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Journal of the European Ceramic Society 35 (2015) 23912401

Systematic optimization of spray drying for YAG transparent ceramics

Le Zhang a,b, , Hao Yang a,b , Xuebin Qiao a,b , Tianyuan Zhou a,b , Zhongying Wang c , Jian Zhang a,b ,
Dingyuan Tang a,b , Deyuan Shen a,b , Qitu Zhang c
b

a School of Physics and Electronic Engineering, Jiangsu Normal University, Xuzhou 221116, China
Jiangsu Key Laboratory of Advanced Laser Materials and Devices, Jiangsu Normal University, Xuzhou 221116, China
c College of Materials Science and Engineering, Nanjing Technological University, Nanjing 210009, China

Received 29 October 2014; received in revised form 4 February 2015; accepted 5 February 2015
Available online 22 February 2015

Abstract
Spray drying parameters have been systematically optimized to granulate a stoichiometric mixture of commercial oxides for YAG transparent
ceramics. The processing parameters and suspension composition were changed in sequence and SEM analysis, EDS, MIP and transmittance
measurements, were used to choose the best spray drying parameters. The optimized inlet and outlet temperatures of drying medium were 75
and 60 C, and its flux and aspiration rate were 25 Hz and 30 Hz, respectively. The balanced suspension composition were: solid content 45 wt.%,
binder PVB 1.0 wt.%, dispersant DS005 0.50 wt.% and the atomizer rotating speed 8000 r/min. The granulated particles exhibited excellent forming
performance with mono-dispersed, spherical and fully dense aggregates, and mean size was 40 m. They could be crushed under 40 MPa. The
homogeneous distribution and microstructure of ceramics assured the high optical quality of YAG ceramics.
2015 Elsevier Ltd. All rights reserved.
Keywords: Spray drying method; Transparent ceramics; YAG; Forming performance

1. Introduction
Since high efficiency Nd:YAG transparent ceramics as laser
gain medium were reported by A. Ikesue in 1995 [12], various
transparent laser materials such as Yb/Nd:YSAG [3], Nd:Y2 O3
[4], Cr:ZnS [5], have been developed. Their optical qualities
have been greatly improved and their applications in physical measurements and medical uses as laser materials are now
well established [6]. Transparent ceramics offer homogeneous
(or gradient) and large dopant concentration, design flexibility,
and large scale required for high power laser. YAG transparent ceramics have been proved to be the best laser host material.
Especially, other rare earth ions (Yb, Ho, etc.) [78] doped YAG
have used to generate different wavelengths, pulse width or tunable laser outputs [910]. Furthermore, composite lasers with
complicated structure of YAG ceramics to improve the thermal

Corresponding author at: School of Physics and Electronic Engineering,

Jiangsu Normal University, Xuzhou 221116, China. Tel.: +86 516 83403242;
fax: +86 516 83403242.
E-mail address: njutzl@163.com (L. Zhang).
http://dx.doi.org/10.1016/j.jeurceramsoc.2015.02.004
0955-2219/ 2015 Elsevier Ltd. All rights reserved.

management and increase the pump efficiency have been widely

reported [1112].
In general, the residual pores, grain boundary impurities and
dopant segregation as optical scattering centers still exist in the
ceramic materials [13]. For laser materials, the technology to
remove those scattering sources becomes extremely important.
Super full-dense ceramics with pore-free structure and clean
grain boundary are needed to be fabricated to lower their optical loss [14]. However, the agglomeration of raw powders for
ceramics results in major microstructure defects before ceramic
forming [15]. The homogeneous distribution of raw powders
becomes more difficult during shaping process. Those unexpected accidents will produce the residual pores or secondary
phases after sintering, severely lowering the optical quality. In
addition, the strong friction force between raw powders with
small size (<1 m) inhibits themselves sufficient filling in the
mold, especially for the fabrication of large size, complex shape
or composite structure ceramics. Together with the agglomeration of powders, their bad flowability and filling property will
lead to a discrepant shrinkage, even severe crack of sintered
ceramics [16].

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L. Zhang et al. / Journal of the European Ceramic Society 35 (2015) 23912401

Spray drying method is a powder processing technique

widely used in the manufacturing of dried food, oxide ceramics
and pharmaceuticals, by which the suspension is transformed
into dry particles by spraying thousands of small droplets into a
hot medium [17]. The solvent dries quickly and the small powders within each droplet form a solid granule [1819]. It is a
powerful technique to granulate powders with good flowability
and great homogeneity of components.
As known, the suspension state (such as density and viscosity)
and process conditions (such as temperature, flux and aspiration
rate of drying medium) play important roles in producing various product shapes and sizes. The spray process is a result of
above many interwoven complex factors and a balance must
be found [20]. In this paper, spray drying method was used to
granulate a stoichiometric mixture of commercial oxides for the
production of YAG transparent ceramics. The suspension composition and processing parameters were changed in sequence,
and the resulting granulated particles were analyzed by SEM
to verify their shapes, sizes and distributions as well as their
crushing behaviors. The aim was to achieve the optimized suspension composition and process parameters for better forming
performance of powders. Furthermore, YAG transparent ceramics have also been fabricated by solid-state reaction sintering to
reinspect the optimized experimental parameters.
2. Materials and experimental details
2.1. Suspension preparation
High purity Al2 O3 (99.99%, TM-DAR, Taimei Chemicals,
Japan), Y2 O3 (99.999%, Jiahua Advanced Materials Resources,
China) powders were used as starting materials. These powders were blended together according to the stoichiometric of
Y3 Al5 O12 and ball-milled for 15 h in anhydrous alcohol with
TEOS (0.5 wt.%) and MgO (0.1 wt.%) as sintering aids, DS005
(0.25, 0.50, 0.75, 1.0 wt.%, Polymer Innovations, Vista, CA) as
dispersant, and polyvinyl butyral, PVB, (0.0, 1.0, 2.0, 3.0 wt.%,
M.W. 40,00070,000, Aladdin) as binder. The starting solid content was 40 wt.%, binder 1.0 wt.%, dispersant 0.25 wt.%.
2.2. Spray drying
The suspensions were dried using a spray dryer (TR120AT6HOP, PRECI, Japan). Spray drying parameters needed to be
optimized including: temperature, flux and aspiration rate of
hot air (inlet/outlet, full capacity (100%) are 50 Hz and 60 Hz,
respectively), atomizer speed (8000, 11,000, 14,000 r/min). The
feeding speed of suspension was fixed at about 30 ml/min standardized by pure ethanol solvent. The starting atomizer speed
was 8000 r/min.
2.3. Ceramic fabrication
The granulated particles were dry-pressed under 40 MPa into
22 disk and then cold isostatically pressed 200 MPa. Green
compacts were firstly calcined at 900 C for 10 h with slow heating rate (0.5 C/min) to completely remove the residual organic

component and then sintered at 1780 C for 8 h under high vacuum (1.0 106 Pa), and finally annealed at 1450 C for 10 h.
2.4. Characterizations
The morphology and microstructure of granulated particles and ceramics were examined using scanning electron
microscopy (SEM, JSM-6510, JEOL, Japan) coupled with an
energy dispersive X-ray spectrometer (EDS). The particle size
distribution was recorded by Image J software. The apparent
density and tap density were measured according to national
standards of China, GB5061-85 and GB5162-85, respectively.
The pore size distribution of green compact was evaluated
by mercury intrusion porosimetry (MIP, Poremaster GT-60,
Quantachrome, USA). Optical transmittance of YAG ceramics was measured using a UV/VIS spectrometer (Lambda 950,
Perkin Elmer, USA). Before the measurements, both surfaces of
samples were polished to 3 mm. All measurements were carried
out at room temperature.
3. Results and discussion
3.1. Optimization of processing parameters
The primary steps of spray drying include atomization,
droplet to particle conversion (solvent evaporation) and particle
collection. The atomization is a key parameter in determining
particle size. Before studying this step, the other processing
parameters such as inlet (Tinlet ) and outlet (Toutlet ) temperatures
of drying air should be determined firstly. Generally, Tinlet varies
in a range of 10 C with respect to the ethanol boiling temperature of 78 C [21]. Toutlet indicates the energy consumed during
drying process and depends on Tinlet , outlet pressure and feed
speed, etc. Meanwhile, in order to obtain a better bond behavior
of binder, the mean temperature in the drying chamber should
be slightly higher than the glass transition temperature (Tg ) of
PVB. In our experiments, the softening temperature of PVB was
61.5 C. Thus, Tinlet and Toutlet were selected at 75 C and 60 C,
respectively.
In fact, for an efficient drying, Tinlet and drying medium
flux (Finlet ) decide the total energy transferred to the droplet.
The aspiration rate (the capacity of outlet blower, Foutlet ) determines the residence time of granules in the chamber, which is
also required to ensure sufficient drying. They work together to
evaporate the solvent completely from the droplet.
When the inlet blower worked at full capacity of 50 Hz
(100%), the excessive Finlet would lead to poorly granulated and
very hard particles (not shown here) due to rapid evaporation of
solvent, which would lead to the formation of large pores during shaping by pressing. These pores could be hardly eliminated
by sintering. Thus, Finlet needed to be decreased to reduce the
energy. As Finlet decreasing, the particle became more spherical
and softer, and the granulated particles showed the best morphology when the inlet blower worked at half capacity of 25 Hz.
The granules size was about 2050 m although its shape was
still apple or doughnut. Meanwhile, the mass collection rate of
granules to theoretical yield increased with the decrease of Finlet

L. Zhang et al. / Journal of the European Ceramic Society 35 (2015) 23912401

Table 1
Collection rates of granules to theoretical yield with different capacities of
blowers.
Capacity (Finlet , Foutlet )

100% (50, 60 Hz)

70% (35, 42 Hz)
50% (25, 30 Hz)

Mass collection rate

Without sieving (%)

100-Mesh sieving (%)

35.7
78.7
94.1

65.9
85.6

(Table 1), and it was higher than 94% without sieving and 85%
after 100-mesh sieving when Finlet and Foutlet decreased to 25 Hz
and 30 Hz, respectively. However, a further decrease of Finlet and
Foutlet lower than 50% would cause the incomplete drying and
obstruction of nozzle. Therefore, Finlet and Foutlet were selected
25 Hz and 30 Hz, respectively.
3.2. Optimization of suspension composition
The atomization is a key parameter in determining particle
size. In this study, the centrifugal force was employed to assist
atomization process. After selecting an atomizer, the empirical
equation of control droplet diameter (Dd ) could be expressed
[22]:



0.25 0.06 0.375 
fL
L
L
Dd = C
(1)
0.375
fL vL + fA vA
A
C is a constant, and it depends on nozzle design. , , , v and
f are density, viscosity, surface tension, velocity and flow rate
of the liquid (L) or hot air (A). This equation indicates that the
suspension composition plays more important role in producing
various product shapes and sizes than processing parameters.
And Dd is mostly proportional to the density, viscosity and
surface tension of suspension. However, these three parameters of suspension are effectively changed by its solid content,
dispersant content and binder content.
3.2.1. Solid content of suspension
As the primary factor, the solid content (Cd ) of droplet (d)
atomized from suspension has a strong influence on the density
(g ) and particle size (Dg ) of granules (g) [23]:
D 3 Cd
g
= d3
d
Dg Cg

(2)

The increase of solid content results in an increase of suspension viscosity and leads to the formation of dense granules
and large size. Fig. 1(a) presents the morphology of granulated
particles atomized from suspension with increased solid content
of 50 wt.%. All granules exhibited better spherical and solid
shape without any pinhole and their mean size was 48.9 m
(Fig. 1(b)). There were great improvement in particle shape
and increase in size compared to that of solid content 40 wt.%,
Fig. 1(c and d), under the same processing parameters determined by above results.
As known, the droplet shrinks because of the fast evaporation of solvent during drying. The solvent moves from inside

2393

to outsize of the droplet and the solid powders are also carried
along. At a lower solid content 40 wt.%, the faster and more
free movement of solid powders would form a soft shell around
the droplet and produce the hollow granules. The shell would
decrease the evaporation rate through the droplet surface. As the
temperature of the droplet inside increasing, the solvent would
begin to evaporate directly from the inside and a void would be
produced inevitably in Fig. 1(c). However, a higher solid content
would shorten the drying process because the movement of solid
powders became more difficult due to the low moisture. Thus,
it avoided the formation of hollow and hard particles [24].
In addition, the granules was formed with spherical shape
and high density when solid content was 50 wt.% in Fig. 1(a),
the extra-large granules were also formed. High solid content
seemed to have a negative effect on the formation of well packed
structure during shaping. Moreover, such high solid content
could cause the obstruction of nozzle in the mid-stage of spray
drying, being difficult to continue work for atomizer. Therefore,
a modest reduction of solid content was needed and 45 wt.% was
selected to continue the optimization of suspension composition.
3.2.2. Binder content of PVB
Generally, binder has to be added in the suspension to create
a mesh that keeps the solid particles combined with each other
and gives the outstanding increase in strengths for granulated
particles. Here, PVB was selected as the binder to optimize its
content.
Fig. 2 shows SEM images and size distribution of granulated
particles with different contents of binder. All the granulated
particles atomized from suspension of PVB content 1.0 wt.%
(Fig. 3(a and b)) exhibited monodispersed and fully dense aggregates with good spherical shape and smooth surface. However,
the binder content increased to more than 2.0 wt.%, a doughnut
or apple shape formed again in most granules (Fig. 3(c)). The
mean particles size gradually became larger from 30 m to
60 m with increasing binder content (Fig. 3(d)). Especially,
the granules exhibited similar mean size 40 m when binder
contents were 0.5 wt.% and 1.0 wt.%. But the maximum size
jumped from 87 m to 101 m when PVB content was from
1.0 wt.% to 2.0 wt.% (Fig. 3(d)). In addition, the size distribution
gradually became wider from = 7.0 to = 23.5 with increasing binder content and the maximum increase occurred when
an excessive addition of PVB 3.0 wt.% (, scale parameter of
distribution, was used to describe the dispersion degree of data
for normal distribution). The granulated particles with binder
content lower than 1.0 wt.% had similar and more standard normal distribution. This was in favor of imparting better forming
performance of granulated particles for green compact.
According to Eq. (1), the granules size is proportional to the
viscosity of suspension, and the binder could result in a significant increase in viscosity, leading to the gradual increase of
granules size. However, the excessive binder would also easily
form a flexible shell with low permeability around the droplets
at the starting stage of droplet-to-particles conversion [25]. It
decreases the evaporation rate of solvent, and the solvent begins
to evaporate directly inside, leading to the formation of central uplifts of droplet. This situation can severely destroy the

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L. Zhang et al. / Journal of the European Ceramic Society 35 (2015) 23912401

Fig. 1. SEM images and size distributions of granulated particles with different solid contents. (a and b) 50 wt.%, (c and d) 40 wt.%.

Fig. 2. SEM images of granulated particles with different binder contents (a) 0 wt.%, (b) 1.0 wt.%, (c) 3.0 wt.% and their size distributions (d).

L. Zhang et al. / Journal of the European Ceramic Society 35 (2015) 23912401

1.7

0.8

2395

(a)

Accumulation/ %

Density/ g cm

-3

TD

1.6

1.5

1.4

AD

(a) Binder

(a)
(b)
(c)
(d)
(e)

0.6
0.4
b

0.2

20 nm

0.0 wt.%
0.5 wt.%
1.0 wt.%
2.0 wt.%
3.0 wt.%

20 m

35 m

0.0

1.3
0.0

1.5

1.4

2.0

Content/ wt.%

3.0

0.01

0.1

40

80120

Pore size/ m
100

TD

(b)

-3

98

Density/ gcm

1.6

Density/ g cm

-3

1.7

1.0

AD

(b) Dispersant

Sintering 1700 C*8h

CIP 200 Mpa
Dry pressing 40 Mpa

96

60
55
50

1.3
0.25

0.50

0.75

Content/ wt.%

1.00

Fig. 3. Apparent density and tap density of granulated particles with different
contents of binder PVB (a) and dispersant DS005 (b).

sphericity degree and produces that doughnut or apple shape,

and decrease the flowability and the apparent density (AD) and
tap density (TD) of granulated particles.
AD and TD of granules with different binder contents are
shown in Fig. 3(a). Obviously, the particles with 1.0 wt.% PVB
had the highest AD and TD values and they were about 1.50 and
1.65 g/cm3 , respectively, reached 33% and 36% of theoretical
density of YAG crystal (4.55 g/cm3 ). Both smaller particle size
and narrower distribution (0.0, 0.5 wt.%), as well as very bigger size and wider distribution with non-spherical shape (2.0,
3.0 wt.%) would decrease AD and TD.
As well known, the value of AD represents the flowability
and filling property of granules, which is determined by the
interacting force between granules. More binder would result in
the increase of particle size that would decrease the Vander Wals
forces between particles, imparting better flowability and higher
filling density [26]. Meanwhile, the increased binder content
is in favor of the formation of fully dense particles that can
also increase AD value. However, the bigger granulated particles
would bring bigger voids content during natural packing that
decreases the filling density. Under the confluence of two factors,
the granules with 1.0 wt.% PVB have the highest AD and TD
and exhibited the best forming performance.
The green compacts from granules with different binder
contents were cold isostatically pressed (CIP) under 200 MPa.
Their pore size distributions are shown in Fig. 4(a). They exhibited only one peak in 20200 nm excepting that the green
compacts with excessive binder, 2.0 and 3.0 wt.%, had another

45
0.0

0.5

1.0

1.5

2.0

2.5

3.0

Binder/ wt.%
Fig. 4. (a) Pore size distributions of green compacts from granulated particles
with different binder contents and (b) the followed density change of ceramics.

distribution peak at about 35 m, representing larger pores in

them. The 1.0 wt.% binder formed green compact had the smallest pore size distribution centered at about 60 nm. This relatively
smaller and more uniform pore size would greatly promote the
densification of ceramics during sintering. Fig. 4(b) shows the
density change of fabricated ceramics under different stages.
The green compacts with 2.0 and 3.0 wt.% PVB showed the
lower density, although they had little difference after CIP.
However, the difference was acutely magnified after vacuum
sintering and the fabricated ceramic with 1.0 wt.% binder had
the highest density 99.3% under a lower sintering temperature 1700 C (they all finished densification >1750 C). This
is consistent with the results of SEM, AD/TD of granules
and MIP analysis of green compacts. In fact, the fabricated
ceramic with 1.0 wt.% binder also had the highest optical transmittance. Therefore, the optimized binder content of PVB is
1.0 wt.%.
3.2.3. Dispersant content of DS005 and speed of atomizer
Solid particles in the suspension have a tendency to agglomerate due to the attractive Van der Waals force. Appropriate
dispersant is needed to eliminate that tendency by changing
the powder surface properties. Through either the electrostatic repulsion or steric hindrance, the repulsive force become
stronger than the attractive force to remain themselves separate
in suspension [20]. DS005 is a strong polymeric dispersant that
are functioning via both electrostatic and steric mechanism due

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L. Zhang et al. / Journal of the European Ceramic Society 35 (2015) 23912401

Fig. 5. SEM images of granulated particles with different dispersant contents (a) 0.25 wt.%, (b) 0.50 wt.%, (c) 1.0 wt.% and their size distributions (d).

to a hydrocarbon chain and a polar ionic part (COOH , SO3 ).

Meanwhile, dispersant addition can dramatically reduce the viscosity and surface tension of suspension, and further change the
particle size according to Eq. (1). In addition, as well known, the
processing parameter, the speed of the centrifugal atomizer can
dramatically change the size of granules due to the change of
shear force [27]. Here, dispersant DS005 for stable suspension
were systematically investigated.
Fig. 5 shows SEM images and size distributions of granulated particles with different dispersant contents. All granules
with 0.25 wt.% and 0.50 wt.% DS005 exhibited monodispersed
and fully dense aggregates with good spherical shape (Fig. 5(a
and b)). However, the binder content increased to 1.0 wt.%,
a apple or even long wax gourd shape formed in most granules (Fig. 5(c)). The mean particles size firstly decreased
from 55 m to 40 m with increasing the dispersant from
0.25 wt.% to 0.50 wt.% (Fig. 5(d)). But a slight increase would
occur with further increasing the dispersant and reached 45 m
for 1.0 wt.% DS005 sample. The 0.50 wt.% DS005 added granules had the smallest particle size. Their size distributions were
similar and all values of were about 10, closing to the normal
distribution. Meanwhile, the granules showed some difference
in AD and TD in Fig. 3(b) that indicated their different forming
performance. And the granules with 0.50 wt.% DS005 had the
best flowability and filling property. Like the decrease of particle
size, the AD and TD had a decrease with increasing the dispersant content, especially the sample of 1.0 wt.% DS005 due to
the poor and not spherical shape.

In addition, in order to obtain different particles sizes and

distributions, the atomizer speed was tuned to finally obtain better forming performance. Unfortunately, these attempts were
failed when the atomizer speed was lower than 8000 r/min.
Because considerable amount suspension was adhered on the
wall of chamber and lots of larger aggregates were formed due
to the lower rotating speed, leading to a low collection rate and
poor morphology of misshapen particles. However, an obvious
regularity was observed in Fig. 6(a) when it was higher than
8000 r/min. With increasing the atomizer speed, the mean size
obviously decreased and it was less sensitivity for dispersant
content gradually. Especially, when the atomizer speed reached
14,000 r/min, the mean size from different dispersant contents
was very similar with each other. This is easily understood that
the reduction effect due to the increased atomizer speed plays
more dominant role than the effect of different dispersant content. In fact, the change of AD/TD with different dispersant
contents was not big, comparing to Fig. 3(a), and the effect of dispersant on the granules properties were less important than that
of binder. However, still the regularity existed that the 0.50 wt.%
DS005 added granules had the smallest size.
In fact, the addition of dispersant can change the suspension viscosity. When the dispersant content is lower (0.25 wt.%),
it could not reach the saturation adsorption on particle surface. The repulsive force between particles is weaker due to
the lower charge density and thinner double electrical layers.
But the Van der Waals force is stronger due to the higher viscosity. The suspension is only partly in decondensation state

L. Zhang et al. / Journal of the European Ceramic Society 35 (2015) 23912401

60.0

3.3. Crushing behavior of granulated particles

(A)

Atomizer speed: r/min

(a)
8000
11000
(b)
(c)
14000

(a)

Mean Size/ m

50.0
(b)

40.0

30.0

(c)

20.0
0.25

0.50

0.75

1.00

Dispersant/ wt.%

Accumulation/ %

0.8

(B)

0.6
0.4
0.2

(a)
(b)
(c)
(d)

0.25 wt.%
0.50 wt.%
0.75 wt.%
1.0 wt.%

c
d

b
a

0.0
0.01

2397

Pore size/ m

0.1

Fig. 6. (A) Mean sizes of granulated particles with different atomizer speeds
and (B) the pore size distributions of green compacts with different dispersant
contents.

and has poor stability. With increasing the dispersant content,

it gradually reaches the saturation adsorption. The repulsive
force becomes stronger. The suspension has been completely
decondensated and has the smallest viscosity and best stability (0.50 wt.%), which assuring the homogeneous distribution
of multi-components. However, when the dispersant content is
more than that of the saturation state needed, the excessive dispersant molecules enter into the solvent and increase the ionic
concentration and decrease the Zeta potential, weakening the
repulsive force. In addition, the excessive dispersant molecules
would form a network by the action of bridge connection [28].
They together lead to the lower viscosity, poorer flowability and
stability of suspension (1.0 wt.%).
Fig. 6(b) is the pore size distributions of the green compacts
with different dispersant contents. Unlike the double peaks of
some samples in Fig. 4(a), all green compacts here exhibited
only one peak in the range of 30100 nm and had similar size
distribution centered at about 60 nm, although the 0.50 wt.%
DS005 formed green compact had the smallest pore size and it
exhibited the best flowability and filling property already being
proved by above AD/TD results in Fig. 3(b).
Therefore, the optimized suspension composition are: solid
content 45 wt.%, binder content of PVB 1.0 wt.%, dispersant
content of DS005 0.50 wt.% and the atomizer rotating speed
suitable for this suspension 8000 r/min.

The crushing behavior of granulated particles during forming is a very important characteristic to evaluate their quality
and it has a significant impact on the density and microstructure
of green compact. Here, SEM images of fracture surfaces and
the density changes of green compact are used to evaluate the
strength of granules. The observation point for SEM was the center of the compact under different CIP pressures of 10100 MPa.
In Fig. 7, a carcass of spherical shape remained until 60 MPa,
but a homogeneous surface structure was completely formed
under 80 MPa. The densities of green compacts showed a gradual increase in Fig. 8(A) and two turning points. The granules
are composed of multi-levels of particles sizes. With increasing
CIP pressure, the granules firstly begin to arrange and fill the
void in 020 MPa. Then, the granules begin to crush into second
particles and filled interspace between granules in 2080 MPa.
Finally, the second particles were crushed into raw particles to
arrange and fill under above 80 MPa. Fig. 8(A) curve (b) is the
total porosity change measured by MIP. It decreased gradually
due to the expulsion of air and had already reached about 40%
after 80 MPa.
Fig. 8(B) shows the pore size distributions of green compacts under different CIP pressures. Obviously, they all exhibited
only one peak indicating the better homogeneity. When pressure was low at 10 MPa, the pore size was in a wide range
of 30 nm1 m. With increasing the pressure, the pore size
distribution gradually shifted to the smaller size. The detailed
change of mean pore size is shown in Fig. 8(B, inset) and
it decreased from 120 nm to 70 nm with gradually narrower
width of distribution, representing the smaller and more homogeneous pore in compact. In addition, an obvious turning point
of pressure was observed at 40 MPa. From 10 MPa to 40 MPa,
the pore size had a great decrease. In these compacts, there
was larger pore (>200 nm). But from 40 MPa to 80 MPa, the
total decrease of pore size was only 10 nm (from 80 nm to
70 nm). This indicated the green compacts pressured under
4080 MPa were in the same stage. Therefore, the granules finished the crush to form dense compact only pressured higher than
40 MPa.
In addition, the transmittance of sintered YAG ceramics also
gradually increased with increasing CIP pressure and the biggest
jump was found before 40 MPa and followed a slight increase
after 60 MPa. It reached 84.20% at 100 MPa, very near to the theoretical transmittance. Generally, a higher pressure, less porosity
and smaller pore size shorten the distance between the particles.
They are in favor of the diffusion and the densification during
sintering process.
These above results indicate the granulated particles have
excellent forming performance. They could form green compacts without inter-granules void only under 40 MPa and are
almost completely crushed under 80 MPa to form the dense and
homogeneous structure. The packing density under 100 MPa is
about 55.9%. Using the granulated particles with good forming
performance and suitable strength, even at low CIP pressure, it
is possible to fabricate transparent ceramics with higher optical
quality.

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L. Zhang et al. / Journal of the European Ceramic Society 35 (2015) 23912401

Fig. 7. SEM images of fracture surfaces of green compacts under different CIP pressures.

3.4. Microstructure and optical transmittance

Density/ gcm

(A)

50
48

2.4

46

Density
Total porosity

2.2

44

2.0

42
1.8
40

Total porosity/ %

-3

2.6

1.6
38
0

20

40

60

80

100

Pressure/ MPa

(B)

120

70 nm

Mean size/ m

Accumulation/ %

0.8

100

0.6
0.4

(a) 10 MPa
(b) 20 MPa
(c) 40 MPa
(d) 60 MPa
(e) 80 MPa
(f) 100 MPa

0.2
0.0
0.01

b
c

80
20

40

60

80

100

Pressure/ MPa

e
f

0.1

10

Pore size/ m
Fig. 8. (A) Densities and total porosities of green compacts under different CIP
pressure, (B) their pore size distributions and the change of mean pore size
(inset).

Fig. 9(A) shows the typical sphere (A1) and its surface (A2)
of one granulated particle with the optimized suspension. Every
granulated particle had very smooth and entirely spherical surface, Fig. 9(A1). Its magnification (20,000 times) of local surface
was Fig. 9(A2), it showed the dense structure with little and
small pore, and different particle morphologies corresponded to
different kinds of raw material, i.e., Al2 O3 and Y2 O3 for small
particle and big sheet, respectively. The micro-region EDS analysis is shown in Fig. 9(A3). The surface showed homogenous
distribution of Y/Al = 0.593, very closing to theoretical value
Y/Al = 3/5 = 0.60. The homogeneous mixing of raw materials
greatly shortens the diffusion distance and rapidly complete
the densification during sintering process. However, the typical composition deviation was observed in the granules without
binder in Fig. 9(B). Although the granulated particle still had
the better spherical shape, Fig. 9(B1), more Al2 O3 particles with
smaller size were on its surface and they seemed to cover the
bigger sheet Y2 O3 particles in Fig. 9(B2). EDS analysis showed
that in that granulated particle without binder, Y/Al = 0.562 was
deviated from the theoretical value 0.60.
In fact, this is known as the microencapsulation phenomenon
due to the big difference in particle sizes of multi-components.
Diffusion plays an important role in the solvent evaporation
and particle self-assembly stages. Different diffusion coefficient
(Dc ) affects the particle movement in the droplet [29]:

Dc = k

KB T
6c Rc

(3)

L. Zhang et al. / Journal of the European Ceramic Society 35 (2015) 23912401

2399

Fig. 9. SEM images of one granulated particle (1) and its surface (2) and the EDS analysis (3) with the optimized suspension (A, binder content 1.0 wt.%) and
without binder (B).

where k, KB , T, c and Rc are diffusion correction factor, Boltzmanns constant, temperature, viscosity and component size,
respectively. Thus, Dc has a negative correlation to the size of
component. The component moves quickly with a decrease of
component size. In our suspension, the particle sizes of Al2 O3
and Y2 O3 were 100200 nm and 1 m, respectively, in Fig. 9.
When the suspension has no binder, Fig. 9(B), the combination
effect between particles would be weakened, comparing to the
suitable addition of binder. Smaller Al2 O3 particles could move
faster under the capillary force in the droplet, and then complete
the self-assembly of particles into close-packed arrays. It is possible for a smaller component to coat a larger component and
result in the composition deviation [30]. Although this deviation
was not big and could be compensated by the followed sintering process, it actually decreases the transmittance of sintered
ceramics. Therefore, a suitable addition of PVB binder is very
important to form homogeneous and dense granules.
The typical microstructures of surface (A1) and fracture surface (A2) of sintered ceramic with the optimized suspension
are shown in Fig. 10(A). They had a homogeneous microstructure and no pores or other defects could be observed. The grain
size was about 10 m with clear and clean grain boundary.
And a predominant transgranular fracture was observed with
little intergranular fracture. This homogeneous microstructure

assured the high optical transmittance. However, the defects like

intra- or inter-crystalline pores were generally observed in the
ceramics with non-optimized suspension or processing parameters. Fig. 10(B) shows the surface (B1) and fracture surface
(B2) of sintered ceramic with 1.0 wt.% DS005. The pores were
simultaneously trapped into the grains on the surface and fracture
surface because of the poor spherical shape of granulated particles, and lower AD/TD values. Therefore, a suitable addition
of dispersant is also important to obtain good spherical granules
and then defect-free ceramics.
Finally, the highest optical transmittance was observed under
our optimized technology in Fig. 11. The transmittance at
1064 nm and 400 nm reached up to 84.74% and 80.17%, respectively, which were high enough for laser application if the
active ions were doped in pure YAG host. In addition, the
non-optimized composition of suspension would lead to the
decrease of transmittance, accompanying with the doughnut
or apple shape of granules. Under different contents of PVB,
the transmittance of YAG ceramic firstly increased and reached
the maximum value at 1.0 wt.% and then decreased with further increasing PVB content in Fig. 11(inset). This is consistent
with the above results of morphology, size distribution, AD/TD,
pore distribution, etc. This indicates that the quality controls
of granulated particles, including particle size, size distribution,

2400

L. Zhang et al. / Journal of the European Ceramic Society 35 (2015) 23912401

Fig. 10. SEM images of surface (1) and fracture surface (2) of ceramics with the dispersant content (A, 0.5 wt.%) and 1.0 wt.% (B).

100
84.74 %

80

Transmittance/ %

Transmittance/ %

80.17 %

60
40
20

80 (a)
60 (b)

20
0

0
500

(a) @ 1064 nm
(b) @ 400 nm

40

0.0 0.5 1.0 1.5 2.0 2.5 3.0

Binder/ wt.%

1000

1500

2000

2500

3000

Wavelength/ nm
Fig. 11. Transmittance of YAG ceramic from the optimized technology and its
change with different binder contents (inset).

morphology and elements distribution, contribute to refine the

microstructure of sintered compact, and then improve the optical
transmittance of YAG ceramics.
In addition, the scaled-up production of granulated particles
for YAG was operated under the optimized technology. The feeding flow was 40 g/min for suspension. The solid content was
45 wt.% and thus the mass yield of granulated particles reached
1.0 kg/h. In a steady work state without nozzle obstruction and
other unexpected accidents, the SEM image of granulated particles is shown in Fig. 12(a) for scaled-up production 10 kg. High
production rate with well mono-dispersed spherical granules
provided more opportunities for their applications, especially
in large scale or thickness, composite structure of YAG. Their
photographs of various transparent YAG products are shown
in Fig. 12(b). They were all transparent and suitable for

Fig. 12. (a) SEM image of granulated particles using the optimized technology for scaled-up production of 10 kg; (b) photographs of their various transparent YAG
products.

L. Zhang et al. / Journal of the European Ceramic Society 35 (2015) 23912401

different applications with excellent forming performance and

high optical quality.
4. Conclusions
In this paper, spherical YAG granulated particles with good
forming performance and transparent ceramics with high optical transmittance were successfully obtained by a systematic
optimization of spray drying. (1) The optimized processing
parameters were: inlet and outlet temperatures of drying air
selected at 75 C and 60 C, its flux and aspiration rate set
at 25 Hz and 30 Hz (at half capacity), respectively, and the
atomizer rotating speed 8000 r/min. The balanced suspension
composition were: solid content 45 wt.%, binder content of
PVB 1.0 wt.%, dispersant content of DS005 0.50 wt.%. (2) The
granulated particles exhibited mono-dispersed and fully dense
aggregates with good spherical shape and smooth surfaces, and
their mean size was about 40 m. The apparent density and tap
density of granules were about 1.50 and 1.65 g/cm3 , respectively.
(3) The compacts pressured only at 40 MPa could eliminate
inter-granules void, indicating suitable strength of granules. The
high optical transmittance of sintered ceramics that at 1064 nm
reached up to 84.74%. (4) The optimized processing parameters
and suspension composition as well as the study methods and
basic principles provided by this paper, could directly serve for
the semi-industrialized productions of optical or other functional
ceramics.
Acknowledgements
The authors acknowledge the generous financial support from
Priority Academic Program Development of Jiangsu Higher
Education Institutions (PAPD), and National Natural Science
Foundation of China (51402133, 51302115, 61405081).
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