PTEC-12516; No of Pages 17

Powder Technology xxx (2017) xxx–xxx

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Powder Technology

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

Caking of crystals: Characterization, mechanisms and prevention

Mingyang Chen a, Songgu Wu a, Shijie Xu a, Bo Yu a, Mohannad Shilbayeh d, Ya Liu a, Xiaowen Zhu e,
Jingkang Wang a,b,c, Junbo Gong a,b,c,⁎
a
School of Chemical Engineering and Technology, Tianjin University, Tianjin, China
b
Key Laboratory Modern Drug Delivery and High Efficiency in Tianjin University, Tianjin, China
c
The Co-Innovation Center of Chemistry and Chemical Engineering of Tianjin, Tianjin, China
d
Faculty of Engineering, Western University, London, ON N6G 1G8, Canada
e
Tianjin University, Tianjin, China

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

Article history: Caking of crystals leads to a great deal of negative impact on the quality of products leading to extra cost to restore
Received 21 December 2016 the products to its original state before caking. It is therefore an undesired phenomenon that should be investi-
Received in revised form 15 April 2017 gated and inhibited. This review considers particle issues (particle science and technology) in a crystallization
Accepted 21 April 2017
view (crystallization science and engineering). 1. Characterization. Caking indices and the relevant characteriza-
Available online xxxx
tion methods are classified. Their advantages and disadvantages are summarized. Particularly, potential novel
Keywords:
characterization methods, e.g. image analysis technique and its application in analysis of caking ratio, are
Caking discussed. 2. Mechanisms. Caking process is organized into three stages: moisture sorption, then liquid bridge,
Crystal and finally crystal bridge. The mechanisms are reconsidered with recent studies (e.g. mass transfer, adhesion ef-
Particle fect of liquid bridge, kinetic of crystal caking) and crystallization science (e.g. nucleation and growth theory, poly-
Crystallization morphism, and phase transition). 3. Prevention. Based on particle and crystal engineering, prevention of crystals
Characterization caking is discussed through controlling ambient conditions (relative humidity, temperature, liquids screening,
Mechanisms and pressure) and improving anticaking property of crystals (particles size, particles shape, impurity, and anti-
Prevention
caking agent). A potential method of simulating crystal caking behavior based on discrete element method
(DEM) and caking mechanisms is presented. With the aid of simulation, the enhanced design of particle and crys-
tal engineering would be available, which could be a key to control these factors systematically.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction and elasticity [4–9], which is significantly different in comparison with

In the crystallization field, most crystalline products are preferred to
be produced as single particles with good flowability and stability. These
crystals are easy to process prior to commercialization. Caking of crys-
tals often occurs after a distinct drying step, e.g. transport, storage and
some drying processes. It can be very problematic due to unusable or
additional equipment being required for de-caking [1]. Quite often 2–
10% of the product is lost during this process [2,3]. To make matters
even worse, the quality of products after the process of de-caking some-
times differs significantly from the original ones, which may cause a se-
ries of problems in the following processes and commercialization.
Hence, in most cases, caking of crystals is undesired and should be
prevented. However, most studies focus on the amorphous powders
in the food engineering field instead of crystals. Caking of amorphous
powders is generally caused by glass transition, a variation of viscosity
⁎ Corresponding author at: School of Chemical Engineering and Technology, Tianjin
University, Tianjin, China.
E-mail address: Junbo_gong@tju.edu.cn (J. Gong).
the caking mechanisms of crystals [1,5,10–13]. The relevant mecha-
nisms of amorphous powders therefore cannot be adapted to crystals.
In addition, polymorphic transitions, phase transitions, chemical reac-
tions, and the debate of nucleation and growth of crystallization compli-
cate the study of crystals caking. Hence, there remains a strong need to
consider particle science and technology with crystallization science
and engineering to overcome these issues (Fig. 1). As a foundation, par-
ticle science and technology provides basic means of characterization,
particle-particle interactions and particle system engineering. Further-
more, the crystallization science and engineering contains nucleation
and growth theory, polymorphism, phase transition, crystal engineer-
ing, etc., which may give crystals caking a profound view on mecha-
nisms and the prevention methods.
This review focuses on the caking of crystals, especially during trans-
port and storage. In the following sections, characterization, mecha-
nisms, and prevention of crystals caking are summarized and
discussed with the aid of recent studies. The motivation of novel caking
indices and devices in particle technology are discussed in the section of
characterization. The mechanisms of crystals caking are reviewed from

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0032-5910/© 2017 Elsevier B.V. All rights reserved.

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2 M. Chen et al. / Powder Technology xxx (2017) xxx–xxx
Fig. 1. Solution of crystal caking combined particle science and technology with crystallization science and engineering.
the viewpoint of crystallization science. The polymorphism, phase tran-
sitions, chemistry reactions, nucleation and growth theory are consid-
ered to discuss the possible research points. Based on particle and
crystal engineering, and the idea of “quality by design”, the factors for
caking prevention are summarized systematically.
2. Characterization
Several indices (Fig. 2) are proposed in characterizing crystal caking.
Caking strength and compressibility are classified as mechanical indices.
Caking strength is used to characterize the force breaking the cake [13,
14]. Compressibility shows the shrinkage of the specimen during cak-
ing, where the pressure is related to the extent of powder caking [15].
Aspect ratio, circularity, convexity, sphericity and bluntness are mor-
phological indices. They characterize the shape and structure of a parti-
cle. Aspect ratio (AR) is the ratio between the major axis and minor axis
of the ellipse encircling the object [16]. Circularity is the ratio of the
object's projected area to the square of the perimeter of the object
[17]. Convexity is the perimeter of the convex hull of the object divided
by its perimeter [16,18]. It presents how spiky a particle is. Sphericity is
the ratio of the surface area of a sphere having the same volume as the
particle to the actual surface area of the particle [18,19]. Bluntness de-
scribes how sharp or round the fine convex structures on the particle
surface are [20]. In general, agglomerates present irregular shapes.
These morphological indices of agglomerates differ a lot from the pri-
mary individual particles, so sorting and filtering on these indices will
quickly identify the level of caking.
Statistical indices include caking ratio, mechanical indices distribu-
tions, and morphological indices distributions. Caking ratio is to calcu-
late the percentage of caked particles, which characterizes the degree
of caking [21–23]. Distributions of mechanical and morphological indi-
ces are statistical data from a mass of individual particles, which show
comprehensive views on the whole sample.
Caking test methods have been developed based on these caking in-
dices. Most available approaches tend to inform the operator whether a
product has caked or not. A highly desirable feature of a caking test is
the ability to diagnose whether caking will occur in the future. The com-
mon and potential caking test methods (Fig. 2) for these caking indices
are introduced below. Mechanical indices are common in literature. The
conventional methods of these indices are summarized in Section 2.1.
Morphological indices are less common than mechanical ones but
could be utilized directly for caking due to the improvement of
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dx.doi.org/10.1016/j.powtec.2017.04.052
techniques in recent years. The novel techniques for these indices are
discussed in Section 2.2. Most of the statistical indices are not common
yet but can be valuable. The potential techniques of these indices and
some potential ideas to obtain more precise and repeatable data are
discussed for further applications in Section 2.3.
2.1. Mechanical indices
Many researchers focused on the mechanical indices in the past
years due to good development of testers. These testers are easy to es-
tablish. Some are even commercial, e.g. shear testers, which motivate
the investigation about mechanical indices, especially caking strength.
Some groups have also developed devices that control humidity, tem-
perature, pressure, and location of particles to fit more specific situa-
tions. These testers are summarized in Table 1.
2.2. Morphological indices
Particle morphology is one of the most important aspects in particle
science and technology. Caked particles have more complex morpho-
logical characteristics, which is valuable to investigate. So far, utilizing
atomic force microscopy (AFM) technology has become the tendency
to investigate particle surface details in nanoscale. With the aid of
AFM, Bode et al. [43,44] observed step pinning of NaCl crystal caused
by the anticaking agents, i.e. ferrocyanide and iron (III) meso-tartaric
acid. The AFM showed that the step heights are only one atomic layer
(2.8 Å). Then, a blocking mechanism for crystal growth of sodium
chloride crystals by ferrocyanide was suggested. Stellacci et al. [45,46]
developed the high-resolution amplitude-modulation atomic force mi-
croscopy (AM-AFM) to improve the precision of AFM significantly. The
images could even show a single molecule or atom. In their subsequent
work, this technology demonstrated that the stearic acid molecules
tend to act as “pinning points” on the calcite's surface and slow down
the crystal's restructuring kinetics [47]. These experiments utilizing
AFM have offered some possible ideas for anticaking agent. Besides,
AFM also provides both morphological microstructure and interactions.
This advantage could provide insights into caking mechanisms. Howev-
er, using AFM is costly, time consuming [48], and limited to the study of
massive particles system. For this problem, optical and scanning elec-
tron microscopes could be adopted. Previously, image analysis based
on optical and scanning electron microscopes primarily depends on
manual measurement of numerous photographs [49,50]. However,
 M. Chen et al. / Powder Technology xxx (2017) xxx–xxx 3

Fig. 2. Caking indices and the relevant test methods.

now, after technical improvement of the optical and scanning electron
microscopes and the image analysis method, more morphological indi-
ces can be obtained. This technology provides number-based statistics.
It means that the data are generated on individual particles as well as
on the sample as a whole (Fig. 3). This may motivate further research
on surfaces and crystal bridge of caked particles. Furthermore, the sta-
tistical indices may be analyzed through properly screening morpholog-
ical indices. In the following section, the statistical index, i.e. caking
ratio, shows this screening operation as an example.
2.3. Statistical indices
A mass of particles at any given time have to be characterized in in-
dustrial production, which means the tests for a single particle or parti-
cles system (e.g. crystal bridge bonding between particles) are not
effective enough. In this situation, it is of great importance to obtain
some statistical data for understanding the products comprehensively.
Theoretically, the distributions of mechanical and morphological indices
could also be regarded as statistical ones as well. It should be noted that
there still remains a need to develop some effective measurement or
analysis methods for these statistical distributions. e.g. to convert
individual data into a statistical one, it is time-consuming and always
impossible to measure caking strength of each crystal bridge for a
mass of particles that have agglomerated into lumps. In fact, the
main reason that mechanical indices distributions are not common
yet is due to these limitations. Although, Wahl et al. [3] presented a
simulation method to predict the crystal bridge strength distribu-
tion, it still needs a lot of work to completely develop it. In regard
to the morphological indices distributions, thanks to the devices
and software, e.g. Morphologi G3 and Particlematric (Phenom,
Netherlands), this kind of statistical indices could be estimated auto-
matically in minutes. Since it is easy to understand, instead of only
presenting morphological indices distributions by these techniques,
an indirect test method for evaluating another important statistical
index, caking ratio, based on the analysis of these distributions is
mainly introduced in the following.
Caking ratio is the proportion of caked particles (mass or number) to
the whole collection of particles [21–23], which is very necessary to
fully understand the extent of caking comprehensively. Thus, it is of im-
portance for both scientific research and industrial manufacture. Two
examples are presented below to show the estimate of caking ratio
based on morphological indices distributions.

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Table 1
Summary of common mechanical indices testers.

Caking indices Testers Summary

Caking strength Shear testers Carson et al. [24] made a general classification of shear testing techniques. Direct shear testers include translational and rotational, while indirect
ones include biaxial and triaxial. Because of easy operation and low investment, the translational shear testers, e.g. shear cell, have become an
industrial standard and been proven to be the most multifunctional shear tester for applications. The shear cell was originally developed by Jenike
[25]. It consists of two concentric rings [25,26], and is usually placed in an environmental chamber to control temperature and relative humidity
[27]. Now it is commonly used to rank granular materials according to their flowability [28].Other shear testers were reported in literatures
[6,24,28,29]. These testers offer unlimited strain, steady-state flow conditions, etc., which are capable of being automated and utilized to study the
shear flow of cohesive, caked particles.
Uniaxial tester A typical uniaxial tester provides compressive stress that is maintained for a specified time. The main advantage is that it provides a
fundamental measure of caking strength at a defined consolidation load [30,31]. The cell walls are smooth enough to reduce the friction
with samples for precision. However, such a device isolates the sample from ambient humidity. Consequently, making the humidity
difficult to be controlled. To overcome the problem of humidity, consumer oriented solids transport technology (COSTT) uniaxial tester
was developed [3]. It differs from typical uniaxial tester in two aspects: due to porous and sintered material, the tester allows fast diffusion
of moisture through the cell walls towards the sample, which indicates that the walls are fairly rough. In addition, the tester has been
equipped with a raised bottom to compensate for the Janssen effect [3]. After that, Calvert et al. [32] developed a uniaxial caking test
method that is capable of simultaneously conditioning and consolidating particle samples. However, uniaxial testers are still not able to
confirm whether the sample has reached environmental equilibrium. Recently, an extended uniaxial tester, the edinburgh powder tester
(EPT) was developed. The main differences between the EPT and previous uniaxial testers lies in the attention to mechanical details, the
level of care directed to the consolidation as well as failure load application, and the strategic intent. In the EPT, boundary effect is
minimized by allowing the powder sample to compress from both the top and bottom [33].
Micromanipula- In 2012, Haider et al. [34] developed MPT to study the influence of environmental conditions on the caking mechanism. It is designed for
tion measuring the compression forces between particles larger than 500 μm in diameter in contact under load and the adhesion forces upon
particle their separation. This device makes it possible to measure the effect of process conditions in pressure agglomeration on particle
tester (MPT) interactions and resulting adhesion: external pressure, compression velocity and physical state of the material. Although the sample used
is amorphous, it could be adopted for the investigation of crystals caking. However, it should be noted that the MPT cannot supply
information about forces in the piconewton range [35].
Device to apply The advantage of DAPP is the ability of applying precise pressure on only two particles. The movable pin of DAPP is connected to a piezo
pressure on electric load cell. The piezo cell and the flexible pin are moved backwards, thus pulling the particles apart by using a stepper motor. The
particles (DAPP) maximum force breaking the bridge between these particles is measured [3]. It therefore is able to investigate the interaction.
Force Force displacement tester measures the peak force required in breaking caked powder. It was applied to investigate the effect of
displacement temperature, relative humidity, and exposure time on caking strength [36,1,37].
tester
Blow tester The blow tester, in its multiple test form, can measure the forces holding the particles together while temperature and relative humidity
are held constant. It has some advantages, e.g. multiple trials can be performed on one sample, unlike methods such as friability or angle of
repose, where the sample is poured out of the container or onto a surface. It also enables the progression of the formation of liquid bridges
to be followed with time [38,39].
Compressibility Penetration test The penetration test method considers the unconfined yield strength of particles [40]. The punch was removed from the sample, and the die with
sample compact inside was placed in the Instron machine to carry out the penetration force measurement. Hassanpour [15] developed a ball
indentation method for evaluating the hardness of a powder. A sample is consolidated into a cylindrical die which is made of low friction materials
in order to reduce the effects of wall friction. The consolidated bed is then indented using a spherical indenter. An advantage of this approach is its
sensitivity and ability to measure the onset of caking. In recent years ball indentation has received further attention to improve our understanding
of this method [41].
ICI caking tester The ICI caking tester is a shallow and sealed mould. Caking is induced using pneumatic pressure. A displacement transducer has also been
used with this tester to evaluate the shrinkage of the specimen during caking [42]. After compression, the top cover of the tester is
removed and a load is applied to the top of the sample until a plug of material is displaced, the pressure at which this occurs can help
determine the extent of powder caking.

Example A: screen by circularity and convexity
The circularity and convexity of caked particles differ a lot from un-
caked ones. They may be the key indices to separate the sample. First of
all, the circularity distribution (Figs. 4 and 5(a) and (c)) show that all
particles in part a have caked while the ones in part c didn't.
Fig. 5(b) shows that the index circularity could not separate the parti-
cles well in part b.
Secondly, the particles in part b of Fig. 4 were analyzed with convex-
ity. Figs. 6 and 7 show that these particles were separated successfully.
Since all these data are number-based, the caking ratio could be estimat-
ed precisely with number of particles.
Example B: screen by primary and secondary particles
Caked particle is secondary particle. Hence, the caked particles could
be identified by analyzing primary and secondary particles. The key
technique is shown in Fig. 8. The spherical particles are successfully an-
alyzed as secondary particles consisting of primary particles. Thus, ac-
cording to the image analysis of number of primary and secondary
particles before and after caking, the caking ratio could be evaluated.
The two examples above show some potential ideas for evaluating
caking ratio. These ideas should be properly modified to fit some specif-
ic conditions of samples, devices, and software.
It should be noted that the common method of measuring caking
ratio is still sieving in recent literature [21–23]. Sieves have been used
to determine the degree of caking. Using a sieve aperture that is larger
than the constituent particles, will allow the free flowing material to
pass it. A certain percentage of the material will not pass if the material
has caked. The caking ratio here is given as the mass fraction of material
that is retained on the sieve. However, there may be a disadvantage.
Sieving causes collision among particles and friction between particles
and sieve apertures. The collision and friction may break the particles
that caked slightly. As a result, the measured caking ratio may be
below the real one. To prevent this error, this sieving method should
only be utilized to measure the particles that caked badly while main-
taining slight movement. Thus, it is preferable to use a sieve shaker ma-
chine where the intensity can be controlled and maintained to allow for
repeated trials. As for the manual sieving, it is necessary to guarantee
the same operator and procedure of movement. e.g. slope the sieves
with given angle of inclination and given times to provide a constant
force because of gravity. Besides, the intensity of sieving could be con-
trolled by the angle of inclination. No matter which sieving method is
utilized, the two piles of separated particles should be checked via mi-
croscope to make sure that the caked particles have been totally sieved.
Sieving methods are low-cost and high-loading, which is preferred
by industrial manufacturers. However, the unexpected breakage of
caked particles during friction and collision leads to the errors on the
low side. On the other hand, although image analysis is high-cost and

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 M. Chen et al. / Powder Technology xxx (2017) xxx–xxx
Fig. 3. Optical microscope images of caked sodium phosphate and image analysis data of one of these crystals. The images and data were provided by a morphology analyzer (Morphologi
G3, Malvern Instruments Ltd., United Kingdom).
low-loading, it provides visual data processing technology, which helps
obtain precise and repeatable results. These advanced technologies
would contribute a lot in the further research.
3. Mechanisms
Generally, caking of crystals occurs during the absorption and de-
sorption of moisture content, e.g. storage and transport under high hu-
midity, drying process with alcohol or other rinsing liquids on the
particles surfaces, etc. The liquid content plays an important role in
the caking process [51]. Most crystals (carbohydrates, organic and
inorganic acids and their salts, and various mineral salts) are polar sub-
stances that dissolve in aqueous solutions. Conversely, apolar molecules
interact primarily with apolar liquids such as chloroform, triacetin, car-
bon acids, carbon acid esters, phthalic acid and toluene [5]. In most stud-
ies of crystals caking, water is widely adopted due to the typical caking
process caused by moisture sorption and desorption under various con-
ditions of humidity and temperature. Theoretically, this process is able
to show the integrated mechanisms of caking by controlling relevant
conditions, which therefore can be referred by other liquids or caking
Fig. 4. Circularity distribution of sodium phosphate particles by Morphologi G3.
Please cite this article as: M. Chen, et al., Caking of crystals: Characterization, mechanisms and prevention, Powder Technol. (2017), http://
dx.doi.org/10.1016/j.powtec.2017.04.052
5
situations, e.g. drying process with mother liquor or rinsing liquid on
crystals surfaces [21]. In this process (Fig. 9), caking of crystals has
three typical stages: 1). moisture sorption, 2). liquid bridges effects,
3). crystal bridges formation [10]. The three stages are reviewed below.
3.1. Moisture sorption
Caking starts from the moisture sorption, which leads to the interac-
tion of water with solids [52]. The crystals have the deliquescence point
RH0 and RHcc that is the critical RH at which capillary condensation re-
sults in liquid bridge formation (Fig. 9, moisture sorption). The illustra-
tion (Fig. 10) shows that the moisture is absorbed slowly under RH0
while it is much faster when exceeding RH0. Due to the difference, one
of two main processes may be facilitated: capillary condensation or del-
iquescence. The two processes are reviewed below.
Capillary condensation can be described as the direct condensation
of moisture at contact points of particles. In capillaries formed by the
contact points, the pressure is lower than surrounding atmosphere. If
the pressure is lowered enough to cause the vapor pressure to be great-
er than the saturated partial pressure above the capillary surface, then
condensation will occur [39].
The Kelvin equation describes the occurrence of capillary bridges de-
pending on the relative humidity RH and the curvature of the meniscus
[11,39,52].
     
P RH γ∙V m 1 1 2∙γ∙ cosθ∙V m
ln ¼ ln ¼ ln ðaW Þ ¼ − ∙ − ¼−
p0 100 R∙T s l r k ∙R∙T
ð1Þ
Where P is external water vapor pressure, p0 is vapor pressure of
pure water, aW is water activity, γ is surface or interfacial tension, Vm
is molar volume of the liquid, R is gas constant, T is temperature, s is ra-
dius of meniscus, l is azimuthal radius of a meniscus, θ is contact angle of
liquid to solid surface, rk is Kelvin radius. Symbols are shown in Fig. 11.
The Kelvin equation can be used to predict the Kelvin radius where
capillary condensation will occur for a range of water activities aW.
6 M. Chen et al. / Powder Technology xxx (2017) xxx–xxx

Fig. 5. Optical microscope images of sodium phosphate by Morphologi G3. a) particles in part a of Fig. 4. b) particles in part b of Fig. 4. c) particles in part c of Fig. 4.

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 M. Chen et al. / Powder Technology xxx (2017) xxx–xxx 7

Fig. 5 (continued).

Capillaries of smaller radius than the Kelvin radius will be full of water/ the chemical potential μ of pure liquid water in equilibrium with its
material solution [39]. vapor:
Deliquescence is a first-order phase transition process whereby a
substance dissolves in atmospheric moisture when the relative hu- μ ¼ μ 0 þ RT ln p0 ð2Þ
midity (RH) reaches or exceeds a certain critical value RH0 [53–57].
Allan et al. [58] summarized the RH0 measurement methods. Where μ0 is the standard chemical potential.
The aqueous solution is thermodynamically favored over the The difference in chemical potential creates a driving force for water
crystalline phase, which is known to occur sharply with increasing to collect on the surface of the crystal as long as the solute is present
relative humidity on reaching free energy equality between the ini- which can be expressed as:
tial (salt particle plus vapor) and final (fully dissolved solution  
drop plus vapor) states [59–61], resulting in spontaneous moisture ps
μ s −μ ¼ RT  ln ¼ RT  ln ðaW Þ ð3Þ
sorption and formation of a condensate film on the surface of the ma- p0
terial. The thermodynamics of deliquescence can be considered by Where μs is chemical potentials of the solution on the crystal sur-
faces, ps is vapor pressure of the solution.
The kinetics of deliquescence increase as the RH increases above RH0
depending on the ratio RH/RH0. The kinetic equation can be simplified as
follows:
 
RH
W ¼ ðC þ F Þ ln ð4Þ
RHo
Where W is the sorption rate, C and F represent the conductive and
radiative terms, respectively. C and F are found to contribute equally
to heat transport.
More details about the thermodynamics and kinetics of deliques-
cence are discussed in references [62,63].
The summary above shows that both capillary condensation and
deliquescence are facilitated depending on the RH. Hence, it is impor-
tant to note that special situations may occur due to the properties of
Fig. 6. Convexity contribution of sodium phosphate particles in part b of Fig. 4. the crystals with water (or other liquids in some conditions), e.g.

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8 M. Chen et al. / Powder Technology xxx (2017) xxx–xxx

Fig. 7. Optical microscope images of sodium phosphate by Morphologi G3. a) particles in part a of Fig. 6. b) particles in part b of Fig. 6.

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 M. Chen et al. / Powder Technology xxx (2017) xxx–xxx
Fig. 8. a) Scanning electron microscope (Phenom ProX, Phenom, Netherlands) of LiCO3
particles. b) Recognition of primary and secondary particles (Particlematric, Phenom,
Netherlands).
polymorphic transitions [13,64–66], phase transitions [67–69], chemi-
cal reaction [59], etc. These phenomena change moisture sorption, as a
result, even further complicating the entire caking process. Listiohadi
et al. [13] investigated the difference of moisture sorption behavior
among lactose polymorphs. They concluded that the polymorphic and
isomeric properties of lactose play a significant role in its hygroscopicity.
The interconversion between the lactose polymorphs changes the α/β
and anhydrous/monohydrate ratio, which has a great impact on mois-
ture sorption and crystal bridge formation. Kwok et al. [59] investigated
the impact of sucrose hydrolysis on moisture sorption. One of the reac-
tions is presented by the following chemical equation:
sucroseðaqÞ þ H2 OðlÞ → glucoseðaqÞ þ fructoseðaqÞ ΔH h ð5Þ
¼ −14:93 KJ=mol
Thermodynamically, the water vapor condenses onto the sucrose
particles surfaces and leads to the reaction. The moisture sorption be-
havior of a mixture therefore differs from that of a pure substance.
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9
3.2. Liquid bridge
Moisture sorption leads to liquid bridges generating between parti-
cles. In a capillary condensation process, the water volume of a steady
liquid bridge could be estimated with Eq. (1). As for a deliquescence
process, the water volume increases continuously and finally results in
a total dissolution of the sample [62,63]. The liquid bridge, or liquid
film to some extent (Fig. 9, liquid film under deliquescence), therefore
keeps increasing with time. Komunjer et al. [70] described the kinetics
of absorption of water vapor and formation of solution with the Knud-
sen formula:
dn KP 0
¼ K ðP−pn Þ ¼ ðRH−RH0 Þ ð6Þ
dt 100
Where n is number of molecules or moles of moisture content enter-
ing the condensed phase, t is time, dndt
is therefore the rate of adsorption
of water onto the crystal surfaces. K is Knudsen coefficient, pn is non-
negligible pressure of condensed phase.
This theoretical approach showed a good agreement with the exper-
imental data. It was concluded that dn dt
remained constant until the crys-
tals completely dissolved. After that, the rate dropped slowly and finally
the equilibrium was reached when pn became equal to P.
Liquid bridges also present forces affecting contact between particles
[71], which may impact crystal bridge formation. The generated forces
are capillary forces first studied by Fisher [72] and Haines [73] in the
mid 1920s. In 2009, Butt reviewed the capillary forces between two par-
ticles or planes [74]. The capillary force f for sphere-sphere contact ge-
ometry (Fig. 11) can be calculated with Eq. (7):
  
1 1
f ¼ π ∙ γ ∙ R1 ∙ sinβ1 ∙ 2 sinðθ1 þ β1 Þ þ R1 ∙ sinβ1 ∙ − ð7Þ
s l
Where R1 is radius of a sphere, β1 and θ1 are filling angle and contact
angle of the liquid to the sphere with radius R1, respectively.
Various contact geometries, e.g. sphere-plane, core-core, core-plane,
plane-plane were also described in detail [74].
In addition, mathematical models of more complex liquid bridges
and alternative methods considering energy of particles system were
also studied. The liquid bridge does not only lead to the formation of a
liquid dimers as mentioned above, but also to more complex liquid
phase morphologies, e.g. liquid trimer, pentamer and tetrahedron.
These liquid morphologies have been observed via the X-ray tomogra-
phy technique [75–77]. Depending on the water content, these liquid
morphologies lead to more complex states of cohesion: pendular (low
water content, forms in dimer, Fig. 12a), funicular (increasing the
water content, forms in trimer, pentamer and tetrahedron, Fig. 12b),
and capillary (nearly saturated, forms in trimer, pentamer and tetrahe-
dron, Fig. 12c) [76,78]. So far, only the pendular state has been investi-
gated systematically. In the 1990s, researchers started to study the
funicular state with the liquid trimer, i.e. the fundamental structure of
this state [78]. The investigation has been developed from two dimen-
sional to three dimensional funicular water bridge between three
spheres so far [79–83]. However, these studies are extremely limited
due to the high complexity of the geometry. For the crystals, one
method of determining the geometry is to create a particle geometry
distribution, e.g. morphological indices distribution in Section 2.3.
Nonetheless, the analytical solutions based on Young-Laplace law are
complicated. The alternative method is obtaining the index that pre-
sents the equilibrium/average states of the samples. This concept is
often related to the study of energy. Based on the “Surface Evolver” by
Brakke [84], a software using calculus of variations to minimize the
inter-facial energy iteratively for the solutions of the Young-Laplace
equation, Cater [85] and Wang [86] concerned the calculation of forces
for three spheres. The effects of inter-particle distance, water volume
and contact angles were investigated qualitatively. For a same fixed
10 M. Chen et al. / Powder Technology xxx (2017) xxx–xxx

Fig. 9. Caking process under different conditions. RH is the environmental relative humidity value, RH0 is the deliquescence point of crystals, and RHcc is the critical RH at which capillary
condensation results in liquid bridge formation, which over time may solidify by mass transfer, without decreasing the RH.

total water volume, the capillary force is weakened by water bridge co-
alescence to a funicular bridge when the spheres are packed together,
but the situation may vary for different contact angles and inter-
particle distances. For the constant mean curvature condition, water
bridge coalescence does not alter capillary force significantly when par-
ticles are packed closely, but the discrepancy is larger by increasing the
gap [86]. Chen et al. [21,23] investigated the adhesion effects of liquid
bridges thermodynamically utilizing the adhesion free energy that
also considered the geometry. The capillary rise method used in the ex-
periments measured the average contact angles of the samples with dif-
ferent geometry. Hence, the adhesion free energy calculated with the
contact angles is a statistical and thermodynamic result. It therefore
presents the average state of samples with geometry in consideration.
Adhesion free energy of liquid bridge between the particles denotes
the effects of repulsion or attraction. Results showed that for the one-
layer samples under static conditions, the critical value that avoids par-
ticles contact is about 60 mJ/m2.
According to the summary, the effects of a liquid bridge depends on
a vary of factors, e.g. liquid content, number of particles, location of par-
ticles, geometry of particles, particle shape, particle size, properties of
particle surfaces, etc. Based on the Young-Laplace equation, the study
on two-particle and three-particle systems is able to establish the math-
ematical models and analyze each factor quantitatively. It is of great ne-
cessity for studying mechanisms. However, this method seems to be
inefficient facing more complicated particle systems. For this situation,
studies with the energy methods provide comprehensive and qualita-
tive results, which may accelerate the development of the former. E.g.
in the near future, the basic conclusions about geometry of liquid trimer
from the energy method would support further studies of the mathe-
matical models. It should be noted, however, that several problems of
energy methods need to be solved. E.g. the Lifshitz-van der Waals
acid-base theory [87] used in adhesion free energy calculation is still
controversial [88–92]. The basic parameters of liquids keep being re-
vised [87]. Besides, more basic parameters of common liquids need to
be measured.
3.3. Crystal bridges
The liquid bridge can be supersaturated due to vaporization of water
or variation of temperature, leading to recrystallization and then crystal
bridge formation between crystals (Fig. 9, recrystallization in crystal
bridge) [1]. Interestingly, Kirsch et al. [93] observed that a time-
dependent mass transfer into the liquid bridge took place, transforming
it into a crystal bridge, which cannot be considered as the typical recrys-
tallization mechanism. This phenomenon is showed in Fig. 9 (mass

Fig. 11. Sphere with radius R1 interacting with sphere with radius R2. Two spheres are
Fig. 10. Moisture sorption behavior of crystalline particles. Formation of sloping is caused bonded by a liquid bridge. s is radius of meniscus, l is azimuthal radius of a meniscus, θ
by RH, moisture sorption rate and time. is contact angle of liquid to solid surface, rk is Kelvin radius, β is filling angle.

Please cite this article as: M. Chen, et al., Caking of crystals: Characterization, mechanisms and prevention, Powder Technol. (2017), http://
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 M. Chen et al. / Powder Technology xxx (2017) xxx–xxx
Fig. 12. Illustrations of three states of liquid presence in particles. Particles are simplified by spheres. a) Pendular state. Isolated liquid bridges are formed between particles. b) Funicular
state. Liquid bridges coalesce into liquid clusters which may connect more than two particles. c) Capillary state. Particles system is nearly saturated with only entrapped air bubbles.
transfer). It occurs during a long time period under strict instant condi-
tions, especially relative humidity and temperature. Scholl et al. [10]
agrees with the explanation of mass transfer, but no relevant compre-
hensive evidence was proposed. In 2015, Vallatos et al. [94] assumed
that the mass transfer takes place through diffusional transport within
a thin layer of solution on the particles surfaces. They applied nuclear
magnetic resonance (NMR) providing the first quantitative measure-
ments of diffusion in thin spherical films. Results showed that the mo-
lecular diffusion coefficients in this film are the same as those found in
bulk solution. The thickness of the liquid layer composed of saturated
urea (crystal sample, same with Kirsch [93]) solution covering the sur-
face of prills were estimated to be on the order of 10−5 m. As a result
of the strict conditions, more similar experiments with different
substances should be carried out to ensure the repeatability and univer-
sality. On the assumption of reasonable mass transfer, this mechanism
may be utilized under both constant and varying ambient conditions.
In this case, the interaction between mass transfer and dissolution-
recrystallization should be considered and more studies in this field
are required.
Due to the diverse explanations of the crystal bridge and the contro-
versial mechanisms of crystal nucleation and growth, so far the kinetics
of crystal bridge formation studies focus on the simple model based on
the typical mechanism of dissolution-recrystallization. An experimental
method on sorption-evaporation kinetics was developed by Komunjer
et al. [70] A theoretical approach describes the process of absorption
of water vapor and formation of solution-evaporation of water-
nucleation and growth of the recrystallized solid. The foundation of
the kinetic model is based on the Knudsen formula. Eq. (6) shows that
the process is governed by the imposed driving force for evaporation
i.e., RH0-RH. The kinetic model was established by connecting the stages
(absorption of water vapor and formation of solution-evaporation of
water-nucleation and growth of the recrystallized solid) to the driving
force with the relevant parameters of pressure and concentration [70].
The contrast between the theoretical and experimental curves provides
useful insight into the kinetics. In addition, the stages affected by anti-
caking agent can be clearly inferred, which is a valuable method for
studying anticaking. The precision of this experimental method was
improved by Langlet et al. [95] utilizing environmental scanning elec-
tronic microscopy (ESEM). Coupled with dynamic vapour sorption
(DVS), measurements were proved to be appropriate means of some
quantitative and accurate determinations, e.g. RH0 of crystals and criti-
cal supersaturation for nucleation.
These studies are significant to give a view from the moisture sorp-
tion to crystal bridge formation. However, the explanations of crystalli-
zation from liquid bridge to solid bridge in these studies are still not
enough. Though researchers are trying to establish the kinetics of nucle-
ation and growth, there are still more theories of crystallization science
that can be applied to crystal caking. E.g. the difference between sorp-
tion and desorption curves is similar with the metastable zone in crys-
tallization [96]; the crystal bridge caused by evaporation may be
inferred from the kinetics of evaporation crystallization [97–102]; the
Please cite this article as: M. Chen, et al., Caking of crystals: Characterization, mechanisms and prevention, Powder Technol. (2017), http://
dx.doi.org/10.1016/j.powtec.2017.04.052
11
crystallization heat should be evaluated for the recrystallization process,
etc. Particularly, due to the recrystallization of the liquid bridges pro-
ceeding by growth starting from the constituent crystal particles and/
or by the formation of 3D nuclei within the liquid bridges, the evapora-
tion crystallization process could have great impact on the shape, size
and composition of crystal bridges. These differences from crystal
bridges may cause a significant effect to the caking strength and caking
ratio. Common shape of crystal bridges is made from a number of
microcrystallites, see Fig. 13(a). While in some special evaporation crys-
tallization, needle-like aggregates generated in a droplet [99]. It means
that the crystal bridge can also be needle-like, see Fig. 13(b). Crystals
with phase transformation properties could also generate a crystal
bridge in different phases [67–69,103], see Fig. 13(c). Hence, it can be
concluded that crystal bridges can be quite complicated and should be
reconsidered with crystallization science instead of simplified models,
e.g. cylinder-shape model.
As mentioned above, crystallization science is of importance in the
understanding of the formation of liquid bridges and crystal bridges,
see Fig. 14. Supersaturation facilitates the crystal growth around the
crystal surfaces, while nucleation occurs further away from these sur-
faces. The two-dimensional nucleation growth [104–107] and spiral
crystal growth (Burton, Cabrera and Frank theory, BCF) [108] then
could be adopted for the growth. Recently, the controversy between
the classical nucleation theory (CNT) [109,110] and the two-step nucle-
ation mechanism [111,112] couldn't be ignored. The focus is liquid-
phase precursors. CNT states that the density fluctuations are concomi-
tant with fluctuations in the order parameter, so that molecular packing
within clusters reflects the possible polymorphs of the solute [113]. The
two-step nucleation mechanism shows that the fluctuations in density
are disconnected from those in order, so that the initial clusters that
form are liquidlike, and crystalline order appears later on [114–116].
This controversy is motivating furhter research on crystal nucleation.
Recently, Bode et al. [117] explained the caking of sodium chloride
dihydrate with crystallization science. They determined the morpholo-
gy of the dihydrate crystals with crystallographic structure. Both classi-
cal and two-step nucleation theories were utilized for the nucleation
rate. The growth rate was measured by taking micrographs. The results
showed that the two-step nucleation theory seems to better fit the nu-
cleation rate of sodium chloride dihydrate. The formation of crystal
bridge was inhibited by the effective anti-caking agent, Fe(III)-LTA,
due to the limitation of crystal growth rather than nucleation. Study of
crystallization always depends on methods of fourier transform infrared
spectroscopy (FTIR), raman spectroscopy, nuclear magnetic resonance
(NMR), molecular simulation, etc. In the near future, based on these the-
ories and methods of crystallization, further investigation of liquid and
crystal bridges would provide more novel views in caking mechanisms.
4. Prevention
The unique properties of crystals, e.g. critical value of humidity, spe-
cific particle geometry, etc., should be considered for the prevention of
12 M. Chen et al. / Powder Technology xxx (2017) xxx–xxx

Fig. 13. Illustrations of crystal bridges generated under different conditions. a.) Crystal bridge made of microcrystallites. b). Crystal bridges made of needle-like crystals. c). Crystal bridge
under condition of phase transformation.

crystal caking. On the one hand, theoretically, controlling the moisture
content is the direct thought of preventing caking. The moisture content
of the product is usually the most important factor in promoting caking.
For most caking mechanisms, the presence of moisture, in the form of
solution phases, is essential. Generally, the higher the degree of drying
at the time of manufacture is, the less active the caking mechanisms
will be [118]. On the other hand, however, the ideal conditions of low
moisture content cannot be always guaranteed in actual industrial pro-
duction. Therefore, improving the anticaking property of crystals against
the unstable ambient conditions is another important consideration.
It must be noted that the experimental research for controlling these
factors systematically is complicated. Instead, utilizing the simulation
technique would be effective. It is a necessary way to achieve the con-
version from scientific research to production and the idea of “quality
by design”. To do this, the combination of particle and crystal engineer-
ing would be the key. According to the computational technique, e.g.
discrete element method (DEM) [119], the behavior of a crystal system
(particles packing, caking mechanisms, also crystallization) would be
simulated. Caking indices then could be predicted. With the systemati-
cally designed ambient conditions and crystal parameters, production
would be properly prepared according to crystal engineering. So far,
there still remains a strong need to develop simulation methods that
consider all the main factors. Hence, in this section, the research of
each main factor is summarized, a simulation of caking based on DEM
method is presented, and the factors that haven't been counted in yet
are discussed for further study of DEM.
4.1. Control ambient conditions
4.1.1. Humidity and temperature
The co-effect of temperature and RH on the product when placed in
storage influences caking tendency. Fig. 15 summarizes the water-solid
interactions of crystals under different RH and temperature. Crystals
present critical values of RH0 and RHcc along with the relevant bound-
aries. It demonstrates that caking caused by deliquescence (RH0) is
the most problematic, while the one caused by condensation capillary
(RHcc) is the easiest to be remedied. Caking can be significantly
inhibited when the co-effect of temperature and RH is under the RHcc
boundary [2].
As mentioned above, the RHcc and RH0 boundaries play key roles in
controlling ambient conditions in industrial production. They could be
measured by DVS. Depending on the substances, the RHcc value may
not be obvious, then the RH0 would be the approximate crucial value.
More precise measurement of the critical value of facilitating caking
was presented by Billings et al. [39]. Based on Eq. (1), they developed
a measurement of critical water activity (RH/100) through a diagram
of relation between Kelvin radius and caking strength. The relevant

Fig. 14. Crystal nucleation and growth in a liquid bridge.

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 M. Chen et al. / Powder Technology xxx (2017) xxx–xxx
Fig. 15. Caking behavior of crystals with RH changing under 25 °C.
critical values of RH and temperature for initiation of caking therefore
can be estimated.
4.1.2. Liquids screening
In addition to transport and storage, caking also occurs in drying pro-
cesses. In a drying process, the crystals contain a mass of the mother liq-
uid or rinsing liquid which constitute the liquid bridges. The effect of
liquid bridges is different based on the liquid used. Chen et al. [21,23] in-
vestigated the effects of liquid bridge made from different liquids on the
particles contact behavior. They concluded that some liquids present re-
pulsion, contrary to the water presenting attraction. The repulsion re-
duces the chance of particles contact and then inhibits the crystal
bridges formation. Hence, the solid-liquid interaction should be consid-
ered for the liquids screening.
4.1.3. Pressure
The pressure exerted at the bottom of a stack or pile of crystals has
an effect on caking. As with storage time, excessive and prolonged pres-
sure will result in an increase in caking. Under pressure, particle defor-
mation may occur, resulting in increased contact area and surface
tension [118,120]. In addition, the increased bulk density may lead to
a more serious effect of capillary condensation.
Though no systematic and effective solutions have been proposed to
prevent the negative impacts of pressure on crystalline products, there
have been a few studies focused on finding possible solutions. Pressure
should also be quantitatively considered to help solve problems such as
how to prevent crystals caking under static high pressure during storage
or dynamic pressure during transportation. It is of great necessity to
adopt the novel caking indices and simulation.
4.2. Improve anticaking property of crystals
As an effective method, anticaking agent changes production pro-
cess little. It therefore seems to be the preferred method to improve an-
ticaking property. However, anticaking agent is limited by the high cost
and difficulty of development and the consequent environmental prob-
lems. To address these issues, the enhancement of crystal engineering
should be considered first based on “quality by design”. With the specif-
ic design of crystal size, shape and impurity, the anticaking property
would be truly improved. As a result, the usage of anticaking agent
would decrease or even be avoided. Hence, improving anticaking prop-
erty should be considered comprehensively at the start of the design
production process to achieve the requirement of high quality, low
cost, and being environment friendly.
Please cite this article as: M. Chen, et al., Caking of crystals: Characterization, mechanisms and prevention, Powder Technol. (2017), http://
dx.doi.org/10.1016/j.powtec.2017.04.052
13
4.2.1. Particle size and shape
Most crystals are larger than 100μm. The effects of particles size and
shape should be both considered. Past studies have shown that large
particles with granulate or sphere-like shape present better properties
in inhibition of moisture sorption [23] and particles contact. These prop-
erties could reduce the caking ratio and caking strength.
For the simulation of caking behavior, utilizing computational tech-
nique, e.g. DEM, to simulate the particles packing is the first step. Hence,
the particles size and shape are the most important factors that should
be primarily considered. The following shows a possible technique rou-
tine to predict caking ratio and strength with DEM. To focus on the rou-
tine, the simulation was simplified by considering particles size only.
PFC3D software that is based on DEM was utilized to simulate the par-
ticles packing with different particles size. Crystalline maltitol was
adopted as the test sample and the moisture-sorption property was in-
vestigated by DVS [70,95]. The results showed that the capillary conden-
sation point was 85% and deliquescence point was 92.5%. The humidity
recycle therefore was set to 90%–45%/day. Calculation of moist sorption
was based on the Kelvin equation. It was assumed that the valid diam-
eter of a crystal bridge is equal to half of diameter of the smaller crystal.
Particles number was set to 100. Particles sizes were set to 225, 375,
525, 675μm and 25 particles for each size.
Fig. 16 shows the simulation result of caking behavior from 1 day to
40 days. The color zones represent the caked particles, where a dark
color indicates larger caking strength. It shows that the crystals with
smaller particles size caked first and formed strong crystal bridges rath-
er quickly. On the other hand, Fig. 16(e) and (f) shows that the shapes of
caked particles from the simulation result were similar with the real
ones.
Based on Figs. 16 and 17 show the caking ratio of these crystals with
time quantitatively. For the whole sample, caking ratio increased signif-
icantly in the first 10 days and then slowed down in next 30 days. The
reason is that the smaller particles contributed over 35% to the caking
ratio at the beginning and in the meantime lead to about 20% larger par-
ticles caking in the first 10 days. While in the next 30 days, most of the
smaller particles had finished caking and larger particles still caked
slowly, which slowed down the caking ratio. Hence, compared with
the larger ones, smaller particles show much more positive caking ten-
dency. To prevent crystals caking, it is therefore of great importance to
improve particles size and narrow the particle size distribution.
The simulation above shows a possible way to predict the caking in-
dices with DEM. It has been pointed out that particle shape is widely
recognized to have a strong influence on the granular systems. To im-
prove the precision, particle shape therefore should be considered
[121–124]. Lu et al. [119] reviewed the DEM for non-spherical particle
systems. Four methods have been developed to represent the non-
spherical particle shapes in DEM: ellipses/ellipsoids, super-quadrics,
14 M. Chen et al. / Powder Technology xxx (2017) xxx–xxx

Fig. 16. Simulation of caking behavior by PFC3D and real caked particles image. a) 1 day, caking ratio = 0%; b) 2 days, caking ratio = 8%; c) 7 days, caking ratio = 48%; d) 19 days, caking
ratio = 69%; e) 40 days, caking ratio = 81%; f) real caked particles images under same simulation conditions (×40). The caking ratio was calculated with number of particles.

polygons/polyhedrons, composite spheres, and composite elements.
The advantage and disadvantage of flexibility, numeral stability, and nu-
meral efficiency for each method have been summarized for modellers
to choose suitable modeling approach for their particular problem.
As for the very fine particles, especially nanoparticles, the effect of
van de Waal's force makes the nanoparticles tend to form very strong
agglomerates and lose their high-surface area due to grain growth or
unavailability of the high surface area where it matters [125]. Studies
have shown that most nanoparticle agglomerates are rather large, ex-
tremely porous, and have a hierarchical fractal structure consisting of
subagglomerates or aggregates at a number of different length scales,
down to individual nano-size particles. As a result, it is still a serious
problem to prevent nanoparticles caking (or aggregation to some ex-
tent). Most studies have focused on the deagglomeration process in-
stead of prevention.
4.2.2. Impurity
Undesired impurity, e.g. small amount of different substances in
crystalline or amorphous forms, also polymorphic transitions and
phase transitions mentioned in Section 3.1, should be avoided. The im-
purity may worsen the anticaking property of crystals by deliquescence
lowing. The presence of impurity may lower the RH0 and cause more
water to condense and initiate dissolution [61]. The effect of impurity
can be investigated through the moisture sorption curve by DVS.

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 M. Chen et al. / Powder Technology xxx (2017) xxx–xxx
Fig. 17. Caking ratio (calculated with number of particles) vs. time. Small crystals include
225 μm and 375 μm maltitol. Large crystals include 525 μm and 675 μm maltitol. Caking
ratio of whole crystals is the sum of the two.
4.2.3. Anticaking agent
Anticaking agents are substances added into products to prevent
caking [126]. For crystals (e.g. ascorbic acid, sodium ascorbate, citric
acid, glucose, sucrose, and sodium chloride), common anticaking agents
include calcium silicate, calcium stearate, silicon dioxide, tricalcium
phosphate, and corn starch [126]. Anticaking agents of crystals may
function by one of several mechanisms: 1). Prevent moisture sorption
and formation of liquid bridges. Some anticaking agents compete with
the host powder for moisture and/or create moisture-protective bar-
riers on the surface of hygroscopic particles or physical barriers between
particles. 2). Smooth surfaces to eliminate inter-particle friction. 3). In-
hibit formation of crystal bridges as a crystal growth inhibitor [43,
127]. Anticaking agents are commonly used in small amounts, nontoxic
and easy to handle. e.g. the current anticaking agent used for NaCl is fer-
rocyanide. A small amount can effectively block further crystal growth
and prevent particles from caking [44]. However, there are drawbacks.
It may decrease the efficiency in the production of chlorine gas with
NaCl by electrolysis. Therefore, a new anticaking agent was introduced:
Fe-mTA. It is almost as effective as ferrocyanide and eliminates the prob-
lem [43,44,117,128].
Screening anticaking agent is still based on the trial and error meth-
od. To decrease the difficulty and high cost of development, predicting
the effect of anticaking would become primary focus in further research.
The simulation mentioned in Section 4.2.1 may be an effective solution.
It would be a key point to combine the simulation technology of parti-
cles packing with the properties of particles that are easy to measure
to predict the complex caking behavior.
5. Conclusions
Caking indices are classified as mechanical (caking strength and
compressibility), morphological (aspect ratio, circularity, convexity,
sphericity, and bluntness), and statistical (mechanical indices distribu-
tions, morphological indices distributions, and caking ratio) ones. The
relevant characterization methods of these indices are summarized. It
has been pointed out that image analysis should be utilized to obtain
both morphological and statistical indices in the further research.
Crystals caking caused by moisture sorption and desorption is
discussed. The process is divided into three steps: moisture sorption,
liquid bridge, and crystal bridge. Depending on the RHcc and RH0, capil-
lary condensation (RHcc b RH b RH0) or deliquescence (RH N RH0)
causes moisture sorption and leads to liquid bridge formation. The ef-
fects of liquid bridge formation include dissolution of crystals and capil-
lary forces. Finally, recrystallization or mass transfer promotes crystal
bridges. For further analysis of the crystal caking process, the model of
capillary forces should consider the actual geometry of particles. The
study of mass transfer may provide more quantitative results and
Please cite this article as: M. Chen, et al., Caking of crystals: Characterization, mechanisms and prevention, Powder Technol. (2017), http://
dx.doi.org/10.1016/j.powtec.2017.04.052
15
models. According to the crystallization science, the mechanism of crys-
tal bridge formation will be further studied.
The prevention of crystals caking includes two aspects. On the one
hand, the ambient conditions should be controlled. Keep RH and tem-
perature lower than RHcc boundary to prevent moisture sorption. Re-
duce pressure to prevent crystals from deformation. Select a proper
rinsing liquid for the drying process that will reduce the adhesion effect
caused by liquid bridge. On the other hand, anticaking property of crys-
tals should be improved. Generally, large crystals with granular/spheri-
cal shape and high purity are hard to cake. However, the caking of nano-
crystals is still a serious problem. Anticaking agent is an effective mean
against caking under the condition that they are nontoxic, easy to han-
dle and only required in small amounts.
The simulation and prediction of crystal caking behavior would be
an important direction. It is able to estimate the extent of caking
under given conditions of temperature, humidity, particles size, parti-
cles shape, the amount of anticaking agent, etc. Thus, it may guide the
enhanced design of crystal engineering. The focus would be a combina-
tion between computational techniques and caking experiments.
Acknowledgements
The authors are grateful to the financial support of National Natural
Science Foundation of China (81361140344, 21676179 and 21376164),
National 863 Program (2015AA021002), major project of Tianjin
(15JCZDJC33200), Major National Scientific Instrument Development
Project 21527812, and Major Science and Technology Program for Wa-
ter Pollution Control and Treatment (2015ZX07202-13).
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