally, the
schematic diagram of freeze-drying and subsequent low tempera-
ture sintering is shown in Fig. 7, which also shows the formation
process of Y6 WO12 , Y2 WO6 and the diffusion layer between W and
Y2 O3 .
The Vickers microhardness of BM sample and FD sample are
351.0 ± 100.7 HV0.2 and 656.6 ± 39.0 HV0.2 , respectively. It can be
seen that the hardness of FD sample is much higher than that of
BM sample. The Vickers microhardness mainly reflects the grain
size and relative density of W based alloys [20,27,40]. On the one
hand, the grain size of BM sample is more than ten times that of
FD sample. According to the principle of fine grain strengthening
[31,48], the hardness of refined grain is higher. On the other hand,
90 W. Hu et al. / Journal of Materials Science & Technology 36 (2020) 84–90
Table 2
Characteristics of BM sample and FD sample.
Sample Powder Grain size Relative Oxygen
preparation density content
process (%) (wt%)
BM Balling milling 5.67 ␮m 84.1 0.51
FD Freeze-drying 510 nm 97.8 0.51
compared with the 84.1% relative densities of BM sample, the FD
sample has a higher relative density of 97.8%. What’s more, the
uniformly dispersed second phase particles also contribute to the
significant increase of hardness of FD sample. In previous study on
the W-Y2 O3 alloy prepared by mechanical ball milling and sinter-
ing, the hardness of 476.5 ± 13.5 HV was obtained when the grain
size of W-Y2 O3 alloys was 3–5 ␮m with a density of 96.8% [23].
While maintaining a high density of 99%, the hardness of sintered
powder after ball milling is 525 HV, and its grain size is 3.7 ␮m
[19]. W-Y2 O3 composite powders prepared by conventional wet
chemical method has a density of 96.28% after SPS sintering, but
large grain size of 5.82 ␮m makes its hardness only 352.92 HV0.2
[40]. Although the hardness of W-Y2 O3 alloys obtained by sol-gel
method and subsequent SPS sintering is about 600 HV, the density
is only 93.8% [49]. Compared with these studies, FD sample in our
work has smaller grain size, higher density and hardness, which
also implies the advantages of freeze-drying and low temperature
sintering method developed in our work. The characteristics of BM
sample and FD sample are summarized in Table 2.
4. Conclusion
The W-Y2 O3 alloys were successfully prepared by freeze-drying
and subsequent low temperature sintering in our work. The aver-
age grain size of W-Y2 O3 composite nano powders synthesized by
freeze-drying method is only 18.1 nm. After low temperature sin-
tering of these composite nanopowders, the formed W-Y2 O3 alloys
possess a smaller W grain size of 510 nm while maintaining a com-
paratively higher density of 97.8%. In addition to a few large Y2 O3
particles (about 100–300 nm) at grain boundaries, more Y2 WO6
particles (about 5–20 nm) distribute both within W grains and at W
grain boundaries. Simultaneously, an interesting phenomenon that
many Y6 WO12 (<10 nm) particles distribute within large Y2 O3 par-
ticles was found. The formation of these ternary phases indicates
that some oxygen impurities in the W matrix can be adsorbed by
these particles, resulting in the purification of W matrix and the
strengthening of phase boundaries. The Vickers microhardness is
as high as 656.6 ± 39.0 HV0.2 . Above results indicate that the pro-
cess of freeze-drying and subsequent low temperature sintering is
a promising way to fabricate high performance oxide-dispersion-
strengthened tungsten based alloys with ultra-fine grain.
Acknowledgements
This work was supported by the National Natural Science Foun-
dation of China (Nos. 51822404 and 51574178), the Science and
Technology Program of Tianjin (No. 18YFZCGX00070), the Nat-
ural Science Foundation of Tianjin (No. 18JCYBJC17900) and the
Seed Foundation of Tianjin University (Nos. 2018XRX-0005 and
2019XYF-0066).
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