Powder Technology 313 (2017) 389–401

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Powder Technology

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

Review

A review of bulk powder caking

U. Zafar a, V. Vivacqua a, G. Calvert a,1, M. Ghadiri a,⁎, J.A.S. Cleaver b
a
Institute of Particle Science and Engineering, School of Chemical and Process Engineering, University of Leeds, Leeds LS2 9JT, UK
b
Department of Chemical and Process Engineering, University of Surrey, Guildford GU2 7XH, England, UK

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

Article history: The handling and storage of bulk powders is common in many industries such as detergent, pharmaceutical, bulk
Received 31 October 2016 chemical and food. A lot of materials are susceptible to changes with time that may lead to bulk powder caking,
Received in revised form 13 February 2017 resulting in an unmanageable powder and process downtime, which impacts upon profitability. In this review
Accepted 14 February 2017
the current state of the art related to powder caking is explored. The relevant interparticle interactions are
Available online 21 February 2017
discussed with respect to elastic and plastic deformations and the development of liquid and solid bridges due
Keywords:
to capillary condensation, sintering and solvent evaporation. The environmental, i.e. temperature and humidity,
Powder caking and the mechanical conditions can heavily influence the transformation of a bulk powder and a number of
Caking mechanism studies are available that attempt to relate these conditions to caking. A significant amount of work related to
Assessing powder caking the caking behaviour of amorphous powders is available in the literature. Amorphous materials are susceptible
to caking due to environmental conditions influencing the glass transition temperature. Once the temperature
of amorphous powders exceeds the glass transition, viscous flow occurs and cake strength increases. Crystalline
solids may undergo transformations leading to caking. It can take a considerable time and cyclic environmental
conditions for caking to occur. However, little research focuses on cyclic conditions and there is limited predictive
capability. Finally the options available for attempting to reduce caking propensity are briefly covered and a
section that discusses the available caking test methods is given.
© 2017 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 390
2. Particle interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 390
2.1. van der Waals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 390
2.2. Electrostatic forces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 390
2.3. Liquid bridge forces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 390
2.4. Contact mechanics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 391
2.4.1. Elastic deformation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 391
2.4.2. Plastic deformation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 391
2.4.3. Surface roughness . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 391
2.5. Solid bridge formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 391
2.5.1. Sintering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 392
2.5.2. Solvent evaporation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 392
3. Amorphous powders . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 393
3.1. Glass transition temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 393
3.2. Viscous flow kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 393
3.3. The effect of composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 394
4. Caking dynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 394
4.1. Heat and mass transfer models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 394
5. Caking reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 395
5.1. Caking reduction additives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 396

⁎ Corresponding author.
E-mail address: m.ghadiri@leeds.ac.uk (M. Ghadiri).
1
Current address: Procter and Gamble, Newcastle Innovation Centre, Newcastle upon Tyne NE12 9BZ, UK.

http://dx.doi.org/10.1016/j.powtec.2017.02.024
0032-5910/© 2017 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
390 U. Zafar et al. / Powder Technology 313 (2017) 389–401

6. Caking test methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 396

6.1. Mechanical test methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 396
6.1.1. Shear cell testing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 396
6.1.2. Uniaxial compression testing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 396
6.1.3. Tensile testing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 397
6.1.4. The ICI caking test . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 397
6.1.5. Creep testing. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 397
6.1.6. Penetration testing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 398
6.1.7. Powder rheometer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 398
6.2. Alternative test methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 398
7. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 399
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 399
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 399

1. Introduction 2.1. van der Waals

The undesirable transformation of bulk powders, such as caking and There are different classes of van der Waals force and more detail is
deliquescence is a common problem in a number of industries including available in the literature [7,12]. The dispersion force is due to local
detergent, food, fertiliser, pharmaceutical and chemical. By definition, polarisation within molecules caused by random fluctuations in
powder caking may be viewed as the detrimental aggregation of parti- electrons and is consequently transient and induced; these are regarded
cles, which transforms a readily free-flowing powder into a coherent as non-specific interactions. Specific van der Waals forces are due to
solid. The amount of caked material can vary from large lumps, which interaction between molecules with permanent dipoles.
willingly break up when stressed, to the irreversible fusion of particles
that are no longer representative of the original material. The environ- 2.2. Electrostatic forces
mental and mechanical conditions a material experiences can consider-
ably influence bulk powder transformation. In certain conditions, a The science of electrostatics is in itself highly challenging as there are
material may be so hygroscopic that it deliquesces. Obviously caking many mechanisms that influence particulate behaviour [14]. Electrostatic
and deliquescence can be a significant problem that may lead to a loss forces may be responsible for particle deposition of airborne particles on
of material functionality and a lower quality product [1]. This could processing walls, which may promote powder make-up; however, there
have a large impact on profitability. is little evidence suggesting that electrostatic forces play a significant
Bulk powder caking is a very challenging topic because there are long term role on powder caking. A possible explanation for this is that
many reported mechanisms that may lead to powder transformation the potential difference between particles dissipates much more rapidly
and few studies have taking a holistic view of the subject [2]. Griffith compared to the time required for caking [2]. However, in the presence
[3] provided a very useful and practical overview of caking and broadly of electric fields, particles adhere strongly to each other due to the
classified the subject into four groups: (a) mechanical; (b) chemical; electro-clamping phenomenon [15].
(c) plastic-flow; and (d) electrical. There are many features that need On the other hand, electrical caking has been implicated as a possible
to be considered when understanding caking propensity. Intrinsic mechanism that may lead to caking; although the cake strength is typical-
factors such as cohesion, elasticity, yield stress, amorphous content, ly relatively weak [3]. For example, the application of a mechanical stress
hygroscopicity, particle size and many others will inevitably influence can induce a charge polarisation in crystals, known as the piezoelectric
caking behaviour; however, extrinsic factors such as temperature, effect, which can promote caking; pyroelectric caking can occur as a result
humidity, stress, strain rate, vibration may also heavily influence caking. of charge polarisation due to heating or cooling crystalline materials; and
This makes it very difficult to reliably predict how a powder will behave. finally, ferroelectric caking may happen when crystals are placed in an
This is especially the case when the timescale for a powder to cake is so electric field.
long that extrapolation of laboratory data is common.
In this review, the current state of the art and the experimental ap- 2.3. Liquid bridge forces
proaches available for investigating bulk powder caking are addressed.
A summary of relevant particle interactions, contact mechanics, caking It is recognised that liquid plays a pivotal role in bulk powder caking
mechanisms and dynamics is given. Finally, a section detailing the and may be present between particles as a result of condensation from
commonly used experimental test methods is provided. vapour, or because it is intentionally added, for example, as a binder. A
more detailed review of capillary forces has been made by Seville et al.
[16]. Capillary forces are an initial mechanism that may lead to subse-
2. Particle interactions quent cake formation and there are many studies that investigate the
relationship between agglomerate strength and interparticle forces
Powders may experience a variety of interparticle forces and these [17–24].
have are classified according to their relative magnitudes, from strongest The capillary force, depicted in Fig. 2.1, is positive, as long as the
to weakest: (a) solid bridges; (b) liquid bridges; (c) van der Waals; liquid wets the solid particles. For particles typically smaller than
(d) electrostatics; and (e) magnetic [4]. There are extensive reviews of 1 mm in diameter, the two components of the capillary force are the
theories and experimental studies available in the literature related to in- reduced hydrostatic pressure and the axial surface tension, and the
terparticle forces [5–13]; consequently, it is unnecessary to focus on resulting capillary force, Fc, is
these interactions in great detail, but rather discuss literature that is rel-
evant to caking. Forces such as van der Waals, electrostatics and liquid
bridges serve to bring particles into contact; however, without extrinsic 2πRγ
Fc ¼
 ð2:1Þ
factors, it is unlikely these forces will spontaneously lead to cake β
1 þ tan
formation. 2
 U. Zafar et al. / Powder Technology 313 (2017) 389–401 391

where Γ is the interface energy and R⁎ is the reduced radius, both are
defined in the below equations.

Γ ¼ γ 1 þ γ 2 −γ 12 ð2:5Þ

1 1 1
¼ þ ð2:6Þ
R R1 R2

where γ1 and γ2 are the surface energies of two particles made of different
materials, γ12 is the interaction energy between the surfaces and R1 and
R2 are the radii of the two particles, respectively. For surfaces of the
Fig. 2.1. Illustration of a liquid bridge. same material, γ12 is zero and, therefore, Γ = 2γ.

2.4.2. Plastic deformation

where R is the particle radius, γ is the interfacial surface tension
If a contact deforms plastically the material will not be able to fully
between the liquid and air, and β is the bridge half-angle. Due to
recover, which will lead to higher contact areas and, consequently,
a reduction in the pressure difference between the liquid in the
higher adhesion forces that may lead to cake formation. A contact will
bridge and the surroundings as the concave radius, r1, increases, the
plastically deform when the contact stress is greater than the yield
capillary force decreases as the bridge volume, represented by β,
stress of the material. The extent of plastic deformation does not have
increases.
to be significant for it to lead to a dramatic increase in bulk powder
If the contact area is significantly smaller than the radius of the
strength [28].
particles, Eq. (2.1) between two equal sized spheres reduces to
The model of Maugis and Pollock [29] has been successfully used to
predict the contact diameter, D, from a plastic contact between two
F c ¼ 2πRγ ð2:2Þ spheres,

4Wd
D2 ¼ ð2:7Þ
3Y
In the case where the liquid does not completely wet the spheres, Eq.
(2.2) is modified to include the contact angle, ϑ, where W is the work of adhesion, d is particle diameter and Y is yield
stress. The above model is related to normal contact deformation;
F c ¼ 2πRγ cosϑ ð2:3Þ however, it is common for contacts to deform plastically due to shear de-
formation, which may be more effective at increasing the interparticle
The above equations for liquid bridges represent a static force and contact area [30]. Cleaver and Looi [31] successfully applied Eq. (2.7) to
will vary as the particle separates. As the two particles move apart, the predict the onset of a plastic contact. Within this study AFM was used
force will be influenced by the liquid viscosity and the separation rate. to investigate the adhesion of polystyrene spheres as a function of
Additionally, as the particles separate it has been observed by Cleaver applied load. It should be noted that smaller particles are more likely to
and Tyrell [25] using atomic force microscopy (AFM) that liquid may deform plastically. This is due to the adhesive force between particles
feed into a bridge from the film coating the particles, which increases being directly proportional to particle diameter; however, contact area
the bridge volume. is proportional to d4/3 and, therefore, the contact area decreases at a
faster rate than the adhesive force.
2.4. Contact mechanics
2.4.3. Surface roughness
Contact mechanics between particles is an important area that An interesting feature of particles is that their surfaces are not per-
should not be ignored when considering bulk powder transformations. fectly smooth, but have asperities that invariably influence particle-
Whatever the bonding mechanism that initially binds particles, the key particle interactions. Contact adhesion is related to the contact area
parameter affecting the interparticle force is the size of the contact and the nature of the asperity contact, i.e. if two asperity peaks are in
area. Particles may deform either elastically or plastically, meaning the contact or if the asperity fits into a trough of the other particle. This
particle will fully recover or is permanently deformed, respectively. In may lead to a smaller or larger area as opposed to smooth surfaces. An-
addition, the role of particle roughness should be considered. In the other feature of surface roughness is that asperities influence the stress
sections below, particle contact mechanics related to bulk caking are acting at the contact and capillary condensation therein. Landi et al. [32]
summarised. For more detail regarding particle contact mechanics, a suggest that even for relatively smooth glass beads water condenses
number of reviews are available (e.g. [16,26,27]). mainly on rough surfaces of the particles, influencing the interparticle
capillary forces. This coupled with high stresses may lead to plastic
2.4.1. Elastic deformation deformation of the asperities, which will increase the overall strength
A particle that deforms elastically will fully recover once the applied of the powder as compared to its initial state. If the condensed liquid
stress is removed. An exception to this statement is when elastically engulfs surface features at high levels of relative humidity, it can change
deformed surfaces are in contact for a significant time that the contact the way the contact behaves by reducing the influence of van der Waals
permanently bonds due to molecular rearrangement, which is time and attraction. This would lead to adhesion being dominated by liquid
strain rate dependent [8]. This type of bonding is likely to yield weak bridges [19,31]. Consequently, the influence of surface roughness
cakes because elastically deformed contacts have adequate residual should not be ignored when considering bulk powder transformations.
elastic strain energy which would assist bond rupture.
The force, Poff, necessary to separate elastically deformed particle con- 2.5. Solid bridge formation
tacts and the contact area can be calculated using the well-established
JKR model [9], As categorised by Simons [4], solid bridges form very strong particle
interactions and it is these interactions that are crucial to forming strong
3 bulk powder cakes. In contrast to van der Waals, electrostatics and
P off ¼ πΓR ð2:4Þ
2 liquid bridges, solid bridges form a continuous solid connection and
392 U. Zafar et al. / Powder Technology 313 (2017) 389–401

can arise from a number of mechanisms including sintering, melting-

solidification, dissolution-crystallisation, chemical reactions and the so-
lidification of a binder.

2.5.1. Sintering
The coalescence of particles is driven by the system minimising the
surface free energy by reducing the surface area [26]. The interparticle
contact time and applied stress are regarded as important parameters
that lead to solid bridges by sintering [33]. The ratio of the contact
spot area to the original surface area of the sphere can be taken as the Fig. 2.2. A summary of different diffusion mechanisms for crystalline particle sintering
amount of sintering, S.R., [26].

 a 2
S:R: ¼ ð2:8Þ
2d where n is an index that depends on the mechanism: 1 for viscous flow,
3 for bulk diffusion and 4 for grain boundary diffusion.
where a is the contact spot diameter. If Eq. (2.8) is scaled according to
the coordination number of the assembly, an estimate of bulk powder
2.5.2. Solvent evaporation
sintering is calculated. However, such an approach would need to con-
If a liquid bridge exists between particles and the liquid contains a
sider the distribution of contact areas that would exist in the sample.
solute material, it is possible that the solute solidifies and creates a
It is possible for sintering to occur in elastic contacts and the extent of
solid bridge upon liquid evaporation. It is common that the solid bridge
caking can be estimated from the JKR theory [9]. When the resistance to
is due to a soluble component in the original powder. The solubility
deformation is elastic, the equilibrium contact size is a balance between
of constituent particles is shown to influence granular strength by
the adhesive force and the elastic restoring force. However, it is not ex-
comparing lactose assemblies exposed to ethanol and water [36]. The
pected that caking through elastic sintering will be a major mechanism
granules formed in ethanol had a lower strength than those produced
driving cake formation.
in water. Lactose is insoluble in ethanol; however, due to lactose being
As previously discussed, the contact area due to plastic deformation
soluble in water this leads to dissolution and re-crystallisation, which
is greater compared to an elastic system; consequently, sintering due to
promotes solid bridge formation. Listiohadi et al. [37–40] suggested
plastic deformation is more significant in caking. The theory of Maugis
that storage below 33% relative humidity is sufficient to prevent severe
and Pollock [29] can be used to estimate the sintered fraction, using
caking in dairy powders, whilst milling causes the formation of more
the common approximation that hardness, H = 3Y, where Y is yield
hygroscopic amorphous lactose and stronger caking tendency. The cak-
stress,
ing characteristics of powders generally depend on the type of lactose
12W polymorph [41]. The caking and stickiness of different water-soluble
S:R: ¼ ð2:9Þ powders are discussed by Palzer and Sommer [42]. In addition, crystal
Hd
expansion between particles has been identified for lactose and manni-
where W is the work of adhesion. The development of a plastic contact tol [43], and for sodium carbonate [44]. The dilation of the bridge leads
area is assumed to be instantaneous; however, in some cases the contact to a recorded negative force as the bridge forces the particles apart,
may develop over time due to viscous flow of the particles. On a bulk which could serve to compress a confined powder.
scale this is referred to as creep. The theory that describes viscous Langlet et al. [45] focused on the kinetics of dissolution followed by
contacts is given by Frenkel [34]. The increase in contact area, based evaporative-recrystallisation of sodium chloride powder as the cause
on the contact diameter, D, between particles increases with contact of caking, showing that the rate of dissolution is proportional to the dif-
time, t, but is inversely proportional to the contact viscosity, η: ference between the imposed relative humidity RH and the deliques-
cence RH and follows a model based on the kinetic theory of gases.
3tWd Tardos and Gupta [44] investigated polymer bridge strength be-
D2 ¼ ð2:10Þ
2η tween two surfaces using an aqueous solution of carbowax (PEG 350).
An amorphous structure between the surfaces was formed, which com-
As particles coalesce it leads to irreversible densification of the bulk prised of a number of strong polymeric strands that tended to rupture
powder. Kendall [26] states that the extent of shrinkage is over predicted during bridge formation. The influence of bridge volume was studied
using Eq. (2.10) due to the presence of stable agglomerates, which resist and smaller bridges exhibited higher strength per unit mass than larger
viscous flow. Current understanding of viscous contacts is that residual bridges.
stresses in the system, that would otherwise promote bond rupture, In a lot of cases, powders will contain many components that will
dissipate, which encourages the formation of cakes [28]. Viscous contacts impact on the caking behaviour of the system. Mixed component sys-
are common with amorphous powders that are above the glass transi- tems have been found to be very complex; Bika et al. [36] determined
tion temperature; due to a decrease in contact viscosity (i.e. an increase the bond strength from granule uniaxial compression tests and found
in molecular mobility). that the compatibility between components affected the cake strength.
In addition to the sintering mechanisms already highlighted, Kendall In fact, it has been suggested that an incompatibility between compo-
[26] discusses five other mechanisms that also play a role in cake forma- nents may reduce caking propensity. Farber et al. [43] modified a
tion: solid-state diffusion, grain boundary diffusion, surface diffusion, texture analyser to accommodate two glass slides, between which a
gas phase transport and liquid layer transport. These are summarised solid bridge was formed; this approach was used to directly measure
in Fig. 2.2. solid bridge strength. Bridges that were formed from pure lactose or
Herring [35] demonstrated that each diffusion mechanism responds mannitol were relatively weak because they were polycrystalline and
differently with respect to the time of the process and the particle diam- brittle, which implied a large number of defects that allowed for crack
eter. The following relationship may be used as a scaling rule depending propagation. The bridge strength greatly increased when small amounts
on the mechanism, of HPC, HPMC and PVP were added to the system. This is in apparent

n contradiction to the study by Bika et al. [36]; but the difference is
t2 d2 most likely due to different methods of producing bridges and deter-
¼ ð2:11Þ
t1 d1 mining bridge strength.
 U. Zafar et al. / Powder Technology 313 (2017) 389–401 393

The discussion thus far has been related to the formation of bridges be predicted from the ratio of the change in specific heat capacity
that remain in a state of equilibrium; however, it is likely that bridges between the glassy and rubbery states [57,58],
will evolve with time. Bagster [46] investigated the shear strength of
sugar samples that had been time consolidated for up to 16 weeks. Before Δcp2
k¼ ð3:2Þ
storage, the samples were free-flowing; however, during storage the Δcp1
shear strength increased and had a maximum after around 30 days and
then at 80 days. Using scanning electron microscopy, the bridge morphol- Typical values of k are given by Roos [50].
ogy was evaluated. It was suggested that bridge strength decreased due Above the glass transition temperature, the material viscosity can be
to the presence of cracks in the bridge as a result of micro-crystallinity. predicted by the Williams-Landel-Ferry (WLF) equation,
Subsequently, these cracks would “heal”, and the shear strength would
increase.  
μ C 1 T−T g
Surface modification and caking with time during constant temper- log ¼   ð3:3Þ
μ g C 2 þ T−T g
ature and humidity conditions has also been observed for boric acid
crystals [47,48]. In this case, the surface changes were attributed to
Ostwald ripening. Atomic force microscopy was used to identify crystal where μ is the viscosity at temperature T, μg is the viscosity at tempera-
growth by the dissolution of convex sub-micron surface features into ture Tg, and C1 and C2 are constants with common values being 17.44 K
the liquid, which leads to a supersaturated layer. It is expected that and 51.6 K, respectively [49,50]. The WLF equation describes the in-
other water soluble systems will exhibit Ostwald surface modification. crease in molecular movement above the glass transition temperature
and can be used to predict crystallisation time as a function of temper-
3. Amorphous powders ature elevation (T − Tg).
A simple mechanistic model was introduced by Downton et al. [55] to
Amorphous materials are complex and exist in a meta-stable state describe the condition of viscous flow of material between the particles.
[49,50]. They possess a glass transition temperature, Tg, that can heavily It is assumed the flow between the particles is driven by surface tension,
influence the caking propensity of a material. Above the glass transition
xγτ
temperature amorphous powders exist as liquid-like rubbers; however, μ¼ ð3:4Þ
Kd
below the glass transition temperature they behave in a rigid, glassy
manner [51,52]. Molecules within an amorphous material possess a mo- where μ is the critical viscosity required for sticking, x is a proportionality
bility, which implies that viscous flow of the material can occur and will constant with an assumed value of unity, γ is the surface tension, τ is the
be more pronounced above the glass transition; inevitably, this will in- contact time and K is the fraction of particle diameter required as a bridge
crease the extent of caking and is a common mechanism. To exacerbate for a sufficiently strong bond [49]. The above can be extended to predict
the situation, the presence of moisture in amorphous materials acts as a caking times. The mechanism of viscous flow caking of amorphous
plasticiser and reduces the glass transition temperature [1]. A material powders was also observed by Lloyd et al. [59]. The onset of viscous
may exhibit substantial caking tendencies above the glass transition flow of the particles was detected by observing an increase in bulk
and this can occur by raising either the environmental temperature or density and the driving force of caking of amorphous materials by
by increasing moisture content. Amorphous powders are common viscous flow is T − Tg. Similar observations have been reported by
within the food industry and a review of stickiness in foods is given by Fitzpatrick et al. [60], Paterson et al. [61] and Foster et al. [62].
Adhikari et al. [53] and Ruan et al. [54].
3.2. Viscous flow kinetics
3.1. Glass transition temperature
The WLF model is a powerful relationship that relates the change in
Below the glass transition temperature, in the glassy state, the viscosity or relaxation time to T − Tg for an amorphous solid above
viscosity of a solid is expected to exceed 1012 Pa [49,55]; therefore, the its glass transition temperature. Aguilera et al. [1] coupled the water
molecular movement is restricted. At the glass transition temperature, sorption isotherm with the Gordon Taylor equation (Eq. (3.1)) to give
the material undergoes a dramatic reduction in viscosity to between the relationship between water content and glass transition tempera-
106 and 108 Pa [55]; furthermore, other properties of the material ture. Aguilera et al. [1] used the WLF equation in the following form:
change, including:
 
τ C 1 T−T g
• increase in free molecular volume; log ¼   ð3:5Þ
• decrease in elastic and plastic moduli; τ g C 2 þ T−T g
• increase in heat capacity;
• increase in thermal expansion coefficient; where τ is the relaxation time at temperature T and τg is the relaxation
• increase in dielectric coefficient. time at the glass transition temperature. Caking studies on hydrolysed
fish protein were conducted by exposing thin layers of powder to
various conditions of relative humidity and temperature. The caking
Water has a glass transition temperature of −135 °C. If a secondary
index, Φ(t), was measured by the fraction of material retained on a
material has a higher glass transition temperature and is mixed with
sieve of a suitable mesh size. The following first order equation was used
water, the secondary materials glass transition temperature reduces.
The mixture glass transition temperature, Tgm, is commonly predicted

Φðt Þ t−t d
by the Gordon and Taylor equation [56]: 1− ¼ exp − ð3:6Þ
100 τ

w1 T g1 þ kw2 T g2 In Eq. (3.6), td is the delay time, which is intended to account for the
T gm ¼ ð3:1Þ
w1 þ kw2 time required for moisture diffusion onto the outer layers of the parti-
cles. Aguilera et al. [1] suggests that knowledge of the sorption isotherm,
where Tg1 and Tg2 are the glass transition temperatures of components 1 glass transition versus moisture content and a WLF plot of relaxation
and 2, respectively, k is a constant and w1 and w2 are taken as the mass times can be used as a useful prediction of the rate of caking.
fractions of the components [55]. Eq. (3.1) can be adapted for mixtures Eq. (3.7) enables the calculation of the ratio between the diameter of
consisting of more than two materials. It has been suggested that k may the sintered bridge, x, and the particle diameter, a, in terms of the
394 U. Zafar et al. / Powder Technology 313 (2017) 389–401

surface tension, γ, the applied force between the particles, Ft, the viscos-
ity, μ, and the contact time, t [34].
x2

4γ 2 Ft t
¼ þ ð3:7Þ
a 5 a 5πa2 μ

Palzer [33] coupled the WLF model with Eq. (3.7) and derived the
following equation for the necessary sintering contact time:

  2
5a2 π x
t¼ μ 10½C ðT−T g Þ=½BþðT−T g Þ ð3:8Þ
4γaπ þ 2F t a

Eq. (3.8) was shown to give a good agreement with experimental

data for the time required for caking [33]. This approach provides a use-
ful tool for predicting the stability of a powdered material, which cakes
through a mechanism of sintering by viscous flow. Hartmann and Palzer
[63] showed that the average sintering bridge diameter, calculated from
Eq. (3.8), can qualitatively be related to the unconfined yield strength
measured by a ring shear cell. Haider et al. [64] developed a theoretical
approach for the prediction of the contact zone formation between two
individual particles. However, fitting of the stress relaxation curves with
a three-parameter viscoelastic kinetic model is required. Stress relaxa-
tion curves are also shown to be an indirect measurement of caking
potential by Kingsly et al. [65].

3.3. The effect of composition

A minor change in a component within a complex mixture can lead

to significant changes in the final product [3]. It is advisable to identify
which material is problematic and substitute them with more agreeable Fig. 4.1. Schematic illustration for predicting amorphous powder caking behaviour with
components; however, this is not always an option and the ability to time [60].
understand the impact of components on a mixture is desirable.
For mixtures of amorphous materials it is possible to use the multi- Johanson and Paul [67] studied the influence of temperature cycling
component version of the Gordon and Taylor equation to predict the on a range of soluble materials including common salt and sucrose.
glass transition temperature for the mixture: When the samples were stored in a sealed container for 1.5 days at con-
n
stant temperature, the salt formed a strong cake. The transformation
∑1 wi ΔC pi T gi was attributed to moisture redistribution until equilibrium was
Tg ¼ n ð3:9Þ
∑1 wi ΔC pi T gi reached. Temperature cycling for salt showed a linear increase in cake
strength with the number of cycles. In contrast, sucrose reached its
For the above equation to be applicable, the components should be maximum cake strength after one cycle. Similarly, Cleaver et al. [48]
effectively mixed on a molecular scale; but there is no evidence this showed a steady increase in caking index with number of temperature
approach is suitable for a blend of different powders. cycles between 20 °C and 40 °C. It was observed that caking was more
Work by Foster et al. [62] investigated the effect of milk fat dairy extensive for particles b250 μm; also a steady increase in cake strength
powders containing amorphous lactose and showed that if sufficient was observed at constant temperature storage in sealed containers. This
fat was present at the particle surface, caking would occur by steady increase was attributed to preferential dissolution of sub-micron
crystallisation of the fat. Perez and Flores [66] showed that high fat con- surface features; this has been referred to as Ostwald caking.
tent in spray dried soymilk reduced flowability. Contrary, Fitzpatrick
et al. [60] demonstrated that the presence of fat reduced the tendency 4.1. Heat and mass transfer models
for caking of the amorphous material because the hydrophobic fat
inhibited formation of aqueous capillary bridges. These two emphasise There are relatively few studies investigating the dependency of
the difficulty with understanding caking mechanisms, on one hand caking with transfer of mass and heat; however, those that do incorpo-
crystallising fat increased caking and on the other hand its hydrophobic rate transfer models have focused on powders that form solid bridges
nature reduced caking. through dissolution and re-crystallisation. It is important to remember
that materials which cake through viscous flow or sintering are also in-
4. Caking dynamics fluenced by temperature and moisture content; consequently, heat and
mass transfer is equally important in these systems.
Bulk powders may undergo transformations with time and this is a Tanaker [24] investigated the formation of crystal bridges by the dis-
dynamic process complicated by changing environmental and mechan- solution of the solid and the subsequent evaporation of water from the
ical conditions. Majority of studies available in the literature are based capillary bridge. The following relationship was derived,
on constant environmental conditions. It is common for heat and mass

0  1
transfer effects to be neglected; however, caking is heavily influenced b 8ε a 1 4
¼ 0:82 Cs X 1−X ð4:1Þ
by temperature and water content profiles within the bulk material, R 3ð1−εc Þ 100
or between the surroundings and the bulk. If these profiles are under-
stood, they could be linked to cake formation and strength. This has where b is the radius of the narrowest portion of the recrystallised solid
been conceptualised by Fitzpatrick et al. [60] with respect to amorphous bridge, R is the particle radius, εc is the porosity of the re-crystallised
materials and has been recreated in Fig. 4.1. bridge and Cs is the saturation concentration of the solute in solution.
 U. Zafar et al. / Powder Technology 313 (2017) 389–401 395

A relationship between b/R and tensile strength of an agglomerate was water adsorption isotherm data. Comparison of the predicted bound
developed, which gave the strength of a fully developed cake; however, water with that measured in a 1-dimensional caking box was favourable.
this approach does not consider time dependency. Tanaker [24] investi- The fresh sugar samples had been exposed at one end to a temperature of
gated the influence of compaction load, temperature, moisture content 10 °C for 12 h, after which the temperature was changed to 30 °C and
and time on the caking behaviour of sodium chloride; the above model moisture content at specific penetration distances were taken after a
showed reasonably good agreement to the experimental data; however, further 12 h. This work demonstrated a reasonable prediction of temper-
Eq. (4.1) requires further validation with more materials. ature and moisture content profiles by use of a relatively simplistic
The diffusion of vapour into a powder at constant temperature was approach.
investigated by Tardos and Gupta [44] and Tardos et al. [68]. The dif- Christakis et al. [17] followed the work of Leaper et al. [70] and
fusion equation for one dimensional ingress was used to calculate considered the case of humidity cycling in the form of a square wave
moisture distribution and total water as a function of time. It was to impose wetting and drying cycles within the powder. Heat and
shown that water uptake was very sensitive to the isotherm form. mass transfer equations were solved using a 3-dimensional, unstruc-
For several systems of detergent and inorganic materials, it was tured finite volume method. It was considered that during a wetting
shown that the solid phase moisture content reached equilibrium rap- cycle material would dissolve and re-crystallise into solid bridges during
idly. Over narrow ranges of RH change, the water adsorption isotherm drying. The correlation of Tanaker [24] was used to estimate the radius
can be considered linear, which means Henry's law is applicable; of crystal bridges and the well-established model by Rumpf [22] was
consequently, an analytical solution to the diffusion equation can be used to calculate the tensile strength of the cake. The model by
obtained giving an expression for the dimensionless vapour phase Christakis et al. [17] was compared with data collected by Leaper et al.
concentration, φ, as [70] and a good agreement between the experimental and predicted
tensile strength was shown. Using the model, the effect of maximum
" # relative humidity, the intervals of oscillations and the effect of bed
c−ci ζ
φ¼ ¼ 1−erf pffiffiffiffiffiffiffiffiffi ð4:2Þ voidage on the tensile strength were investigated. It was demonstrated
co −ci Deq t
that both the relative humidity and voidage had a significant effect on
the predicted tensile strength.
where c represents the water concentration in the vapour phase, with Specht [71] used a finite element method based within the COMSOL
the subscript i corresponding to the initial concentration at time t = Multiphysics software to investigate caking by moisture migration whilst
0, and the subscript o the maximum or reference value of the concen- modelling temperature and moisture content profiles. The contribution
tration. ζ is the depth below the powder surface and Deq is the of natural convection to the moisture transport by comparing the pre-
equivalent diffusion coefficient that defines physical characteristics dicted temperature profiles with and without the convection term was
of the system. This equation was used to determine the depth of pen- evaluated. Natural convection in a cell was shown to be the dominant
etration of moisture into the powder. Percolation of conditioned air mode of heat transfer through evaluating the magnitude of the Peclet
through the sample is a much more effective method for rapid sample number. The diffusion in to the cell was predicted using the temperature
equilibration, as shown by Tardos et al. [68], whereby equilibrium was profile; hence, the moisture content as a function of space and time was
reached around an order of magnitude more rapidly than if the air calculated. Sodium carbonate formed solid bridges between particles by
was stagnant. During diffusion, the system porosity may change due dissolution and re-crystallisation in its monohydrate form. In addition,
to capillary bridges and particles may undergo swelling, amorphous Specht [71] suggested the contact force distribution within a powder
collapse or phase transition due to water of crystallisation. bed will heavily influence the cake strength. The influence of force chains
The heat and mass transfer within sugar storage silos has been ex- was evaluated using the discrete element method (DEM). The concept of
perimentally and theoretically studied by Rastikian and Capart [69]. “granularity” was used, which is the spacing between the major force
With knowledge of the water sorption isotherm and thermal conductiv- chains, to evaluate the strength of the powder. An inverse dependence
ity, a modelling approach was developed that brought together a heat between granularity and consolidation stress was observed through
and mass balance equation. Axial distributions of temperature, sucrose the simulation work.
water content and air humidity were determined for a simulated Billings et al. [72] have studied the caking of sucrose due to capil-
“maturation” process. The mass transfer coefficient was calculated by lary condensation in humid environment. Billings and Paterson [73]
comparing experimental and calculated values of sugar moisture and used a mass and heat transfer model to predict the onset of caking
air humidity. The coefficient was shown to vary during the maturation of sucrose. The approach investigates moisture migration in a sample
process, increasing exponentially with sucrose moisture content. due to temperature differences and suggests that migration can
Using this modelling approach, regions within the silo were identified significantly influence caking propensity. Full details of the model
as a risk for caking due to the relative humidity exceeding 80%. The are given by Bronlund and Paterson [74]. This model is useful for
high humidity in these regions was due to cold wall temperatures; predicting possible caking conditions if there is knowledge of
consequently, Rastikian and Capart [69] made suggestions to prevent the water activity and the hot and cold temperature conditions the
caking of sucrose, i.e. good thermal insulation of the wall, a sufficient powder experiences.
air flow rate and a relative humidity of the air not exceeding 75%. It is
important to note that this work is based on forced convection through 5. Caking reduction
the system and may not be applicable to cases when diffusive transfer or
natural convection is present. Through understanding the powder being handled and its interaction
Leaper et al. [70] considered caking of sugar in big bag containers. with other components, sensible precautions can be taken to mitigate
The heat transfer was only in the radial direction and was driven by a caking; however, knowledge of the dominating caking mechanisms
temperature difference between the surroundings and the walls. The is not always known and may be difficult to ascertain. A number of
modelling technique evaluated temperature changes experienced by common sense approaches are available that may reduce the caking
an axial core of material using a finite difference method. A reasonable propensity of a material:
agreement with experimental data obtained from a big bag study was
found. The temperature profile was then used as a tool to predict the 1. decreasing the fines content of the powder;
solids moisture content and relative humidity of the interstitial air. 2. minimising moisture content;
The relationship between solids moisture content and the relative 3. identifying the major caking component and identify if an alternative
humidity was obtained by fitting empirical equations to measured is available;
396 U. Zafar et al. / Powder Technology 313 (2017) 389–401

4. reducing temperature and humidity cycling where appropriate; impractical, especially for high-value or hazardous materials.
5. reducing consolidation load where appropriate. Cleaver [2] states the attributes of an ideal caking test are:

To be effective at minimising caking it is beneficial to under- • provides predictive indication of caking extent and intensity;
stand the prevailing caking mechanisms and the role of material • maximises useful information by appropriate instrumentation;
properties and process conditions. In addition to the above ap- • minimises random error through careful parameter control;
proaches, caking can be reduced by using anti-caking additives • uses a minimum quantity of sample.
[75].
An important attribute of a caking test is the ability to predict whether
5.1. Caking reduction additives caking will occur in the future. The challenge of accelerating caking is that
it may be necessary to increase moisture content and/or temperature, or
Caking propensity can be reduced through use of suitable additives use a compressive force that is excessively large. Changing the conditions
and operate by a variety of mechanisms. Adhikari et al. [53] provide a the material is exposed to can have a profound effect on the phase chem-
nice summary of common flow conditioners used in food systems as istry of the material; consequently, accelerating caking may lead to mis-
well as various methods used to reduce stickiness in spray-drying leading information. The aim of a rapid test should allow for prediction
operations. Aguilera et al. [1] give a good overview of caking additive of caking propensity whilst remaining within the parametric envelope
mechanisms, which include: for normal operation. The extrapolation from accelerated caking test
data to predict caking requires detailed knowledge of the relevant mate-
1. competing with a host powder for available moisture. These materials rial properties and their response to changes in moisture content and
are usually porous with a high capacity for moisture adsorption; temperature whilst under realistic levels of compressive stress.
2. acting as a surface barrier between the host particles, preventing the
formation of liquid bridges, decreasing inter-particle friction, dissipat- 6.1. Mechanical test methods
ing electrostatic forces, or inhibiting crystal growth of solid bridges;
3. increasing the glass transition temperature of the amorphous phase, A variety of mechanical test methods are available for investigating
usually by adding a high molecular weight material; the flow behaviour of bulk powders and these can be used for evaluating
4. forming a moisture protective barrier on the surface of hygroscopic caking behaviour. In this section a brief overview of the techniques
powders by using, for example, lipids. employed for caking is given.

The effectiveness of a variety of inorganic inhibitors on the caking 6.1.1. Shear cell testing
behaviour of different industrial materials, including salt, sugar, milk Shear cells have been used for many years to determine bulk powder
powder and a fertiliser, has been studied [76]. The inhibitors included flow properties [84]. Three main classes of shear cell are available,
tricalcium phosphate, magnesium carbonate, calcium silicate, calcium the Jenike shear cell, the annular shear cell and the Peschl shear cell;
sulphate, starch and kaolin. Calcium stearate and silicon dioxide have the latter two being rotational devices with infinite shear strain [85].
also proved to be effective in reducing moisture sorption [77,78] Shear cells have been used by a number of researchers to study the
in single deliquescent food ingredients (sodium chloride, sucrose, caking and flow behaviour of powders [46,86–88]. In order to control
fructose, and citric acid) and binary systems (sodium chloride blended the environment (temperature and relative humidity), the shear cell is
with sucrose, fructose, or citric acid). The effect of inhibitor particle usually placed in an environmental chamber [60,86,87]. The ability to
size was studied and it was shown that finer particles were more control temperature and relative humidity whilst a sample is under a
effective at the same mass concentration, which is assumed to be compressive stress makes the shear cell a good candidate for predictive
due to a greater surface coverage. In this regard, it was found that caking tests.
pulverization of juice powder with powdered cane sugar as anticaking
agent is effective for reducing caking and hygroscopicity of the 6.1.2. Uniaxial compression testing
product [79]. In this instance, the anticaking mechanism is physical Uniaxial compression is used to form a cylindrical column of materi-
separation. al that has been compressed axially. After consolidation the confining
Further studies have concluded that approaches may be taken that walls are removed and the column is in an unconfined state around its
restricts the growth of crystal bridges between particles; consequently circumference; subsequently, a load is reapplied to the sample and the
reducing the caking tendency. Chen and Chou [80] investigated the ef- measured stress at failure is taken as the unconfined yield strength.
fect of surfactants on the caking of ammonium perchlorate and showed A uniaxial tester has been developed for caking studies and the test
that lauryl amine and sodium dodecyl sulphonate were both effective. procedure by Weigl et al. [89]. Prior to testing, the sample is conditioned
In this case the surfactants did not affect the amount of water adsorbed at a constant temperature, humidity and compression for a specified
by the material; but rather inhibited the growth of crystal bridges. Sim- time. The cylindrical confining walls are porous to allow moisture mi-
ilar evidence was observed by Hansen et al. [81] for potash treated with gration, but whether thermal and moisture equilibrium is achieved is
an amine, and by Komunjer and Affolter [82] for ammonium nitrate unknown. This approach is useful for comparing caking tendency of
treated with fuchsine acid. similar materials; however, with this conditioning approach it may
require abnormally high environmental or mechanical conditions to ac-
6. Caking test methods celerate caking in a reasonable timescale. An interesting conclusion
from the work of Weigl et al. [89] is that the uniaxial caking test proce-
A number of caking test methods are available and range from dure needs to be very closely specified and adhered to if consistent and
simplistic approaches, such as dropping a 50 kg bag of fertiliser meaningful results are to be achieved. More recently, a similar approach
from waist height and quantifying the extent of caking by the has been followed by Calvert et al. [90], having accelerated caking
amount of free flowing material [83], to more complex methods facility by percolating humid air through the packed powder bed (see
such as shear cell testing. Most approaches available tend to inform below).
the operator whether a product has caked or not, but provide no The technique of uniaxial cake strength testing is based on materials
predictive capability. The lack of instrumentation and control failing in a plastic, ductile manner; however, caked material may exhibit
used undermines data reliability and minimises the information more brittle failure and the underlying assumptions and associated
obtainable from the test. Finally the large sample size may be stress analysis for plastic deformation may not be valid. An additional
 U. Zafar et al. / Powder Technology 313 (2017) 389–401 397

problem associated with the uniaxial tester is the aspect ratio of the 6.1.3. Tensile testing
bed. The height to diameter ratio should be N 1 and likely close to 2 Pietsch et al. [20] used a tensile tester; however, it is experimentally
in order that the gradient of the slip plane passes through the side very challenging due to difficulties in applying the tensile load to the
of the cake; although, large bed heights may lead to a non-uniform specimen and controlling the failure plane location. Tensile testing
stress field. The following equation is used to calculate the slip was also used by Nikolakakis and Pilpel [94] to investigate the effect of
plane angle, particle size and shape, and by Pierrat and Caram [18] to study the effect
of water content. It has not become a widely used approach to study
caking, due to its difficulties, and its advantage is overshadowed by
φ
α ¼ 45 ° þ ð6:1Þ the ease of use of other techniques such as the shear cell.
2

6.1.4. The ICI caking test

where φ is the angle of internal friction of the powder [88]. Care Thompson [95] developed the ICI caking test to eradicate the short-
should also be taken when removing the caked powder from the comings of the high aspect ratio uniaxial testers, as mentioned in the
confining cylinder; if the cake is weak, removal may damage the previous section. A shallow, sealed mould, lined with a polythene
sample. sheet, to produce the cake by application of pneumatic pressure was de-
Wahl et al. [91] employed a modified design of uniaxial tester with veloped. The tester was placed under isothermal conditions and a dis-
the walls of the measurement cell made of porous, sintered material placement transducer was used to monitor the shrinkage of the
to allow fast diffusion of moisture through the cell walls towards the specimen during caking; this is an important phenomenon of caking,
sample. To minimise wall friction, the sample is positioned on top of a as investigated by Lloyd et al. [59] and Walker et al. [96]. After compres-
stand and enclosed by walls which “hang” from the sample. sion the top cover of the tester and a circular plug underneath the sam-
Thakur et al. [92] conducted an experimental and numerical study of ple are removed. The load on top of the sample is reapplied until a plug
the packing, compression, and caking behaviour of spray dried detergent of material is displaced. The pressure at which this occurs is related to
(SDD) powders using an extended uniaxial tester (Edinburgh Powder the degree of powder caking. It was reported that the repeatability
Tester-EPT). It was found that higher moisture content leads to lower with this approach was typically within 5%. The tester has been used
bulk porosity but higher compressibility and cake strength. A discrete el- to study the effect of storage temperature, time, load and moisture con-
ement method (DEM) approach, based on a simplified contact model, tent on fertiliser samples, which led to useful empirical relationships. A
was also employed and proved capable of capturing the compression be- similar test was developed by Fitzpatrick et al. [97,98], where the cake
haviour reasonably. However, the importance of considering a time- strength was determined from the force required to displace a plug of
dependent inter-particle cohesion force in the contact model has been caked material. The measured cake strength correlated well with the
stressed elsewhere [93]. flow function values obtained by the ring shear tester, and a relationship
Another new method developed by Calvert et al. [90] for assessing between the two techniques based on a scale factor has been proposed
powder caking propensity based on uniaxial compression is the Envi- [99].
ronmental Caking Rig (ECR), where an accelerated caking process is
used. A schematic illustration of the ECR is given in Fig. 6.1. This test 6.1.5. Creep testing
method uses conditioning air, which percolates through the powder It is useful to monitor the change in volume of a sample as a function
sample to rapidly equilibrate the bulk sample with the desired environ- of time as a means of understanding the effect of storage time and envi-
mental condition. The powder is compacted using dead weights and the ronmental conditions on caking. The inline determination of cake thick-
caking tester is placed in an environmental controlled chamber, where ness can, for example, be determined by a pressure-displacement
the temperature, relative humidity at the inlet and outlet of the powder measurement [100]. Creep testing was adopted by Walker et al. [96]
bed and the rate of compaction are recoded. The caking propensity of for granular fertilisers using the ICI caking tester. Investigating the effect
highly hygroscopic and deliquescent powders has been investigated, of load and time allowed for comparisons between creep rates, which
where the effect of different environmental conditions on the consolida- were used to predict the future condition of the material. Walker et al.
tion and development of cake strength at realistic storage conditions [96] concluded that the strength of a powder was directly proportional
have been delineated. A linear relationship is shown to prevail between to the reduction in voidage due to plastic creep and they recommended
the cake strength and the extent of bulk deformation. determining empirical constants for each material.

Fig. 6.1. A schematic illustration of ECR setup [90].

398 U. Zafar et al. / Powder Technology 313 (2017) 389–401

If the various creep mechanisms are understood, creep testing is a

promising predictive tool for evaluating caking propensity. The assess-
ment of creep is relatively quick and could be used to predict by extrap-
olation the future behaviour of powders.

6.1.6. Penetration testing

Knight and Johnson [101] developed a penetration test method that
considered the unconfined yield strength, fc, of a powder to be related to
the measured force, F, and the penetration depth, d, by the following re-
lationship:

F
f c ¼ afc 2
ð6:2Þ
d
Fig. 6.3. Geometry for measurement of indentation hardness of weak powder compacts
where afc is a constant that is related to the dynamic coefficient of [103].
friction between the indenter and the powder and the dynamic angle of
internal friction for the powder. The test method is illustrated in Fig. 6.2.
For a range of powders a good comparison with unconfined yield surface caking, where the internal bulk powder would not yet have
strength measurements from shear cell tests were observed when afc caked. It has recently been used in the study of surface caking of phar-
was equal to 1.4. This approach shows promise for investigating the maceutical excipients by Chen et al. [107], who have shown that the
caking propensity of powders. The method is intended for materials onset of caking is readily detected by changes in the surface hardness.
that fail plastically; if brittle failure is observed, the results would have
to be interpreted using fracture toughness. 6.1.7. Powder rheometer
Penetration testing has been used specifically for investigating cak- Powder rheometry has been used in more recent years for assessing
ing propensity by Ozkan et al. [102] and Ozkan et al. [104]. The samples powder behaviour. One of the well-known testers is the FT4 Powder
were subjected to controlled temperature, consolidation and time and Rheometer by Freeman Technology, Tewkesbury, UK. This method de-
when the load is removed the penetration force was measured using termines bulk powder behaviour under dynamic conditions and has
an Instron mechanical tester. This approach is empirical and was used been used by many researchers mainly to measure powder flowability
for comparison between different conditions and powders. An im- (e.g. [108–110]). Chávez Montes et al. [111] used FT4 Powder Rheome-
proved methodology for measuring penetration behaviour of powders ter for investigating caking of cocoa powders, for which the energy
has been developed by Hassanpour and Ghadiri [103], Pasha et al. required to move the rotating blade down into the caked powder was
[105], and Zafar et al. [106] to characterise the flowability of cohesive measured and compared with that for breaking of the cake using a
powders and is depicted in Fig. 6.3. In this method, the resistance to uniaxial tester. Both test methods were able to differentiate between
bulk plastic deformation (hardness), representing the material flow samples; however, with the FT4 Rheometer it is possible to assess a
stress, is obtained from the ratio of the maximum indentation load to broader range of environmental conditions. Furthermore, FT4 Rheome-
the projected area of the impression, which is calculated from the in- ter can quantify caking as a function of height whilst most of the other
denter diameter and the penetration depth. One major advantage of techniques provide an average value for the whole sample for caking
the ball indentation technique compared to conventional methods for assessment [112].
assessing powder behaviour is that a sample size of only a few mm3 of
material is required. Another significant advantage of this method is 6.2. Alternative test methods
its sensitivity and ability to detect the onset of caking very quickly.
The caking kinetics can be determined as a function of the exposed tem- A number of alternative methods are available for evaluating the
perature, humidity and applied stress. The technique measures free caking behaviour of powders. Sensory analysis or sieving is employed

Fig. 6.2. (a) Cross section of failure surface for a conical indenter penetrating an unconfined powder; (b) sample preparation method [101].
 U. Zafar et al. / Powder Technology 313 (2017) 389–401 399

in the food industry [113]. Sieves, in particular, can be used to classify and mechanical conditions on a powder; however, in most instances
the degree of caking. Ordinarily a free flowing material will pass the samples are subjected to constant environmental conditions. In reality
through a sieve aperture that is larger than the constituent particles. If powders within a supply chain experience environmental changes that
the material has caked, a certain percentage of the material will not lead to thermal and moisture gradients within the bulk. This is an area
pass. The caking index test is given as the mass fraction of material within the literature that should be further investigated to understand
that is retained on the sieve. A number of researchers have successfully the evolution of bridging between particles.
used the caking index such as Irani et al. [76] to quantify the perfor- There are a number of test methods available that provide empirical
mance of anti-caking additives, by Aguilera et al. [1] to quantify the ef- understanding of caking, but limited predictive ability. There is a need to
fect of storage time when investigating caking kinetics, and by Cleaver develop a new experimental device that provides reproducible results
et al. [48] in an attempt to develop an accelerated caking test. The caking and enables future predictions.
index test should be treated with caution, it is rapid and simple, but it is
not possible to make meaningful comparisons between caking indices
measured for different materials. Acknowledgements
The blow tester was developed to measure the cohesiveness and
caking of diary powders [61,114]. The powder is first conditioned by The material in this review is partially based on a literature review by
air at a controlled humidity and temperature. Once the powder is condi- J.A.S. Cleaver, supported by the International Fine Particle Research
tioned, an impinging jet of air is introduced to the powder surface. The Institute. It was subsequently developed further by G. Calvert as part of
velocity of the air is gradually increased until a channel is cut through his visiting fellowship at Procter and Gamble, Longbenton, UK, supported
the powder; the flow rate that this occurs is related to the cohesiveness by the Technology Strategy Board through the Knowledge Transfer
or cake strength of the material. Partnership with the University of Leeds. The review has been updated
The accepted mechanism for caking of materials above their glass by U. Zafar, supported by a Knowledge Transfer Secondment from the Im-
transition temperature is by viscous flow of the particles in contact. A pact Accelerated Award to the University of Leeds by the Engineering and
sticking point tester was developed by Lazar et al. [115]. The viscosity Physical Sciences Research Council (Grant Ref. EP/K503836/1), working at
required for particle sticking has been explored by Downton et al. [55] Procter & Gamble, and by V. Vivacqua, through a research fellowship sup-
by conducting sticking point experiments for fructose and sucrose pow- ported by Advanced Manufacturing Supply Chain Initiative through the
ders. Sticking point tests involve continuous stirring of a powder in a research grant entitled Advanced Digital Design of Pharmaceutical
sealed vessel whilst slowly increasing the temperature. The sticky Therapeutics.
point is observed by a sudden increase in the torque required for stir-
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