Author’s Accepted Manuscript

Controlling the morphology of ceramic and

Agnese Stunda-Zujeva, Zilgma Irbe, Liga Berzina-

PII: S0272-8842(17)30823-4
DOI: http://dx.doi.org/10.1016/j.ceramint.2017.05.023
Reference: CERI15183
To appear in: Ceramics International
Received date: 15 February 2017
Revised date: 2 May 2017
Accepted date: 3 May 2017
Cite this article as: Agnese Stunda-Zujeva, Zilgma Irbe and Liga Berzina-
Cimdina, Controlling the morphology of ceramic and composite powders
obtained via spray drying - A review, Ceramics International,
http://dx.doi.org/10.1016/j.ceramint.2017.05.023
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Controlling the morphology of ceramic and composite powders obtained via spray

drying - A review

Agnese Stunda-Zujeva, Zilgma Irbe, Liga Berzina-Cimdina*

Rudolfs Cimdins Riga Biomaterials Innovations and Development Centre of RTU,

Institute of General Chemical Engineering, Faculty of Materials Science and Applied

Chemistry, Riga Technical University, Pulka 3, Riga, LV-1007, Latvia

Development Centre of RTU, Institute of General Chemical Engineering, Faculty of

Materials Science and Applied Chemistry, Riga Technical University, Pulka 3, Riga,

LV-1007, Latvia. Tel.: +371 67089275; Fax: +371 67089619. liga.berzina-

[email protected]

Abstract

Spray drying is one of the most convenient methods for drying suspensions (slurries)

and for granulation of materials. Spray dried powders have good flowability, narrow

size distribution and controllable morphology. Morphology of powder particles (also

called granules or microspheres) strongly affects the use and handling of powders. This

review discusses the latest research on parameters that affect morphology and size of

granules obtained by spray drying: atomization parameters, properties of sprayed slurry,

mass transfer etc. The formation of hollow and dense granules is extensively reviewed.

Granule size is affected by droplet size, slurry concentration and initial particle size.

Morphology mostly depends on size distribution of initial ceramic particles,

agglomeration tendency in the slurry and mechanical strength of the shell of a granule

during the drying process compared to capillary force of the suspension liquid. Polymer

1
additives (e.g. binders and lubricants) change the properties of granule shell and the

evaporation of moisture; thus, polymer additives significantly affect morphology.

Keywords: drying (A), spray drying

1. Introduction

Powders with certain properties are required in industrial processes, both as a

raw material in production and as a final product. The ability to obtain a powder with

required properties is a crucial step in the powder production process. Properties of the

powder are determined by morphology and composition of powder granules. One of the

most powerful and convenient methods to produce rounded particles with narrow size

distribution, controllable morphology and composition is spray drying.

Spray drying is applied for emulsions, suspensions and solutions. Either organic

or inorganic substances can be dried in such way. The obtained powders are used for

production of ceramics, pharmaceuticals, sorbents, catalysts, foodstuffs etc. Although

the first industrial application of spray drying was almost a century ago [1], the number

of investigations of spray drying is increasing. There are research articles available on

various aspects of spray drying: air flow, wall deposition, particle separation, droplet

drying and particle formation. In Scopus database the amount of original research

articles containing the term ‘spray drying’ in the title (or in the abstract) has increased

from 63 (167) in 2004 to 201 (423) in 2014 and in Web of Science database – from 122

to 307 in the title of the article, from 222 to 596 in the topic of the article and from 299

to 1850 patents per year. However, there is still a lack of detailed understanding of

process-product regularities.

2
 An extensive review on various morphologies that can be produced by spray

drying is given by A. B. D. Nandiyanto and K. Okuyama in [2]. But so far there is a

lack of comprehensive reviews about controlling the morphology of ceramic powder

granules. Spray drying of ceramic suspensions (often called slurries) requires a different

approach than spray drying of solutions and emulsions of organic matter. In this review

the parameters that affect the morphology of ceramic powder granules obtained by

spray drying are discussed. Research articles that have been published mostly in the last

decade are summarized.

The particles obtained by spray drying are often called granules, grains,

spherical powders, granulized powders and microspheres. In this review the term

“granules” is used. This is the most popular term in scientific literature concerned with

spray drying of ceramic powders. However, in commercial or popular literature the

most common term is microspheres to stress that sphericity is an important parameter.

1.1. Spray drying: process and equipment

The spray drying process is usually described in three steps:

1) droplet generation (atomization or spraying);

2) droplet-to-particle conversion by drying (solvent evaporation);

3) particle collection (separation from drying gas).

Granule morphology forms during the first two steps. The diagram of common

laboratory scale spray dryer is shown in Fig. 1. Droplet drying physics and some

modelling approaches are discussed in [3]. Mass and heat balances are given in [4].

Spray drier design details – atomizer devices (rotary atomizers; hydraulic (pressure)

nozzles; pneumatic nozzles, ultrasonic nozzles etc.), drying chambers, and the collection

3
of the dried powder are described in detail in [1]. Spray dryers are energy consuming

devices; the improvement of energy efficiency of industrial spray dryers is described in

[4]. In this review the properties of feed slurry and settings of spray drier along with

fundamentals of mass transfer are discussed.

The spray drying process and the formation of granules are affected by a large

quantity of factors – a summary of them is show in Fig. 2. The properties of granules

are divided into two groups: primary properties and secondary properties. The primary

properties are controlled in the spray drier and they characterise the drying process; the

secondary properties are crucial for powder application. During the investigation and

the optimisation of spray drying process and the development of the preferred

morphology, primary properties are crucial; however, only size of granule is important

during the application of powder. Primary properties are controlled in spray drier;

secondary properties are important for powder application.

The general factors that affect the properties (see chapter 2) of granules are: the

size of sprayed droplet (see chapter 3) and interaction of solid particles with each other

and with the solvent (see chapter 4). The most important parameter that affects droplet

size of ceramic suspension and subsequently the size of dried granules is the energy

applied to atomization or the so-called atomizing gas rate. Drying or droplet-to-particle

conversion is determined by mass and heat transfer. There are two main mass transfer

processes. (1) Migration of solid in droplet to form the shell of the droplet. This is

mainly affected by concentration of slurry, initial particle size and capillary forces. (2)

Diffusivity of vapour through the shell and permeability (porosity) of the shell. Mass

transfer process strongly depends on particle size and the presence of binders as well as

equipment type and geometry.

4
1.2. Applications of spray drying

a) Granulation. Spray drying of ceramic powder is used to obtain granular

powder with good flowability and to reduce the amount of dust. Spray drying is the

most common method for producing granulate for green body formation by granular

pressing or dry pressing. It is the most economical method for drying wet-processed

dispersed clay slips [5]. The main advantages of using granulation are: high flowability

of resulting powders, high packing density (see chapter 2) and strong compactability

[6,7]. Granular pressing or dry pressing is important technique in production of tiles and

tableware [6,8] and production of advanced ceramics, e. g., Yb:yttrium aluminium

garnet (YAG) [9] and Nd:YAG [10] laser grade ceramic materials and solar heat-

reflective roofing granules [11].

b) Producing nanoparticles. Spray drying is a rapid drying method and the use

of additives limits agglomeration; therefore, it is suitable for obtaining nanoparticles

from colloidal or true solutions. The use of spray drying and related methods, e. g.,

spray pyrolysis and electrospray pyrolysis, to produce nanoparticles (nanocrystaline

mesoporous granules with average diameter under 300 nm) is described in [12]. The

production of organic and inorganic functional nanoparticles with various morphologies

is summarized in [13] and [2].

c) Producing composites. The most ceramic composite materials obtained by

spray drying are by encapsulation or entrapment of ceramic particles in polymer matrix

or co-precipitation of composite ceramic. For example, hydroxyapatite nanoparticles

were incorporated in chitosan matrix for bone repair and drug delivery systems [14];

encapsulation by spray drying is reviewed in [15]. Montmorillonite clay was used as an

alternative matrix former for spray dried drug nanosuspensions [16]. Composites of

5
Na2FePO4F with multi-walled carbon nanotubes in sodium iron fluorophosphate

electrodes were obtained for lithium- or sodium-ion batteries [17]. TiO2/mica and h-BN

powder were mechanically mixed and spray dried to synthesize composite powder for

use as sun protection filling in suncreams [18]. Al2O3–ZrO2 composite ceramic

nanopowders with polymer additives are prepared for use in production of advanced

ceramics [6,19]. Titania nanoparticles were stabilized by anionic carboxylated

polyelectrolyte to produce redispersible granules [20].

d) Synthesis. Spray drying is a simple and effective way to synthesize spherical

powders with controlled number of small ions, for example, Li+ [21]. Metal oxide–

reduced graphene oxide composite powder can be obtained from solution containing

water-soluble metal salt and graphene oxide nanosheets [22].

e) Crystallization. During spray drying crystallization can occur. It can be used

for solid (like NaCl) formation in predicted granule morphology [23] or for co-

precipitated two component nanopowder, for example Al2O3–ZrO2. In contrast, spray

drying is also used to produce amorphous solid dispersions due to rapid evaporation of

solvent [21,24].

f) Obtaining controlled morphology. Various morphologies accompanied with

relatively high flowability and narrow size distribution or mesoporous particles can be

produced for applications as catalysts or sorbents, e. g. gadolinium doped cerium

dioxide [25], silica [26] and calcium oxide [27]. Spray drying can also be used to

prepare randomly oriented clay or other platelike particle powders for qualitative X-ray

powder diffraction analysis instead of highly texturized powder obtained by

conventional drying on a plate [28]. Controlling the morphology is discussed in

chapter 4.

6
2. The effect of granule morphology on the powder properties

The morphology of granules affects the properties of the powder, thus

determining the use and handling of the dried powder. The spray dried ceramic powders

can be divided in two large groups. First group is characterized by dense and smooth

granules, high flowability and apparent density of the corresponding powder.

Flowability of ceramic powder is especially important in manufacture of dense and

transparent ceramics. Second group is highly porous and hollow granules forming a

powder with high surface area, and, therefore, is used in sorbents, drug delivery systems

or in catalysis. However, due to the wide variety of morphologies, these are extreme

cases or groups; in practice powders have various combinations of properties applicable

for a number of special applications.

2.1. Flowability

One of the advantages of drying mineral suspensions by spray drying is that the

granules are free-flowing, and, therefore, they are easier to handle than milled powder.

For example, powdered kaolin clay has an angle of repose of about 90° and, therefore,

the powdered clay resists flow through chutes and hoppers unless vibrators or air

lancers are used. Spray dried clay granules, in contrast, normally assume an angle of

repose of about 45° and flow readily in hoppers and chutes without vibrators or lancers

[5]. Good flowability is important, for example, for filler powder in paper production

[5]; in ceramic shaping, for example, if fully dense and mechanically strong ceramics of

a complex shape should be obtained [10]; in liquid chromatography the efficiency is

improved with sphericity of packing material in column [29]. The relatively higher

flowability can be attributed to the hard shell of granule which favours the free flow

7
[30]. Spherical granules of powder are also used in cosmetic products due to their

excellent tactility, called ball bearing effect, if compared to milled particles [31].

2.2. Apparent and tapped density

Apparent density is the powder mass per one unit of volume (this volume

includes pores within particles and voids between particles). Tap density or tapped

density is obtained by tapping or vibrating the powder until the minimum and constant

volume is reached. Both of these quantities depend on porosity and shape of the

particles that, in turn, determine flowability and packing density. The maximum of

apparent density for (Y0.995Nd0.005)3Al5O12 granules was found with solid concentration

in slurry at 50 wt. %, and decreasing for higher and lower concentrations. In

comparison, the tap density maximum was at slurry concentration 42 wt. %. The

difference is explained thus: increased solid content at first increased of granule bulk

density, then above some level granule shell becomes dense and does not let moisture to

evaporate, so that the increased vapour pressure inside caused a ballooning effect, that

resulted in doughnut or apple shape granules [32].

The difference between apparent density and tapping density is the Hausner

ratio or compressibility index. For powders with good flowability values of both

apparent density and tapped density are similar and the Hausner ratio is closer to 1.

Powder classification with the Hausner ratio: non-flowing and cohesive > 1.4, free-

flowing 1 – 1.25 [33]. Hausner ratio for smooth doughnut-shaped and spherical

granules was found to be similar (1.17 and 1.20 respectively). Both of these powders

had good flowability [34]. Granules with high flowability and low intergranular friction

are expected to have lesser packing flaws. Hausner ratio of fine powder of initial

particles compared to spray dried granules decreased two to four times [30].

8
2.3. Morphology of granules for special applications

It is possible to produce various morphologies of granules using spray drying:

hollow, dense, porous or nanostructured granules, as well as microcapsules [2].

Additionally, spray drying gives particles with relatively narrow size distribution

compared to ceramic powder obtained by milling [13]. The ability to control the size of

granule as will be discussed later.

Morphology of the granulated powder can impact chemical properties, for

example, dissolution preferentially occurs on locations of looser structures and higher

porosity [35]. Thermal properties and light absorption can change compared to starting

materials [18]. However, some authors have found that spray drying creates

agglomerates that have the same reactivity [36] and surface area [37] as initial particles

but improved powder handling properties.

3. Controlling the size of granules

Droplet size and concentration of the slurry are key parameters that determine

granule size. Other parameters – equipment and spray dryer settings – have a minor

effect on granule size.

3.1. The effect of droplet size

Droplet size is mostly determined by atomizer type and atomization parameters.

3.1.1. Atomizer types

Each type of atomizer gives a range of possible droplet diameters. By changing

settings the droplet size can by varied within the range of respective atomizer type. For

example, granules with diameter 50 – 400 μm can be produced by hydraulic nozzles,

while granules smaller than 1 μm can be produced by four-fluid nozzle [1]. Two-fluid

9
nozzle produced granules with diameter 0.5 – 10 μm [38] and 0.5 – 5 μm [9]. Very

small granules with sizes from 20 to 30 nm can be obtained from diluted slurries (for

example, 0.01 mol/L) if various modifications of electrospray pyrolysis are used [12].

The two-fluid atomization nozzle diameter has no influence on granule size for dilute

suspension (10 vol.% Al2O3 and TiO2 mixture), if the air pressure is kept constant, but

has great effect on more concentrated solutions (15 vol.%) [39].

3.1.2. Atomization parameters

The average size of a droplet is inversely proportional to atomizing energy, e.g.

air flow rate in two-fluid nozzle [2,40]. Additionally, droplet size depends on the liquid

flow rate, surface tension and viscosity of the slurry.

The droplets are generated when the slurry liquid is broken up by aerodynamic

disruptive forces and consolidating forces of surface tension and viscosity. In a two-

fluid nozzle relative flow velocity difference between liquid and gas is the main driving

force of the atomization process, and it is controlled by liquid feed flow rates,

atomization gas flow rate, and by nozzle geometry [41]. Thus, the droplet diameter Dd

can be described by equation:

( )( )

where C is a constant that depends on nozzle design; ρ, μ, σ, v and f are density,

viscosity, surface tension, velocity and flow rate of the liquid (L) or atomization gas (A)

[10]. The diameter of generated droplets also has been described using another similar

equation where slightly different parameters are used:

[ ( √ ) ]

10
where C is a constant that depends on nozzle design; ρ, v, σ and f are density, kinematic

viscosity, surface tension, velocity of the liquid (L) or atomization gas (A) [41].

Air flow in the nozzle changes the size of granules more significantly than slurry

feed rate. For example, decrease of air flow from 15 to 5 L/min enlarged hydroxyapatite

granule mean size twice – from 3.47 to 6.27 μm for 20 g/L slurry and even more – from

3.1 to 7.71 μm for less concentrated slurry (10 g/L), while slurry feed rate increase from

5 to 15 and 25 r/min did not change granule size significantly (2.86, 3.11 and 2.92 μm,

respectively) [42].

The size distribution of dry granules does not depend on spray dryer settings

[38,42]. Drying time increases, if droplet diameter is increased, and it is proportional to

the square of initial droplet diameter. Outlet temperature and solvent volatility should be

increased to increase evaporation rate, whereas the relative saturation of the drying gas

should be decreased [41]. Therefore, maximum droplet size additionally to settings of

atomization is limited by height of drying chamber (or available drying time), maximal

available temperature (limited by equipment or dried material), volatility of solvent and

moisture of drying gas.

3.2. The effect of concentration of initial slurry

Concentration of slurry or solution to be spray dried is another important

parameter that determines the size of dried granules. This is one of drying parameters of

ceramic slurry that differs from drying of polymer solutions and emulsions due to

differences in viscosity increase and mass transfer though the shell of drying granule. In

case of drying ceramic slurry, higher concentration leads to larger granule size,

increased density, and process effectivity.

11
 Mean granule size of ceramic powder increased nearly linearly from 25 to

60 μm with increasing solid content in the range from 40 to 50 wt.% [32]. The

comparison of increase of granule size with solid content for various powders is shown

in Table 1. It can be seen that increase of granule size with composition can be

significant at various concentrations of ceramic powder. In contrast, in spray drying of

carbohydrate solutions particle size increases substantially only in case of dilute

solutions (1 – 5% w/w), but remains constant for more concentrated solutions. At higher

concentrations (> 10 wt.%) carbohydrate granule size is determined by droplet size

produced during atomization process [41].

Maximum possible solid content is a function of the size distribution of the

powder, particle shape, and the electric double-layer thickness of colloidal suspension.

Maximum possible micrometre-sized solid content for a fluid suspension is 40 –

50 vol.%. Stable concentrated suspension can be obtained more easily from large and

round particles rather than from fine and plate- or needle-shaped particles [40]. The

nature of particles is also important, for example, the concentration of the water-

swellable clay mineral should not be higher than 20 % by weight. At concentrations

exceeding 20 % by weight, the water-swellable clay gel viscosity is high; therefore, the

delivery of the liquid to a spraying nozzle is difficult, and clogging of the nozzle may

occur [29].

3.3. Other parameters

Additionally to droplet size and concentration of slurry, granule size also

depends on other parameters, for example, nozzle diameter and air pressure in nozzle

[39,42,43]. Granules spray dried at high temperatures are larger and denser than

granules obtained by freeze spray drying [39].

12
 Dispersant was found to affect the size of granules that were obtained at lower

atomizer speeds, but the presence of dispersant had no effect at higher speeds. The use

of a binder can increase the size of granules almost twice [10]. The size of granules was

found to correlate with the size of initial particles (investigated range of d50 was from

0.25 to 6 μm) [30] and grain morphology due to shrinkage – hollow and porous particles

are larger than corresponding dense particles obtained from droplets with the same

diameter [30,44]. However, other authors have investigated two kinds of particles: in

size range d10 – d90 0.2 – 1.4 μm (monomodal distribution with peak at 1.1 μm) and in

size range 0.1 – 1.1 μm (polymodal distribution, mean particle size less than 1.1 μm),

and obtained spray dried granules with similar size distribution: d10 – d90 4.6 – 23.6 μm

and 7.3 – 25.5 μm. The fact that larger initial particles gave more granules in small-size

range was explained by formation of agglomerates instead of granules [45]. This also

was shown by shape analysis of granules – larger granules were more often round

shaped (width and length ratio close to 1) than smaller ones (Fig. 3) [37].

4. Controlling the morphology of granules

The morphology of dried granules is determined by mass and heat transfer

during drying [2], by the balance of solid particle cohesion strength (including diffusion

and shell flexibility), and compressive stresses resulting from evaporation and capillary

forces [46]. There are different morphologies of granules that can be produced by spray

drying, for example, spheres, doughnuts, capsules, porous, hollow and hairy granules,

raspberry-shaped granules. All granule shapes, except hairy, can be prepared from

ceramic suspensions with additives [2].

13
 The morphology is strongly affected by the composition of slurry and by the

properties of granule shell. The morphology is affected by interaction between particles

which is a strongly composition sensitive parameter. For example, polymer suspensions

or emulsions have higher viscosity due to long molecule chains and shell of granule is

more elastic while the morphology of solid ceramic particles depends on initial solid

particle size, agglomeration rate, dispersants etc. – as will be discussed in this chapter.

Also, temperature sensitivity of organic components is much higher than that of ceramic

compositions. Thus, there is a fundamental difference between slurry behaviours during

the drying of ceramic dispersions and during the drying of polymer dispersions.

4.1. Formation of morphology

Simulations of granule morphology evolution during drying of droplets

containing suspended particles have been developed lately by several authors. These

authors divide droplet drying process into two steps – (1) shell formation and (2) core

drying [3,23,47]. The model was based on drying a suspension of silica nanoparticles.

Handscomb et al. [48] gives extensive review of models of droplet drying and describes

physics of drying after shell formation. Droplet drying is described by four sub-models:

shell thickening, wet shell, dry shell and slow boiling. The first one describes

continuing shrinkage while shell growth occurs. The dry shell sub-model is similar to

classical shrinkage theory in which shell is assumed to be dry and vapour migrates

through the shell. The wet shell sub-model describes cases in which shell is formed, but

is still saturated with solvent and evaporation proceeds from the external surface of the

shell – this indicates the formation of a hollow granule. The slow boiling sub-model

depends on droplet morphology when boiling starts – if a dry shell is formed, then

boiling commences at the evaporative front and the shell does not crack. If boiling starts

14
during shell thickening, that is – in the wet shell regime, then bubbles are formed and

the droplet inflates. In these models initial particle size, shape, and distribution in the

droplet are important; also density of drying gas and binary diffusion coefficient of the

gas and water (moisture) vapour are important.

Breinlinger et al. [46] used capillary surface tension to model the mean density

of a dried granule – as neck geometry and capillary force were not known, pressure

gradient and line tension acting on the particle were used for the simulations. A non-

linear correlation was found – particle density increases with surface tension and mode

of correlation itself depends on the cohesion of the shell forming particles.

Mezhericher also found that the main parameters that affect granule morphology

are shell strength and capillary stress. The morphology of dry granules correlates with

the droplet radius at the end of the first drying stage when shell is formed. This model

suggests that hollow granules will form from less concentrated slurries [47]. He also

compared 2D and 3D flow models [49] and found that 3D model gives much more

precise data on drying kinetics in the drying chamber of the spray dryer. This model

calculates the maximal temperature that granule will reach during drying and the

optimal droplet size for respective drying conditions.

4.2. The effect of size and size distribution of initial ceramic particles

Properties of initial particles affect the morphology of granules, for example,

initial particle size distribution determines theoretical packing density of particles and

affects the capillary forces in intergranular voids within the forming shell of a granule

[46]. Random close packing of uniformly sized spheres in three dimensions is not a

well-defined arrangement – possible packing densities range from 6 to 65 %, and the

highest theoretically possible packing density is 74 %. Due to capillary forces, size

15
distribution and non-ideal sphere shape of initial particles, the real packing density of

these particles is higher than that of uniform spheres and should be determined

experimentally [3].

Walton and Mumford found that the critical particle size is 1 μm; smaller initial

particles formed hollow granules, and larger initial particles formed solid granules. The

distribution of particle sizes in calculations can be replaced by surface area per unit

volume. Particle size correlates with the vapour pressure in the forming particle – for

smaller particles the pressure is higher. The modelling showed that slurry with initial

particles in a range of 50 nm and 1 μm produces hollow granules [48]. However, there

are other parameters limiting the diffusivity of particles and moisture – as will be

discussed further.

In practice, the size distribution, besides the average size of initial particles, also

has a major effect on the shell properties, on the density of powder, and on the

morphology of granules. An experimental study [30] showed that large alumina

particles (D50 = 6 μm) gave porous, rough and doughnut shaped granules with apparent

powder density only 0.63 g/cm3. Smoother and denser (apparent density 0.96 g/cm3)

granules were obtained from finer initial particles (D50 = 0.8 μm) with wide size

distribution. The use of very fine initial particles (D50 = 0.25 μm) with narrow size

distribution resulted in a ballooning effect on the dried granules due to formation of

dense shells and, therefore, the apparent density of the resulting powder was 0.85 g/cm3.

4.3. The effect of agglomeration of initial particles in a slurry

The agglomeration of initial particles affects the viscosity of the slurry and also

the properties of the shell during drying. Well dispersed slurries create dense and thin

16
shell that results in hollow granules; flocculated slurries (or slurries containing large

agglomerates) result in denser granules.

Bertrand and Roy [50] has shown that shell thickness is proportional to

sedimentation rate or agglomeration of initial particles – high sedimentation rate

linearly correlates with the increase of shell thickness. Thin shells can be obtained from

well dispersed suspensions due to higher solid particle mobility than in the case of

aggregated suspension.

Lukasiewicz [40] described the colloidal behaviour of slurries used in spray

drying and the necessity to deflocculate the system to obtain lower viscosity for highly

concentrated slurries. He also suggested that the concentration of slurry should be given

in volume percent and not in weight percent for easier evaluation of packing density.

Deflocculation of suspension leads to formation of hollow granules, but drying a

flocculated slurry results in slightly porous but homogeneously dense granules [51,52].

Similar results were obtained Mahdjoub et al. [53]. He carried out extensive research of

sedimentation stability of suspensions with various amounts of two binders in wide pH

range and the impact of these parameters on shell thickness of spray dried granules.

Addition of binder to the suspension changes the state of the dispersion depending on

the used solvent and the nature of the binder. At pH 4 addition of only 1 % of binder

severely reduced flocculation, while at pH 7 zirconia particles were well dispersed and

binder did not have much impact on the sedimentation behaviour. Hollow granules

were formed in the case of dispersed slurries (low sedimentation height – relative

sediment height RSH < 53 %), whereas full granules were obtained using flocculated

slurries (high RSH > 62 %). This is in agreement with [44]; this study also found that

shrinkage of particles obtained from dispersed slurries is smaller than from flocculated

17
slurries. This can also be interpreted as the fact that granules formed from solid (non-

agglomerated) particles have higher shrinkage or droplet to dried granule diameter ratio

than hollow granules. To better understand the formation process of granules, the

movement of liquid through the shell during the thickening process can be likened to

the growth of a filter cake [48].

Well dispersed slurry can result in highly re-dispersible granules. The effect of

several dispersants on production of re-disperible granules containing well dispersed

nanoparticles are described in [20]. The agglomeration can be also controlled by adding

binders as discussed in next section.

4.4. The effect of binders and dispersants

Polymer additives are commonly used to modify the properties of ceramic

particles. Most common roles of polymer additives are binders and dispersants. The

effect of amount and kind of binders and dispersants on granule morphology is a very

wide topic. There are no strict differences between the effects of polymer. In small

amounts, polymer is, for example, a dispersant and reduces agglomeration of particles

and viscosity of the slurry, while in large amounts it forms composite material with

significantly different properties of granules. Binder is usually used to improve the

mechanical strength of granules, to increase the elasticity of granules and to create

composites; alternatively the binder can be burned out by thermal treatment afterwards

to obtain larger surface area of the granules.

The selection criteria for the binder used in spray drying raw material for

ceramic production are based on its ability to form granules that readily deform during

compaction, to burn-out cleanly before sintering, and to give a high compact density

and strength [6]. The nature of the binder – solubility and particle size affects the wall

18
thickness of the hollow granules, e.g., latex was embedded inside zirconia flocs and full

grains formed compared to hollow granules obtained with hydrosoluble polyvinyl

alcohol additive [53].

There are various results on binder impact on the size and shape of granules.

Dispersant ammonium polyacrylate in combination with increasing amount of polyvinyl

alcohol (PVA) binder (3, 5 and 7 wt%) in zirconia slurry (initial particle size D90 was

2,62 μm) resulted in increase of granule size D90 from 10 μm to 29 μm and 65 μm,

respectively; however, the higher binder concentration resulted in high moisture content

in granules, so the agglomeration of granules and adhesion to drying chamber walls

occurred [54]. Increase of polyvinyl butyral (PVB) amount from 1 to 3 wt.% slightly

decreased apparent and tap density of powder due to doughnut shape and increased final

size of granule after drying [10]. In contrast 3 wt.% polyvinyl pyrrolidone (PVP)

addition to Li4Ti5O12 did not affect the well-rounded shape and increased tapped density

and size of granules [55]. Alumina granules prepared using 0.35 wt.% ammonium

polyacrylate (0.14 mg/m2), were of solid, whereas, using 1 % deflocculant resulted in

hollow granules [52]. More spherical Al2O3-ZrO2 granules were obtained from the

slurry containing polyethylene glycol–hydroxyethyl cellulose cobinder (PEG–HEC)

compared to polyvinyl pyrrolidone PVP. The sphericity of granules was improved as

the viscosity of solution increased [6].

Additives can increase the density of granules and densification ceramic during

pressing and sintering. For example, PVA addition to alumina during spray drying

increased the density of ceramics produced from the spray dried powder, and lubricant

stearic acid was able to replace binder PVA to obtain dense ceramic [7]. Granules that

are used to form transparent Yb:YAG polycrystalline material were obtained from

19
Y2O3, Al2O3 and Yb3O3 with 1 wt.% PEG 400 as dispersant and 0.5 wt.% tetraethyl

orthosilicate (TEOS) as sintering aid [9].

The binder can be used to inhibit the segregation of compositions, for example

polyvinyl butyral (PVB) for spay drying mixture of Al2O3, Y2O3 and Nd2O3 powders

[56].

Binder can increase the viscosity of slurry; increase of the viscosity leads to an

increase of granule size. However, excess use of binders can also lead to formation of a

flexible shell with low permeability around the droplet that decreases the evaporation

rate of solvent and the solvent begins to evaporate inside the granule. This situation, in

turn, leads to formation of doughnut-shaped granules instead of spherical granules [10].

If high surface area and porosity is necessary, polymer binders can be used to trap

vapour as bubbles (pores), and after removal of binder a very porous ceramic matrix is

obtained [25].

Migration of binder during drying should be considered as it affects morphology

and other properties of spray dried granules. Organic binders (especially water soluble)

have a tendency to migrate to the surface of the granule during drying together with

moisture. Migration causes higher binder concentration on the surface of the granule

that results in heterogenous chemical and mechanical properties across granule.

Macroscopic moisture flow and binder migration can occur only if there is a continuous

liquid network within the droplet or during constant rate drying period [40]. Lately, a

model describing the enrichment of the surface with a slowly diffusing component has

been created. Model is applicable for different initial total solid masses, mass fractions

of slowly diffusing component in the bulk, and drying temperatures [57].

20
 4.5 Formation of hollow granules and porous granules

Some applications, e.g. sorbents, catalysts, controlled release capsules of drugs

etc. require particles with high surface area, low density and spherical shape. There are

several methods to produce hollow granules, e.g., templating method, emulsion

processing, high temperature smelting, layer-by-layer self-assembly technique, but

spray drying is the most promising [58]. Hollow, doughnut and apple shaped granules

are formed if during the spray drying a bubble is formed inside the shell.

Walker [52] has summarized four mechanisms leading to formation of hollow

granules: (1) ballooning, where the internal pressure causes the droplet to expand; (2)

moisture evaporating at a faster rate than diffusion of solids back into the droplet

interior, leaving air voids; (3) suspended solids being drawn to the droplet surface as

liquid migrates because of capillary action; and (4) entrapped air in the feed slurry

persisting as voids.

Also, several authors have investigated mechanisms of formation of hollow

granules. Seydel [23] suggests that a bubble can originate if solvent is transported to the

surface by capillary forces and the pressure inside the droplet decreases. This forces the

solvent to evaporate or, alternatively, drying gas permeates the shell as pressure inside

and outside of the granule is equalized. If the shell is impermeable, it can break or

shrink as the pressure forces inside the droplet exceed the mechanical strength of the

shell. In another model it was found that bubble formation occurs when the negative

capillary pressure exceeds the tensile strength of the fluid [48]. As discussed above,

shell properties are important. Mezhericher [47] describes a model where the shrinkage

of the shell stops if the strength of the shell is greater than capillary stress; then shell

turns into crust and, if the volume of droplet is greater than the volume of solid particle

21
with porosity ε, a hollow particle forms. However, no critical ε is given, but the strength

of the shell that inhibits the shrinkage of droplet is concluded to be the most crucial

parameter to form hollow granules.

The most important parameters that affect the porosity of a dried granule (for a

single droplet drying in an acoustic levitator) were found to be: the median diameter of

initial particles, the concentration of feed slurry and the flocculation state. The influence

of temperature of the drying gas and initial volume of the droplet was not relevant to the

porosity of dried granules [51].

Mostly doughnut shaped granules formed from 10 vol.% rather than 15 vol.%

slurry [39], when binder content was increased to more than 2.0 wt.% [10], and more

from basic than from acidic slurry [43]. Drying at lower temperatures tended to result in

more shrinkage and deformation or collapse of granules [48].

Highly porous granules can be obtained using freeze spray drying instead of

high-temperature spray drying; however, these granules have also poor flowability [39].

Highly porous and hollow granules can also be formed also by using foaming agents

[35] or pore template materials [27]. The pore formers (e. g. Pluronic P123) during

thermal after-treatment of spray dried powder can increase the volume of particle

several times [25].

5. Discussion

The morphology of dried granules can be controlled. The repeatability between

batches is good, but the morphology of dried granules slightly differs even in the same

batch. The impact of parameters has a cumulative effect; therefore even slight changes

in several of them can affect the result. Parameters that affect size and morphology of

22
dried granules can be divided in several groups: 1) formulation or composition of slurry,

2) drying process 3) equipment and 4) environment. The list of parameters of each

group is shown in Fig. 4. The formulation and process parameters are easily adjustable

while equipment usually is the same and changing parts of it (nozzle size or design)

request additional costs. The environment is crucial if drying agent and carrier is air.

The air is the cheapest drying agent, but the humidity of it can highly differ and affect

drying process.

The most crucial parameters that depend on slurry formulation are ceramic

particle size and size distribution, concentration and agglomeration in initial suspension.

Theoretically, the critical size of initial particles under which hollow granules are

formed is 1 μm [48]; however, experiments [30] show that size distribution can have a

major effect. Unfortunately, the authors of this article did not find any research on

particle shape effects on morphology of granules. The agglomeration can be controlled

by adding dispersants or binders and by adjusting pH. Capillary forces between solid

particles and liquid in drying granule are used successfully for modelling; it is a

complex variable influenced by above mentioned slurry parameters.

The most important drying process parameters are: droplet size generated in

atomization and drying temperature. It is well defined that droplet size strongly

correlates with granule size if morphology of granule is the same. The droplet size

mostly depends on slurry flow (feed) rate and gas flow rate or atomization energy if

another atomizer type is used instead of two-fluid nozzle. The droplet size depends also

on formulation parameters – density, viscosity, surface tension; however, in case of

ceramic suspensions these effects have not yet been in investigated more thoroughly.

23
The formulas for calculation droplet diameter cannot be widely used as necessary

variables are not easily available or measurable.

6. Conclusions

Spray drying of various materials is commonly used in commercial and research

applications – from the necessity to dry suspensions or solutions to producing advanced

materials with defined properties. The required properties of granules vary widely

depending on their intended application. However, mostly granules are characterized by

two properties – granule size and morphology. Other properties, such as flowability,

density, porosity, shell thickness and roughness, result from granule size and

morphology. The size and the morphology of the granules are not independent

variables: the size of the granules is related to the morphology, and the morphology of

granules can change with size.

The morphology of spray dried powder granules can be controlled and is highly

repeatable. The main parameters that affect the morphology of spray dried granules are:

the size, size distribution and the agglomeration of initial particles. The main parameters

affecting the size of spray dried granules are: droplet size and concentration of slurry.

One of the main challenges of investigation of the relationships between

parameters during drying is the ability to measure some important parameters, e. g.

capillary pressure and properties of shell during drying. The other challenge is large

thermal and concentration gradient in any spray dryer of laboratory or industrial scale.

These gradients can be eliminated by using single droplet drying techniques for

theoretical studies; however, this is not a solution for producing a large amounts of

powder.

24
 In general, some uncertainties about spray drying process still exist; however,

great progress has been accomplished lately in understanding the processes of ceramic

suspension droplet drying and ability to model and control the granule size and

morphology. The most challenging task in spray drying is to predict if hollow or dense

granule will be formed for the specific formulation.

Acknowledgements

The research has been supported by the National Research Program of Latvia

2014-2017 within the program No.6 project No.4. “Investigation of geological

resources – new products and technologies (Earth)”.

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Fig.1. Diagram of a common laboratory scale spray dryer. Droplets and granules are

depicted oversized for better visibility.

33
Fig. 2. Summary of variables affecting mass transfer in the droplet during spray drying

and resulting properties of dried granules.

3.0

2.5
Length-width ratio

2.0

1.5

1.0
1.5 2.5 3.5 4.5 5.5 6.5 7.5
The average diameter of granule, μm

Fig. 3. Shape and diameter correlation of spray dried illite clay granules. Each dot

represents a granule. [37]

34
Fig. 4. Ishikawa diagram showing factors affecting morphology and granule size of

spray dried granules; the most significant parameters are in bold.

Table 1. Comparison of solid content increase and respective mean granule size increase

Composition Solid content Mean Reference

in slurry granule size,

μm

Y3Al5O12 40 to 50 wt.% 41.4 to 48.9 [10]

(ball milled particles)

(Y0.995Nd0.005)3Al5O12 30 to 40 wt.% 28 to 31 [32]

(ball milled, < 1 μm 40 to 50 wt.% 31 to 50

with dispersant and 50 to 55 wt.% 50 to 58

binder)

Hydroxyapatite 5 to 10 g/L 2.6 to 3.1 [42]

10 to 20 g/L 3.1 to 3.5

Al2O3 and Al2O3– 10 to 15 vol% 6.8 to 11 [39]

TiO2 nanoparticles (various 7.1 to 17.3

35
 pressure and 6.5 to 26.6

nozzle

diameter)

TiO2 nanoparticles 10 to 30 vol% 76 to [34]

(62 wt. %) 63*

* at this (higher) concentration agglomerates were formed additionally to granules

Highlights

 Parameters that affect morphology of spray dried granules are summarized.

 Hollow, doughnut-shaped and dense granule formation is discussed.

 Morphology is affected by size distribution and agglomeration of initial

particles.

 Morphology is also affected by permeability and mechanical strength of granule

shell.

 Great progress has been made in understanding droplet drying process during

the last decade.

36