J. Ceram. Sci. Technol.

, 09 [3] 327-336 (2018)

DOI: 10.4416/JCST2018-00022
available online at: http://www.ceramic-science.com
© 2018 Göller Verlag

Slurry Development for Spray Granulation of

Ceramic Multicomponent Batches
P. Höhne *, B, Mieller, T. Rabe
BAM Federal Institute for Materials Research and Testing, Division 5.5 – Advanced
Technical Ceramics, Unter den Eichen 44 – 46, D-12203 Berlin, Germany
received March 7, 2018; received in revised form May 16, 2018; accepted May 17, 2018

Abstract
The granules commonly yielded by spray drying procedures exhibit a hard shell and an irregular, dimpled shape,
which is often described as donut-like morphology. Sintered parts produced from such granules suffer from mi-
crostructural defects and reduced mechanical properties resulting from these disadvantageous granule properties.
Using the example of alumina, zirconia and zirconia-toughened alumina (ZTA) batches, this paper shows that the
morphology of the granules can be tuned by adjusting slurry stability. High zeta potential is essential to optimally
disperse the particles. But to achieve spherical and soft granules the electrostatic repulsion forces between the particles
should be reduced before spray granulation. Electrostatic repulsion forces were changed with the addition of nitric
acid. Measurements of zeta potential and viscosity, as well as sedimentation investigations with an optical centrifuge
were used for precise slurry assessment as a major precondition for optimal and reproducible adjustment of slurries be-
fore spray drying. Sedimentation analysis using an optical centrifuge was performed to investigate different influences
like that of additive composition, solids content or pH-value on the sedimentation behavior. Adequately flocculated
slurries lead to homogeneous, soft granules that can be easily deformed and pressed. The fraction of donut-shaped
particles and the rigidity of granules were reduced. Consequently, the sintered parts produced from these granulates
show improvements regarding porosity, pore size distribution, sintered density and biaxial strength.
Keywords: Slurry optimization, optical centrifugation, destabilization, spray drying, biaxial strength

I. Introduction scale. But strength-reducing internal microstructural de-

Powder compaction by means of uniaxial or isostatic fects caused by spray-dried granules with hollow and hard
pressing is a widely used shaping method in ceramic pro- shells are often observed in compacted green and sintered
duction, because of rapid shaping, automation, no prod- ceramics. Hence, the characteristics of the granules have
uct-drying requirement and comparatively low produc- to be optimized for better compaction behavior and a re-
tion cost. Dry pressing requires the use of free-flowing duced number and size of flaws in the powder compact.
powders to allow rapid die filling and to avoid packing de- Many authors have extensively studied and described
fect development. Many powders, because of their small typical microstructural defects 4 – 6 caused by spray-dried
size, irregular shape or surface characteristics, are cohesive granules. Two defect categories are described in the liter-
and do not flow well. Hence, granulation methods are used ature 4, round-shaped large pores resulting from hollows
to transform fine raw material to coarser granules. Such or dimples in the granules and crack-like porosities. Both
granules have a larger size and more spherical shape than defect types originate from an incomplete destruction of
initial powder particles. Both are contributing factors and granules under compaction pressure.
their modification improves the flow properties. The ideal To understand this behavior of granules, a detailed con-
granule for dry-pressing should be spherical with a diam- sideration of the spray-drying process is helpful. The
eter of about 50 to 100 lm, ensuring good flowability 1. spray-drying process uses a ceramic suspension, which
Different granulation methods are competing in pow- is a mixture of a liquid carrier phase and the solid ceramic
der metallurgy and ceramics 2, 3. Starting from a slurry, particles suspended within. Depending on different pa-
spray drying, fluidized bed techniques and (spray) freeze rameters such as dispersant content and pH-value, the
granulation are available. Furthermore, granulates may be solid particles are either well dispersed or agglomerated.
formed by the appropriate admixing of a binder solution
Two sequential steps have to be controlled in the process
and other organic additives into a stirred dry powder, that
of granulate formation: atomization and droplet drying 5.
is pelletization.
In the two-fluid nozzle, the relative velocity between the
Spray-drying granulation appears to be the best method
liquid and gas is the main driving force of the atomization
for obtaining granules with high flowability on industrial
process and is controlled by nozzle geometry and rates
* Corresponding author: [email protected] of liquid feed and atomization gas flow. Droplets injected
328 Journal of Ceramic Science and Technology —P. Höhne et al. Vol. 9, No. 3

into a spray-dryer chamber dry as a result of the evapo- profile consists of numerous individual transmission val-
ration of water from the surface. Hard granules with hol- ues. At a user-defined time interval, the transmission of
lows arise when well-dispersed feed slurries are used. This all detectors is measured at once, delivering a transmis-
phenomenon originates from the fast particle and binder sion profile for this specific time over the whole cuvette
migration to the periphery, as droplet drying proceeds. A height. This allows the detection of minor changes in tur-
dense dried layer forms instantaneously at the droplet sur- bidity anywhere within the slurry height. Fig. 1 shows a
face. Another typical source of flaws in dry-pressed parts typical transmission diagram of an 80 wt% alumina slurry
is the incomplete cohesion of granules, which can lead to measured with the centrifuge. Values that can be extract-
crack-like defects at the granule boundaries. This behavior ed from such measurement are, for example, the sediment
has been imputed to an uneven distribution of the binder height (indicator of the packing density), the sedimenta-
in the pressed bodies, caused by its migration toward the tion rate (measured by the distance between successively
granule surface during drying 6, 7. Hence, the interparticle recorded transmission profiles), and the slope of the trans-
forces, which are responsible for the suspension stability mission profiles. The sediment height is assessed relative-
(dispersed or destabilized), play an important role in the ly, because the filling height shows small differences that
evaluation of the granule morphology. need to be considered. The relative sediment height (RSH)
Interparticle forces and resultant granules properties can is calculated using the following formula (1):
be effectively manipulated by adapting the properties of h
the slurry, especially the level of flocculation, as will be RSH = sed (1)
hmen
demonstrated in this paper. A link between formation of With subscripts indicating the extracted values with h sed
hollow granules and level of flocculation of the slurry was for the sediment height and h men the height of the menis-
for the first time discussed by Lee et al. 8. They have found cus (corresponds to the filling height). The slope of the
that homogeneous granules form at low dispersant levels transmission profile is an indicator of the particle size dis-
for non-aqueous silicon nitride slurries with PVB binder tribution. The smaller the slope the more expanded is the
and PEG plasticizer, but hollow granules form when a sedimentation front since larger particles sediment faster,
high dispersant level is used. They have also found that leaving behind smaller particles which slightly affect the
the particle-packing density in homogeneous granules is transmission. In contrast, a nearly vertical transmission
lower than in the hollow granules. Takahashi et al. 9 have profile indicates a well-defined sharp front which comes
reported similar results in aqueous silicon nitride slurries from either a very narrow particle size distribution or an
when the level of flocculation is controlled by varying the established particle network structure in the slurry. Fur-
slurry pH-value. The pH-dependent zeta potential con- ther information is provided by the distance between the
trols the slurry flocculation through its dominant effect on transmission profiles. A fixed time between each trans-
the electrostatic repulsion between the particles. To avoid mission measurement is set. So, the distance between suc-
particle migration during the drying step, they suggest the cessive transmission profiles can be used to calculate the
use of slightly flocculated slurries. sedimentation rate of the particles. The sedimentation rate
Subsequent investigations confirmed that the floccula- and the final relative sediment height are useful for eval-
tion level of a slurry has a major influence on the final uating the stability of a suspension. A low sedimenta-
granule properties also in the case of using other ceramic tion rate, indicated by narrow spaces between adjacent
raw materials, as alumina 10, 11, 12, zirconia 13, and ceram- transmission profiles, is desired. Furthermore, a low sedi-
ic composites 14, 15, 16. Nevertheless, even now many sin- ment height is desired, which correlates to individual sed-
tered components produced from commercially available imentation of each particle, allowing close packing. The
granules contain typical microstructural defects caused by possibility to simultaneously measure the transmission
unsuitable granule properties. over the whole cuvette height in a user-defined time in-
Although several investigations prove the reduction or terval and user-defined centrifugation force allows a more
prevention of dimpled, hard-shelled hollow granules with precise slurry characterization than conventional setups,
the use of flocculated slurries, little attention has been paid where turbidity is measured at a fixed height in the cuvette.
to the final properties of sintered ceramics. Therefore, a
systematic investigation of alumina, zirconia and zirconia-
toughened alumina (ZTA) batches was conducted. Dis-
persed and flocculated slurries were developed and spray-
dried with a two-fluid nozzle in a lab spray dryer under
identical conditions. Properties of granules, pressed and
sintered bodies are compared to demonstrate the effect and
potential of slurry optimization.
Furthermore, this paper presents for the first time the op-
tical centrifuge as a characterization tool for slurries used
in spray granulation. The turbidity of a sedimenting slurry
can thereby be measured as a function of time and position
in the cuvette. With 2500 detectors distributed over the
cuvette height, a high spatial resolution regarding trans- Fig. 1: Evolution of transmission profiles for an 80 wt% alumina
mission behavior is possible. Each recorded transmission slurry containing 0.577 wt% CE64 measured at 2300 G.
September 2018 Slurry Development for Spray Granulation of Ceramic Multicomponent Batches 329

Further advantages are the low required sample quanti- (2) Testing procedures
ty of only 0.5 mL and the opportunity to measure up to The particle size distribution of the starting powders
12 samples simultaneously under identical conditions. Re- was determined in aqueous dispersions with a Mastersiz-
sults of the optical centrifuge complement conclusions ob- er 2000 (Malvern, United Kingdom). Powders were sus-
tained from particle charge titration analyzer and viscome- pended in deionized water and treated with ultrasound
ter. for 3 minutes. The test suspensions were cooled to room
temperature before the measurement. The specific surface
II. Experimental area (BET) was measured based on nitrogen adsorption
with a NOVA 2200 (Quantachrome Instruments, USA).
(1) Materials and preparation Phase content was measured by means of X-ray diffrac-
Alumina powder AES-11 (Sumitomo Chemical, Japan) tion (Bruker D8, Germany).
or/and zirconia powder TZ-3YS-E (Tosoh Corporation, The effectiveness of the dispersant was assessed with zeta
Japan) were used in all experiments. For granulation and potential measurements based on the streaming potential
dry pressing, organic additives Dolapix CE64 (disper- of the ceramic slurries by means of particle charge titration
sant), Optapix AC 95 (binder) and Zusoplast 9002 (lu- analysis (Stabino, Particle Metrix GmbH, Germany). Sus-
bricant) all produced by Zschimmer & Schwarz GmbH pensions with 20 wt% solids content, the maximum solids
& Co KG (Germany) were selected and used as received. content measurable across the whole pH-range, were test-
Optapix AC95 and Zusoplast 9002 were chosen, based ed. Although zeta potentials of slurries with a practical
on recommendations of the manufacturer stating a special solids content of up to 80 wt% are not measurable, conclu-
suitability for spray drying. Diluted nitric acid (10.6 wt%) sions can still be drawn, although they can only be adapted
was used to destabilize the slurries. qualitatively. Absolute values of the zeta potential above
Aqueous slurries of three different powder batches 30 mV commonly indicate sufficient stabilization 17, but
were prepared: 100 wt% alumina, 100 wt% zirconia and for safe processing a large distance to the isoelectric point
80 wt% alumina + 20 wt% zirconia, respectively. Grind- (IEP), meaning the point of zero charge where electrostatic
ing bodies (alumina or zirconia balls) and dispersant were stabilization is no longer present, is required additionally.
Sedimentation behavior of well-dispersed and destabi-
added to the suspension fluid (deionized water, 1 lS/cm),
lized slurries was monitored and quantified using an op-
followed by the addition of ceramic powder. Mixing
tical centrifuge (LUMiSizer©, LUM GmbH, Germany),
and homogenization of the slurry were conducted in a
which allows slurry investigation under centrifugal forces
polyethylene container, rotating at 40 rpm for 14 hours.
up to 2300 G (rotational speed of 4000 rpm) 18. For the
After the grinding bodies had been removed by sieving,
determination of a suitable dispersant concentration,
binder and lubricant were added using a pipette while
80 wt% alumina suspensions with varying dispersant con-
the slurry was stirred. For the preparation of destabilized
centrations were measured at maximum rotational speed.
slurries, nitric acid was added last using a pipette.
Measurements of spray-drying slurries were performed
Granulation via spray drying was carried out in a lab
with 2000 rpm (centrifugal force of 530 G) and 30 s time
spray dryer (Atomizer Minor, Niro, Denmark). The spray interval between profiles. A well-dispersed alumina slur-
dryer was run in fountain mode with an external mix two- ry with 70 wt% solids content and a destabilized alumina
stream nozzle which had a slurry feed orifice diameter of slurry with 65 wt% solids content were investigated.
1.5 mm. The air as atomizing fluid was vortexed within the Slurry viscosity was monitored using a standard rheome-
nozzle by a swirl disc right before the slurry was atomized. ter (Physica MCR 300, Anton Paar, Austria). For the
Process parameters such as slurry feed rate (17 – 25 mL/ spray-drying process, a viscosity below 0.2 Pa⋅s at a shear
min), atomization gas flow rate (38 – 40 L/min), and gas rate of 100 s -1 was required.
outlet temperature (100 – 105 °C) were kept constant in The size distribution of spray-dried granules was mea-
all spray-drying experiments. For each material (alumi- sured with a Mastersizer S (Malvern, United Kingdom)
na, zirconia, and ZTA), a well-dispersed and a destabilized using the dispersion unit for dry samples with a feed rate
slurry was spray-dried. Destabilized alumina and zirconia of 20 % and a pressure of 0.16 bar. The shape was deter-
slurries contained 65 wt% solids content, the other slur- mined with a light optical microscope Axiotech 30 (Zeiss;
ries contained 70 wt% solids content. Germany). Flowability measurements and determination
From the spray-dried granules, cylindrical green com- of untapped bulk density of granules were conducted in
pacts with a diameter of 20 mm and a height of about 2 mm compliance with standards 19, 20 with apparatus conform-
were pressed with a uniaxial pressure of 100 MPa using a ing to standards (Landgraf Laborsysteme HLL GmbH,
hand-lever press (Paul-Otto Weber GmbH, Germany). Germany).
Thermal processes were performed in a box furnace The green density of the dry-pressed samples was de-
(FHT 16/8, Ceram-Aix, Germany), starting with a slow termined by measuring mass and geometry. The sinter-
heating rate of 1 K/min and a dwell time of 30 minutes ing density was measured with the Archimedes method 21.
at 450 °C for debinding. Afterwards, the samples were Light optical microscope Axiotech 30 and SEM Gemini
heated at 5 K/min to the maximum process temperature Supra 40 (both Zeiss GmbH, Germany) were used for mi-
of 1580 °C for Al 2O 3 and ZTA (60 min dwell time) or crostructural investigations. Evaluation of sintered body
1500 °C for ZrO 2 (30 min dwell time), respectively. A cross-sections in respect of porosity was performed by
cooling rate of 5 K/min was held up to 300 °C. means of image processing with PxF Workbench software
330 Journal of Ceramic Science and Technology —P. Höhne et al. Vol. 9, No. 3

with phase fraction expansion module (PixelFerber, Ger- shifts the IEP to lower pH-values (Fig. 3). The alumi-
many). na slurry containing the dispersing agent reaches a f = -
Biaxial strength of four samples per batch was deter- 53 mV at a pH = 9.6 with the IEP now shifted to pH = 5.5.
mined with as-fired sintered samples on a ball-on-three- The zirconia even shows a charge reversal, the formerly
balls (B3B) setup 22, 23. In the B3B-test, one surface of a positive surface became negative, leading to a f = -82 mV
disc-shaped specimen is supported on three balls equidis- at a pH = 8.8. The new isoelectric point at pH IEP = 4.9 has
tant from its center. The opposite face is centrally loaded a good distance from the initial pH value, similar to the
with a fourth ball normal to the orientation of the plane. conditions in the alumina slurry.
The sample holder was used in a testing machine (Zwick/
Roell, Germany), which can apply a maximum force of
5 kN. The preload on each specimen was 30 N and the
loading rate was 0.03 mm/s.
III. Results and Discussion
Table 1 summarizes results of the characterization of
both submicron starting powders. Alumina and zirconia
powders are similar in terms of granulometric properties,
advantageous for preparation of batches with homoge-
neous distribution of both components.

Table 1: Properties of alumina and zirconia powders.

Powder Alumina Zirconia

properties (type AES-11) (type TZ-3YS-E)
Fig. 2: Starting conditions of both slurries were marked with a black
cross. Lines show the evolution of the zeta potential versus the pH
Density / g⋅cm -3 3.94 5.93 for slurries of 20 wt% solids content without dispersing agent for
Specific 6.46 6.71 alumina and zirconia.
surface / m²⋅g -1
Mean particle size 0.58 0.53
d 50 / lm
Phase content a-Al 2O 3 tetragonal +
low amount
monoclinic ZrO 2

(1) Development of slurries with optimum dispersed

particles
The results of zeta potential analysis of alumina and zir-
conia suspensions without any dispersant are shown in
Fig. 2. An aqueous suspension with 20 wt% solids con-
tent consisting only of the pure raw material delivered a
zeta potential of f = -31 mV at a pH = 9.3 and an isoelectric
point (pH IEP) of 8.6 in case of the used alumina (continu-
ous line in Fig. 2), while pure zirconia delivered f = +67 mV
at pH = 5.3 and pH IEP of 7.0 (dotted line in Fig. 2). The Fig. 3: Starting situation of both slurries marked with black cross
rather small distances of the IEP from the initial pH-values and evolution of the zeta potential versus pH for slurries with
in case of the dispersing-agent-free suspensions of both 20 wt% solids content of alumina and zirconia, both containing
raw materials indicate a rather unstable state unsuitable for 0.577 wt% CE64 with reference to the solid fraction.
safe processing despite the sufficiently high absolute zeta
potential. Additionally, a well-dispersed and stable multi- The effect of the different dispersant concentrations on
component ZTA system consisting of both materials is not sedimentation behavior is shown exemplarily in Table 2.
possible, since a mixture of both materials would agglom- Stated dispersant concentrations refer to the solids content
erate owing to the opposite surface charge. Thus, the use and usage of dispersant as received. The lowest sediment
of a dispersing agent is inevitable for the ZTA powder. height and the slowest sedimentation velocity, both were
Comprehensive studies, conducted in a previous re- observed for a concentration of 0.577 wt% CE64 and indi-
search project 24, showed the most promising results re- cate the highest degree of dispersion and best stabilization
garding sedimentation and slurry viscosity for the com- of the powder particles. The active substance amount in
mercially available CE64 as dispersing agent. Besides in- the delivered form of 65 % and the fraction of it being cit-
creased absolute zeta potentials, the dispersing agent also ric acid based on investigations of Kosmač et al. 25 leads
September 2018 Slurry Development for Spray Granulation of Ceramic Multicomponent Batches 331

to a theoretical citric acid content of 0.225 wt%. There- the particles’ packing behavior in a centrifugation process
fore, the determined amount with optimal dispersing ef- can qualitatively be transferred to the packing behavior
fect of 1.8 ⋅ 10 -6 mol/m 2 is slightly above the adsorption of drying droplets in the spray drying process. Adjust-
value of 1.2 ⋅ 10 -6 mol/m 2, published for a higher-purity ments of the degree of flocculation in ceramic slurries can
alumina 26. be achieved by changing either the amount of dispersant or
As promising and powerful the centrifugation analysis is, the pH-value. The amount of dispersant is already given,
it needs to be accompanied by viscosity measurements, be- because the slurry preparation needed the dispersing agent
cause sufficient stability is not necessarily associated with to homogeneously disperse and afterwards stabilize the
a processable viscosity below 0.2 Pa⋅s at a shear rate of particles. Furthermore, the dispersing agent is necessary
100 s -1, which is required for the spraying process. The to achieve the required high solids content and the surface
addition of 0.577 wt% CE64 again yielded the best result, charge reversal of the zirconia material. With the disper-
here the lowest viscosity (dotted line in Fig. 4). Since all sant amount fixed, the option left for a defined destabiliza-
tested dispersant concentrations yielded sufficient viscosi- tion leading to a specific flocculation is the adjustment of
ties at the determined shear rate of 100 s -1, the optimal the slurry’s pH.
concentration of 0.577 wt% of dispersant formerly deter-
mined by sedimentation analysis, was selected for use in
Table 2: Sediment height and sedimentation velocity in
spray slurry preparation.
an 80 wt% alumina slurry depending on dispersing agent
Since the process route contains a dry pressing step as
concentration of CE64 at 4000 rpm (2300 g).
the shaping procedure, additional binder and lubricating
agent are required to achieve stable green bodies. The ide-
al concentrations were determined via statistical design of Concentra- Relative sed- Sedimentation
experiment yielding the highest sinter density for compar- tion of dispersing iment height / % velocity / lm⋅s -1
atively low amounts of 1 wt% of binder and 0.5 % of the agent / wt%
lubricating agent. Addition of the organic components to 0.385 77.4 5.6
the slurry showed a negligible influence on the viscosity.
Since the additives have only 50 wt% solids content, the 0.577 75.5 4.7
minor effect observed is simply caused by the slight dilu- 0.654 76.0 4.9
tion owing to the introduction of water. 0.769 76.5 5.2
The ratio of the organic additives was kept constant for
both raw materials to finally apply the optimizations to the The optical centrifuge was used for the determination of
multicomponent ZTA material. As result of comprehen- the necessary amount of nitric acid to reach a specific de-
sive qualitative and quantitative variations, identical or- gree of flocculation. The required degree of flocculation
ganic additives (0.577 wt% dispersant + 1 wt% binder + is reached when the slope of the individual transmission
0.5 wt% lubricant) were used for preparation of alumina, profile is nearly vertical. The reduction of the pH and ap-
zirconia and ZTA spray slurries, respectively. proaching the IEP was realized by the addition of diluted
nitric acid (10.6 wt%). Results of sedimentation analysis
are depicted in Fig. 5 and show an increase in the sedimen-
tation rate (increased distance between transmission pro-
files). Assessing the relative sediment heights, it needs to
be noted that the recorded spectrum at the bottom (Fig. 5)
is of a slurry with only 65 wt% solids content (reduced
by 5 wt% compared to the measurement shown on top of
Fig. 5) and still leads to sediment that is nevertheless high-
er. The destabilized 65 wt% slurry yields a relative sedi-
ment height of 68.3 % while the dispersed 70 wt% slurry
yielded a relative sediment height of 64.8 %.
The higher final relative sediment height achieved in-
dicates a less dense packing in the cuvette in the case of
acid addition. This higher final relative sediment height
by reduction in packing density even overrules the low-
er overall filling height and reduced solids content. So, this
Fig. 4: Viscosity versus shear rate of an 80 wt% alumina slurry with destabilization leads to a pronounced reduction in packing
different amounts of CE64 (continuous line 0,385 wt%; dotted line
0,577 wt%; dashed line 0,65 wt%). density. The reduced packing density enables shrinking of
the atomized droplet during drying and therefore mainte-
nance of its spherical shape.
(2) Development of destabilized slurries The apparently narrow particle size distribution indicat-
From the correlation of suspension stability and gran- ed by the vertical slope of the transmission profiles in the
ule morphology shown in the literature and the influence spectrum of the destabilized slurry is the result of a net-
of suspension stability on the packing density of the sedi- work structure established in the slurry. The desired de-
ment in the centrifugation, the conclusion was drawn that gree of flocculation for alumina is achieved for a pH value
332 Journal of Ceramic Science and Technology —P. Höhne et al. Vol. 9, No. 3

of approximately pH = 8. The pH shift leads to a gener- Further acid addition and therefore increased floccula-
ation of charges on the particle surface and the formerly tion of the slurry does not lead to an improvement of prop-
optimized weight ratio of the dispersant becomes insuf- erties. The stabilization sustained in the case of the de-
ficient. The generated unsaturated surface charges are at- fined flocculation is lost and the slurry completely floc-
tracting dispersant molecules even though they might al- culates. Thereby, slurry viscosity increases and safe slur-
ready be bound to another particle. These bridging con- ry processing cannot be assured. Since shrinkage of the at-
nections 27 of dispersant molecules lead to a network for- omized droplets leading to bulky soft granules is already
mation and therefore defined partial flocculation in the possible in partially destabilized slurries, there is no neces-
destabilized system. sity for further flocculation. With the defined flocculation
realized, the viscosity rose to values above the workable
limit of g = 0.2 Pa⋅s at a shear rate of 100 s -1. The param-
eters strongly affecting the viscosity are dispersant con-
centration and the solids content. Since the desired floc-
culation is based on impoverishment of the dispersant, the
second major influencing factor needed adjustment. The
solids content had to be reduced to maintain or regain a
processable range of the viscosity. The required viscosity
was achieved by reducing the solids content of the pure
powder slurries (alumina and zirconia) to 65 wt%. The de-
pendence of the viscosity on the solids content is shown by
way of example for alumina in Fig. 7. The well-dispersed
slurry appears as a flat base line (depicted as a dashed line in
Fig. 7) compared to the destabilized slurries. The viscosity
of the 70 wt% destabilized slurry (dotted line) is too high
for the upcoming atomization process, while the 65 wt%
destabilized slurry (continuous line) regains suitable vis-
cosity and was further used for the subsequent spray dry-
Fig. 5: Effect of the destabilization on the sedimentation behavior. ing procedure.
The images show the transmission profiles of a dispersed 70 wt%
(top) and destabilized 65 wt% (bottom) alumina, both slurries con-
tain 0.577 wt% CE64. (measured at 2000 rpm; 530 G).

In the case of alumina, the required amount of nitric acid

was V acid = 14.9 lL/g (additions refer to the powder mass),
while the zirconia slurry only needed V acid = 9.0 lL/g.
The pH required for the desired degree of flocculation for
both raw powder materials is in the range marked in Fig. 6
and therefore, applicable as well as for the ZTA composite.
The ZTA slurry required V acid = 12.0 lL/g for sufficient
destabilization.

Fig. 7: Effect of pH adjustment on slurry viscosity as an example

for alumina slurries.

(3) Spray drying and green body characterization

All slurries were atomized with a two-fluid nozzle using
pressurized air. Table 3 lists the solids content, the pH-
values of slurries and the corresponding granulate yield
of all batches produced from dispersed and destabilized
slurries, respectively. The given granule yield is the coarser
fraction produced in the spraying process. The fine dust-
like fraction is not included in the granulation yield since it
Fig. 6: The plot shows zeta potential versus pH for slurries con-
taining CE64, indicating the process window of flocculated slurries is unsuitable for dry pressing processes. The process yield
(gray area) and their initial pH values (black crosses) for alumina is only slightly affected by the destabilization of the slurry
and zirconia. without an explicit tendency.
September 2018 Slurry Development for Spray Granulation of Ceramic Multicomponent Batches 333

Granules made of well-dispersed slurries show the typi- flowability by 6.9 %. This observed correlation between
cal morphology for spray-dried granules, with one side of flowability and particle size is in agreement with investi-
the granule curved inwards (dimple), resembling a kicked- gations already described in the literature 1. The untapped
in football. The irregular granules made of well-dispersed
bulk density of the granules is reduced by the slurry desta-
slurries of the different materials are depicted in the top
row of Fig. 8. The irregular shape seems not to depend on bilization as the destabilization prevents a dense packing
the granules’ size. The dimpled shape can be found over in the drying step.
the whole granule size range.
In contrast, granules made of the destabilized slurries
Table 3: Characteristics of the spray drying experiments.
show in all cases a reduced fraction of dimpled particles
and are depicted in Fig. 8 d) – f) for all three materials.
Table 4 gives an overview regarding the different granule Batch name Solids content / wt% pH Granulate
properties. The size distribution of the granules is differ- yield / %
ently affected by destabilization for the different materials. Al disp 70 9.5 44
The size of granules prepared from destabilized slurries
compared to stable slurries is slightly decreased for alumi- Zr disp 70 9.1 62
na, strongly decreased for zirconia, but strongly increased ZTA disp 70 9.5 58
for ZTA. The granule flowability depends on the granule
size and increases with increasing granule diameter. Thus, Al destab 65 7.8 42
destabilization of alumina and zirconia slurries reduces the Zr destab 65 6.6 62
granule flowability by 18.5 % and 54.5 %, respectively. In
ZTA destab 70 8.3 47
the case of ZTA, slurry destabilization improves granule

Fig. 8: Light microscope images of granules of alumina (a and d), zirconia (b and e) and ZTA (c and f) from slurries with well-dispersed particles
(a - c) and destabilized slurries (d - f).

Table 4: Characteristics of granules and pressed compacts produced by dispersed and destabilized slurries.

Al disp Al dest Zr disp Zr dest ZTA dis ZTA dest

Granules d 10 / lm 16 11 16 7 15 19
Granules d 50 / lm 53 42 50 27 49 74
Granules d 90 / lm 132 118 118 65 112 170
Granules’ flowability / g⋅s -1 0.81 0.66 1.23 0.56 0.87 0.93
Granules’ untapped bulk density / g⋅cm -3 1.25 1.10 1.60 1.43 1.32 1.23
Pressed compacts’ green density / g⋅cm -3 2.23 2.20 2.86 2.83 2.37 2.31
334 Journal of Ceramic Science and Technology —P. Höhne et al. Vol. 9, No. 3

Despite large differences in granules untapped bulk den- compared to sintered bodies made with granules of desta-
sity, the granule compactibility is only slightly affected bilized slurries (Fig. 10). The reduction in pore number
by slurry destabilization. Sample body preparation by dry and size was observed for all three materials. The pore area
pressing of granules made of destabilized slurries leads to in these microstructure images was determined (Table 5)
green bodies with a slightly reduced density compared to and supports this finding with a pore fraction reduction
sample bodies of granules from well-dispersed slurries. in the sintered bodies originating from destabilized slur-
An important difference in the fabricated sample bod- ries to approximately one third compared to sinter bodies
ies can be observed when green sample bodies are broken. originating from well-dispersed slurries.
Evaluating the fracture surface, the sample body made of As shown in Fig. 10, the sintered bodies originating from
granules from a dispersed slurry shows round, sphere like destabilized slurries, show a more dense and homoge-
residues of the granules (depicted exemplarily for alumi- neous microstructure. This trend is expressed in the sin-
na in the left image of Fig. 9). In contrast, no sphere-like tered body density, too. For all investigated materials, the
granule residues are obvious at the fracture surface of the sintered bodies originating from destabilized slurries yield
green body made from destabilized slurry. The crack does a higher density, which is listed in Table 5.
not propagate along the borders of maintained granules, Results of biaxial strength measurements for the differ-
but instead randomly through the granule volume (right ent materials are listed in Table 5 and shown in Fig. 11.
image in Fig. 9), indicating soft granules without hollow In all cases, the sintered bodies (originating from destabi-
cores and hard shells. lized slurries) show higher values for the mean strength as
well as for the minimal strength, but these improvements
(4) Sintered body properties should be considered as a tendency. Zirconia shows a par-
Sintered bodies produced with granules from well-dis- ticularly strong increase but an increased standard devia-
persed slurries show overall a higher number of pores tion as well.

Fig. 9: Light images of fracture areas of alumina green samples made of granules from the dispersed slurry (a) and destabilized slurry (b).

Fig. 10: Polished cross-sections of sintered bodies produced from granules of well-dispersed slurries (a-c) of alumina (a and d), zirconia (b and
e) and ZTA (e and f) and corresponding cross-sections of sintered bodies from granules made of destabilized slurries (d-f).
September 2018 Slurry Development for Spray Granulation of Ceramic Multicomponent Batches 335

Table 5: Characteristic values of sintered alumina, zirconia and ZTA bodies, made of the differently treated slurries

Al disp Al dest Zr disp Zr dest ZTA dis ZTA dest

Porosity / % 4.0 1.4 2.8 1.2 1.4 0.5
Sintered density / g⋅cm -3 with standard 3.863 3.882 5.962 5.992 4.172 4.183
deviation ± 0.008 ± 0.005 ± 0.010 ± 0.002 ± 0.001 ± 0.004
Mean strength / MPa 409 498 518 ± 5.6 % 818 603 644
and standard deviation / % ± 10.8 % ± 11.6 % ± 25.3 % ± 17.1 % ± 15.6%
Minimal strength / MPa 348 427 493 563 487 519

exhibited a higher sintered density, reduced pore fraction,

reduced maximum pore size and increased biaxial strength
compared to sintered bodies from conventional well-dis-
persed slurries. The efficacy of the strategy to improve the
microstructure and strength of green and sintered bodies
by precisely adjusting the initial slurry stability has been
proven for single-component ceramics (alumina and zir-
conia) as well as for multicomponent ceramic materials
(ZTA).

Acknowledgements
The authors would like to thank the Federal Institute for
Economic Affairs and Energy (Germany) and the Cen-
tral Innovation Programme for SMEs for financial sup-
port (grant KF2201088AG4). Further, we should like to
thank Wolfgang Güther (BAM Division 5.5) for his ex-
tensive support with spray drying and sample prepara-
Fig. 11: Influence of destabilization on sintered body strength for tion, Franziska Lindemann (BAM Division 5.5) for pow-
alumina, zirconia and ZTA. der and sample body characterization and Dagmar Nico-
laides (BAM Division 5.4) for biaxial strength measure-
ments.
IV. Summary
The influence of the initial slurry stability on the proper- References
ties of granules, green and sintered bodies has been investi- 1 German, R.M.: Particle Packing Characteristics, Metal Powder
gated for alumina, zirconia and ZTA composite materials. Industries Federation: Princeton New Jersey, (1989).
Zeta potential and viscosity measurements as well as sedi- 2 Zhang, Y., Binner, J., Rielly, C., Vaidhyanathan, B.: Compari-
mentation investigations with optical centrifuge were used son of spray freeze dried nanozirconia granules using ultrason-
for precise slurry assessment as a major precondition for ication and twin-fluid atomisation, J. Eur. Ceram. Soc., 34, [4],
optimum and reproducible adjustment of slurries before 1001 – 1008, (2014).
3 Rosenberger, N., Compson, C., Adria, J.: Comparative study
spray drying. Sedimentation analysis with optical cen-
on lab-scale granulation techniques, cfi Ber. DKG, 92, [4], E29
trifuge (LUMiSizer©) has been used to investigate differ-
– E31, (2015).
ent influences like additive composition, solids content or 4 Shinohara, N., Okumiya, M., Hotta, T., Nakahira, K., Naito,
pH-value on the sedimentation behavior. Granules were M., Uematsu, K.: Morphological changes in process-related
prepared from well-dispersed and destabilized slurries. large pores of granular compacted and sintered alumina, J. Am.
The prepared granules have been used to fabricate green Ceram. Soc., 83, [7], 1633 – 1640, (2000).
bodies which were subsequently sintered. 5 Vicente, J., Pinto, J., Menezes, J., Gaspar, F.: Fundamental anal-
Granules produced by spray drying of well-dispersed ysis of particle formation in spray drying, Powder Technol.,
slurries have the donut like morphology that is common 247, 1 – 7, (2013).
and well known for conventional, commercially available 6 Baklouti, S., Chartier, T., Baumard, J.F.: Binder distribution in
granules. Spray drying of destabilized slurries leads to a spray-dried alumina agglomerates, J. Eur. Ceram. Soc., 18, [14],
lower granule bulk density and a strongly decreased frac- 2117 – 2121, (1998).
7 Tanaka, S., Pin, C.C., Uematsu, K.: Effect of organic binder
tion of granules with a disadvantageous hard shell and
segregation on sintered strength of dry-pressed alumina, J. Am.
donut-like morphology. Typical inhomogeneities in the
Ceram. Soc., 89, [6], 1903 – 1907, (2006).
microstructure as they result from hollow granule cores 8 Lee, H.-W., Song, G., and Suk, I.-S.: Effect of suspension
or hard granule shells were found in dry-pressed, and af- property on granule morphology and compaction behavior,
terwards broken, green sample bodies. In contrast, such pp. 41 – 50 in 96. annual meeting of the American Ceramic
inhomogeneities were not observed in broken green bod- Society (ACS). (1995).
ies made of granules of destabilized slurries. Sintered sam- 9 Takahashi, H., Shinohara, N., Okumiya, M., Uematsu, K.,
ple bodies based on the specifically destabilized slurries Junichiro, T., Iwamoto, Y., Kamiya, H.: Influence of slurry
336 Journal of Ceramic Science and Technology —P. Höhne et al. Vol. 9, No. 3

flocculation on the character and compaction of spray-dried 19 EN ISO 14629:2016 (German version); Fine ceramics (ad-
silicon-nitride granules, J. Am. Ceram. Soc., 78, [4], 903 – 908, vanced ceramics, advanced technical ceramics) - Determination
(1995). of flowability of ceramic powders (ISO 14629:2012); in CEN,
10 Bertrand, G., Filiatre, C., Mahdjoub, H., Foissy, A., and Cod- Brussels, 2016.
det, C.: Influence of slurry characteristics on the morphology 20 EN 725 – 9:2006 (German version); Advanced technical ceram-
of spray-dried alumina powders, J. Eur. Ceram. Soc., 23, [2], ics – Methods of test for ceramic powders - Part 9: Determi-
263 – 271, (2003). nation of untapped bulk density (EN 725 – 9:2006); in CEN,
11 Tsubaki, J., Yamakawa, H., Mori, T., Mori, H.: Optimization Brussels, 2006.
of granules and slurries for press forming, J. Ceram. Soc. Japan, 21 EN 623 – 2 Advanced technical ceramics - Monolithic ceramics
110, [10], 894 – 898, (2002). - General and textural properties - Part 2: Determination of
12 Walker, W.J., Reed, J.S., Verma, S.K.: Influence of slurry pa- density and porosity. in CEN, Brussels, 1993.
rameters on the characteristics of spray-dried granules, J. Am. 22 Borger, A., Supancic, P., Danzer, R.: The ball on three balls test
Ceram. Soc., 82, [7], 1711 – 1719, (1999). for strength testing of brittle discs: Part II: Analysis of possible
13 Mahdjoub, H., Roy, P., Filiatre, C., Bertrand, G., Coddet, C.: errors in the strength determination, J. Eur. Ceram. Soc., 24,
The effect of the slurry formulation upon the morphology of [10 – 11], 2917 – 2928, (2004).
spray-dried yttria stabilised zirconia particles, J. Eur. Ceram. 23 Danzer, R., Harrer, W., Supancic, P., Lube, T., Wang, Z. H.,
Soc., 23, [10], 1637 – 1648, (2003). Borger, A.: The ball on three balls test - strength and failure
14 Cao, X.Q., Vassen, R., Schwartz, S., Jungen, W., Tietz, F., Sto- analysis of different materials, J. Eur. Ceram. Soc., 27, [2 – 3],
ever, D.: Spray-drying of ceramics for plasma-spray coating, J. 1481 – 1485, (2007).
Eur. Ceram. Soc., 20, [14 – 15], 2433 – 2439, (2000). 24 Final Report of ZIM Project: Ultrasonic supported, energy-
15 Kim, D.J., Jung, I.Y.: Granule performance of zirconia/alumina efficient spray granule synthesis, Support code KF2201088,
composite powders spray-dried using polyvinyl pyrrolidone BAM Berlin, (2016).
binder, J. Eur. Ceram. Soc., 27, [10], 3177 – 3182, (2007). 25 Aleš, D., Tomaž, K.: Weakly flocculated aqueous alumina sus-
16 Naglieri, V., Gutknecht, D., Garnier, V., Palmero, P., Chevalier, pensions prepared by the addition of Mg(II) ions, J. Am. Cer-
J., Montanaro, L.: Optimized slurries for spray Drying: differ- am. Soc., 83, [3], 666 – 668, (2000).
ent approaches to obtain homogeneous and deformable alumi- 26 Hidber, P.C., Graule, T.J., Gauckler, L.J.: Competitive adsorp-
na-zirconia granules, Materials, 6, [11], 5382 – 5397, (2013). tion of citric acid and Poly(vinyl alcohol) onto alumina and its
17 Greenwood, R.: Review of the measurement of zeta poten- influence on the binder migration during drying, J. Am. Cer-
tials in concentrated aqueous suspensions using electroacous- am. Soc., 78, [7], 1775 – 1780, (1995).
tics, Adv. Colloid Interfac., 106, [1], 55 – 81, (2003). 27 Shojai, F., Pettersson, A.B.A., Mäntylä, T., Rosenholm, J.B.:
18 Lerche, D., Sobisch, T.: Evaluation of particle interactions by Electrostatic and electrosteric stabilization of aqueous slips
in situ visualization of separation behaviour, Colloid Surface A, of 3Y-ZrO 2 powder, J. Eur. Ceram. Soc., 20, [3], 277 – 283,
440, 122 – 130, (2014). (2000).