Chinese Journal of Chemical Engineering 27 (2019) 1429–1438

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Chinese Journal of Chemical Engineering

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Review

Amorphous and humidity caking: A review☆

Mingyang Chen 1, Dejiang Zhang 1, Weibing Dong 1,2, Zhilong Luo 3, Chao Kang 3, Haichao Li 2,
Gang Wang 2, Junbo Gong 1,4,5,⁎
1
School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China
2
College of Chemistry and Chemical Engineering, QingHai Nationalities University, Xining 810007, China
3
Xi'an Modern Chemistry Research Institute, Xi'an 710000, China
4
Key Laboratory Modern Drug Delivery and High Efficiency in Tianjin University, Tianjin 300072, China
5
The Co-Innovation Center of Chemistry and Chemical Engineering of Tianjin, Tianjin 300072, China

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

Article history: Caking of products is a common and undesired phenomenon in food, chemical, pharmaceutical, and fertilizer
Received 25 June 2018 industries which leads to extra cost and irregular quality. In general, caking processes could be identified as
Received in revised form 21 December 2018 amorphous caking or humidity caking. In this review, history of studying caking, formation, methods, and pros-
Accepted 17 February 2019
pects of these two caking processes are summarized and discussed. The relevant studies from the 1920s to today
Available online 21 February 2019
are mentioned briefly. According to the different properties (i.e. hygrocapacity, hygrosensitivity, mechanical
Keywords:
properties, and diffusion behavior) of amorphous powders and crystals, the conditions and mechanisms of amor-
Agglomeration phous and humidity caking are discussed. It is summarized that glass transition, moisture sorption, quantitative
Particle methods characterizing caking, accelerated caking tests, and simulation of caking behaviors are the main aspects
Powder technology that should be studied for a caking process. The methods for these five aspects are reviewed. Potential research
Amorphous caking points are proposed including caking of mixed particles, caking with phase transition or polymorph transition,
Humidity caking non-homogenous caking, and simulation of caking.
© 2019 The Chemical Industry and Engineering Society of China, and Chemical Industry Press Co., Ltd.
All rights reserved.

1. Introduction
Bulk solids handling is the most common industrial activity in the
world. Most materials in food, chemical, pharmaceutical, and fertilizer
industries are preferred to be free-flowing, so that would be suitable
for manufacturing processes and final application [1]. However, under
the reasonable conditions, e.g. transport, storage and drying processes,
some materials tend to be lumps for extended periods. This is referred
to as “caking”. Caking is first defined as the agglomeration of a free-
flowing powder into lumps [2,3]. Now it is commonly described as a
phenomenon by which a low moisture, free-flowing powder is first
transformed into lumps, then into an agglomerated solid, resulting
in loss of functionality and lowered quality [4]. Formation of caking
is complex. The mechanisms depend on substances and conditions.
For instance, amorphous powders facilitate amorphous caking, while
crystals facilitate humidity caking. Furthermore, different mechanisms
☆ The authors are grateful to the financial support of Major National Science
and Technology Projects (2017ZX07402003), Innovative Group Project 21621004 and
Major Science and Technology Program for Water Pollution Control and Treatment
(NO.2015ZX07202-013).
⁎ Corresponding author at: School of Chemical Engineering and Technology, Tianjin
University, Tianjin 300072, China.
E-mail address: Junbo_gong@tju.edu.cn (J. Gong).
occur with a same substance due to proper conditions. Besides, the
mechanisms of humidity caking of amorphous powders differ signifi-
cantly from the one of crystals [5]. Nonetheless, a caking process could
be identified macroscopically. Fig. 1 shows the changes of two morpho-
logical indices of key states in a typical caking process: the ratio of
instant system porosity to initial system porosity, p/p0; and the ratio
of interparticle bridge diameter to particle diameter, Db/Dp. At the
start, the individual particles contact. The p/p0 is the highest and Db/Dp
is the lowest due to no liquid/solid bridges or deformation. Then
bridging occurs as a result of liquid bridge between particles, or surface
deformation and sticking, etc. It generates forces among particles and
leads to adhesion. As a result, the p/p0 begins to decrease while Db/Dp
increases significantly. Eventually the solid bridges are generated
based on the bridging situation. Particles are transformed into lumps.
Hence the p/p0 and Db/Dp remain fairly unchanged. Based on the men-
tioned above, caking is an agglomeration process. Agglomeration can
be either desirable or undesirable [6]. It is defined as a process to gather
into a mass or cluster; to collect or come together in a mass; to collect
into a ball, heap, or mass, specifically: clustered or growing together
but not coherent [7]. For the desired processes, e.g. agglomeration
technique in fluidized bed, spray dryer, rotating drum granulation,
and spherical agglomeration in crystallization [8–10], size enlargement
by agglomeration is the generic term for that unit operation of mechan-
ical process engineering which is characterized by combination with

https://doi.org/10.1016/j.cjche.2019.02.004
1004-9541/© 2019 The Chemical Industry and Engineering Society of China, and Chemical Industry Press Co., Ltd. All rights reserved.
1430 M. Chen et al. / Chinese Journal of Chemical Engineering 27 (2019) 1429–1438
Fig. 1. Typical stages in a caking process, indicating the changes in system porosity p/p0 and
the ratio of interparticle bridge diameter to particle diameter Db/Dp at each stage [4,11].
change in particle size [7]. Caking is one of the undesired agglomeration
processes. It is only utilized to describe the agglomeration after produc-
tion, e.g. drying, package, storage, transportation, and sale.
Caking results in loss of product and in process interruption [12].
De-caking manufacture is necessary, which costs extra time, man
power and additional equipment. Nonetheless, 2%–10% products are
lost and the de-caked products present irregular quality [4,13]. Caked
materials cause a drop in the production rate, and in the worst complete
stop of production [14]. In China, some typical undesired caking
phenomena have also been reported. Fertilizers cake badly after storage,
package, transportation, and sale due to their tendency of moisture
sorption. The caked fertilizers could not meet the requirements of
mechanized manufacture, even could not be used [15]. The ideal prod-
uct ratio of urea of a company form Shanxi is 98%. However, up to 50%
caking ratio limited the actual qualified product ratio to be 80%–95%.
Caking of NaCl and sugar is a serious problem during the transportation
between north and south of China due to the difference of temperature
and humidity, which has limited the business seriously [16].
Due to the severely negative impact on the quality of products and
the complex mechanisms, researchers have focused on caking issues
since 1920s. The research has involved fertilizer, food, pharmaceutical
fields. Mechanisms have been investigated from macroscopic measure-
ments, microscopic forces calculation, mathematical models to simula-
tion. This review focuses on the most typical caking processes:
amorphous caking and humidity caking. Relevant studies in the past
one hundred years are summarized. Based on these studies, formations
of the two caking processes are organized depending on amorphous and
crystalline powders. The key research methods of caking are summa-
rized. The potential research aspects are discussed.
It must be noted that, aggregation processes are not involved in this
review. Aggregation describes a process that particles collide and
adhere steadily via the Van der Waals attraction [11,17–19]. There are
no solid bridges among particles. Aggregates can withstand small
shear stresses, but are frequently broken down by larger stresses [20],
which significantly differ from agglomerates.
2. History
In the past one hundred years, caking was studied from macroscopic
scale to microscopic views. Methods, apparatus and testers, mecha-
nisms, and models were gradually established. The history was summa-
rized in Table 1.
3. Formation of Caking
3.1. Properties of amorphous powder and crystal
Substances could be distinguished by two supra-molecular struc-
tures: (1) Amorphous. Molecules are arranged statistically with an
energetically high level. It is a liquid-like state including a molecular
disorder. The molecules are randomly distributed within a more or
less rigid molecular matrix. An amorphous matrix is called a glass if it
has a high viscosity. While heating such a glass, it gradually transforms
into a rubbery structure and finally it liquefies. (2) Crystalline. Ions or
molecules are highly tri-dimensional ordered with an energetically
lower level. It might consist of polymer chains orientated in parallel,
or be built of atoms and molecules arranged in form of a repeating
three-dimensional geometrical pattern [94]. Molecular mobility deter-
mines the supra-molecular structures (Fig. 2). Free volume, the non-
occupied space in a molecular matrix, changes differently with temper-
ature, which reflects the crystalline or amorphous structure. It increases
continuously and steadily by heating an amorphous glass. A relatively
obvious temperature interval could be observed after which the free
volume increases more significantly. The lower border or the mean of
this interval is glass transition temperature Tg. During or above this
temperature, molecule clusters are set free and start to rotate and slip
past each other. This state of amorphous powder is defined as glass tran-
sition. In contrast, discontinuous and critical temperature point which is
called melting temperature Tm could be observed by heating a crystal.
Blow this melting point, the vibration of molecules about their position
in lattice increases, while above that, the crystalline structure breaks
down totally. Due to the difference of amorphous powder and crystal,
substance properties, i.e. hygrocapacity, hygrosensitivity, mechanical
properties, and diffusion behavior, differ significantly, which deter-
mines various caking mechanisms.
Hygrocapacity is the ability to bind water by absorption on the
surface and into the molecular matrix, which describes an extent
that the thermoplastic properties change as a result of absorption
of water [94]. Water content of the product is usually considered to
be the most important factor in promoting caking. In some caking
situations, the presence of moisture is essential [33]. Hygrocapacity
behavior therefore determines activation, extent, rate of some caking
processes. In general, a substance in amorphous state presents higher
hygrocapacity than that in crystalline state (Fig. 3). Due to the molecular
mobility (Fig. 2), an amorphous moisture sorption curve is continuous
and steady while a crystalline one increases significantly above a critical
relative humidity that is generally called deliquesces point [95].
Hygrosensitivity is the changes in physico-chemical properties of
substance linked to changing water content. For amorphous powders,
water migrates into the molecular matrix and changes the free volume,
which presents a decrease of glass transition temperature [94]. With the
increasing water content, these powders absorb the water molecules
and the viscosity decreases steadily until they disintegrate into single
molecules. In contrast, crystals maintain the mechanical properties
with increasing humidity until they dissolve at the critical relative
humidity. Crystals dissolve layer by layer from the outside without
water migration into the supra-molecular structure.
Mechanical properties refer to viscous and elastic elements.
Amorphous powders in glassy state behave more like elastic solids,
while in rubbery or viscous state they exhibit liquid-like properties.
As a result of these mechanical properties, amorphous powders
tend to present sticky surface and plastification. Powders therefore
are preferable to contact, adhere, and cake. For the crystals, the me-
chanical properties are comparably much more constant against
temperature and humidity. In general, crystals present low viscosity
and elasticity.
Diffusion behavior is the permeability of water or solution into mol-
ecules matrices. Due to the high free volume and macroscopic porosity,
diffusion of amorphous powders is fast and easy to form a liquid film on
 M. Chen et al. / Chinese Journal of Chemical Engineering 27 (2019) 1429–1438 1431

Table 1
History of caking study

Time Keywords Reviews

1920s • Caking of salts Lowry and Hemmings [2] reported a systematically research about caking of salts. Nitrate, anhydrous compounds,
• Macroscopic and qualitative study hydrated salts, loss of sulfur dioxide during caking, contraction during caking of copper sulfate were studied
• Causes and prevention of caking macroscopically and qualitatively. The common causes of caking in soluble salts were summarized: (1) evaporation of
moisture from a wet salt; (2) mechanical stress; (3) recrystallization of fine particles; (4) recrystallization of
metastable crystalline forms; (5) recrystallization of amorphous material. Based on the static long-term caking tests,
the caking behaviors of the salts were described qualitatively. It was concluded that caking of salts is most likely to take
place: (1) in crystalline salts that are very soluble; (2) in hygroscopic and deliquescent substances; (3) in crystalline
hydrates; (4) in substances that are liable to decompose in the presence of moisture. In order to minimize the trouble
of caking, the following measures were suggested: (1) minimize the number and amount of soluble impurities;
(2) large crystals are preferred; (3) minute unground crystals for a finer product; (4) drying with agitation after
grinding; (5) temperature and humidity of production process, drying, grinding, package, and storage are preferred
to be low and constant. Special methods of preventing caking were also discussed theoretically. Foreign materials,
e.g. other salts or colloid, so-called anti-caking agent in some extent nowadays, could be mixed into the product to
decrease the risk of caking. However, it was thought to be impracticable for industrial purposes due to the limitation of
test results (large amount of foreign materials). In 1922, Lowry continued caking research about expansion and
shrinkage of salts caking. This phenomenon was explained by the conversion of hydrates [21].
1950s • Fertilizers caking Researchers paid more attention to caking of fertilizers. More macroscopic investigations were reported with the methods of
• Bag-storage tests bag-storage tests and photograph analysis. Based on these studies, “bonding-phase” was thought to be responsible for
• X-ray crystallographic method caking formation [22]. In the meantime, with the aid of X-ray crystallographic and optical methods, and caking testers for
• Surface active agents determination of strength under compression, some quantitative studies about temperature, humidity, stress began to be
reported. Small needle-shaped crystals of ammonium chloride growing outwards from the granules in the presence of
moisture were observed, which was supposed to be the cause of caking [23,24]. On the other hand, the influence of surface
active agents to caking caused controversy. Some agents were found to be effective of preventing caking. However, more
evidences of plant scale tests showed no significant reduction in caking tendency during a long-term storage [25].
1960s • Fertilizers caking Research about caking of fertilizers was developed due to improvement of caking apparatus and testers [26]. Tucker and
• Food caking Roy [26] proposed a relative reliable technique routine for the fertilizers caking. A caking apparatus was utilized to
• Caking apparatus and tester simulate a loading force which would be experienced by a bag of fertilizer at the bottom so that the caking process was
• Salt bridge/crystal bridge accelerated instead of time-consuming plant scale tests. Furthermore, conditions of temperature, humidity and stress
• Anti-caking agent could be relative constant. A breaking strength apparatus was utilized to measure the sample's breaking strength which
could be defined as caking intensity today. X-ray Diffraction was adopted for the microscopic study. Based on this routine,
the bonding phase, also called salt bridge or crystal bridge in this research, was analyzed as a complex salt. The
relationship between caking of ammonium phosphate fertilizer, the titration mole ratio and moisture content was
investigated. Results showed that caking was enhanced by increasing the amount of the complex present and structure,
moisture content, and fluctuation of moisture. In the meantime, anti-caking agent began to be adopted for solving caking
problems of food powders. Peleg et al. investigated the influence of 17 anti-caking agents, including calcium stearate,
aluminum silicate, etc., on onion powder. Due to no method for the prediction of the tendency of a powder to undergo
caking, or for measuring the rate of caking, similar bag-storage test was adopted for the effective anti-caking agents and
proper storage condition of moisture content and temperature [27].
1970s– • Accelerated caking test Accelerated caking tests, the caking experiments with controlling stress, recycle of temperature and humidity, and
1980s • Caking mechanism developed caking testers on lab scale, were developed to simulate the real caking behavior of bag storage on plant scale
• Crystallization [28]. These accelerated caking tests overcame the problems of time-consuming, large amount of samples, accuracy of
• Phase transition ambient conditions. Sjolin studies the mechanism of caking of ammonium nitrate prills via X-ray diffractography,
• Model of caking strength scanning-electron microscopy, and tests in a climate chamber. The key was found to be the transition of IV and III at 32 °C
and depends on the dissolution and recrystallization of the solid at this phase transition [29]. Lafci et al. investigate the
ammonium nitrate with an optimized caking apparatus whose molds can be split into halves so that the cake formed can
be taken without any breakage to measure its hardness. The results supported Lafci's conclusions [30]. Otsuka proved the
salt bridge of caking via moisture sorption isotherm. Result shows a relationship between porosity and caking intensity
[31]. It must be noted that, in 1978, Tanaka developed a model to evaluate the ultimate caking strength of powder. It is
based on the contacting spheres with pendular water. Solubility, mass transfer rates, strength of crystalline structure were
considered for the evaluation. Results showed good agreement with order, various ambient conditions and time [32].
1990s • Review of fertilizer caking Caking of amorphous powders and crystalline substances were both reviewed. Rutland et al. reviewed the mechanisms,
• Review of amorphous food powders caking factors and prevention of fertilizer caking. Compared with the summary of Lowry et al. in 1920, this review emphasized
• NMR (nuclear magnetic resonance) the attribution of salt/crystal bridge in caking process. The influential factors included not only chemical composition,
moisture content, mechanical strength, hygroscopic properties, product temperature, ambient conditions, and storage
pressure, but also particle structure and storage time. In addition, anti-caking agent was regarded as the one of most
effective methods of preventing caking. The types, action, and screening of anti-caking agents for fertilizers were
discussed [33]. Aguilera et al. reviewed the amorphous caking of food powders. The mechanism was considered to be the
glass transition. Characterization, kinetics, microstructural were summarized. Anti-caking agent was the first method of
preventing caking mentioned in this review. Others are increasing Tg and forming a moisture-protective liquid barrier [4].
NMR technique was adopted to measure Tg by Logyd et al. [34]. Accelerate caking tests continued to be developed as an
important method on lab scale up to now [35]. In those years, caking of powders containing oily material, swelling
phenomenon during hydrate formation in crystalline caking processes, screening anti-caking agents via crystallization
experiments, the influence of particle size on caking were also studied [36,37].
2000s to • Novel caking testers A number of studies focused on the macroscopic behavior of caking. In the meantime, the novel analyzing techniques
now • TGA/SDTA (thermal gravimetric analysis provided an insight of molecular mobility and microscopic surface properties of caked powders. Simulation of caking
integrated with single differential behavior was developed based on the research above. Basically, three aspects of research were provided:
thermal analysis) (1) Macroscopic research includes novel caking testers, influential factors of caking, anti-caking agents, and the basic
• AFM (atomic force microscopy) models. Accelerated caking tests with novel testers were kept being developed to investigate the influential factors on
• Microscopic caking behavior solid/liquid bridge, moisture sorption, glass transition, caking strength, compression, intensity, deliquescence lowing,
• Caking simulation etc. [12,38–71]. Thermodynamic and kinetic models for moisture behavior and formation of liquid/solid bridges were
proposed [72–80]. The impacts of anti-caking agents on caking behavior and these impacts under various ambient
conditions were investigated [61,81–83].
(2) Novel application of technique and theory for study of microscopic caking behavior. Chung et al. selected 23 food
powders and ingredients for glass transition measurement via NMR technique. Two types of physical changes during

(continued on next page)

1432 M. Chen et al. / Chinese Journal of Chemical Engineering 27 (2019) 1429–1438

Table 1 (continued)

Time Keywords Reviews

the temperature scans from 20 to 110 °C had been observed: slow and gradual agglomeration and water vaporization;
abrupt caking. According to the temperature curve patterns, the caking behaviors of powders were divided into 4
groups. These differences of NMR data reflected the molecular mobility and indicated the caking mechanisms [84–86].
An increase of molecular mobility could be analyzed when caking occurs [87]. In the work of Listiohadi et al., the
thermal profiles of the dairy powders were described by TGA/SDTA and used to monitor the water content of the
powders (i.e. free water, water of crystallization, bound water by compounds such as protein and total water) [88].
AFM (atomic force microscopy) was adopted for characterizing microscopic morphology of particle surfaces during
caking in the work of Prime et al. [89]. Bode et al. utilized AFM to observe step pinning of NaCl crystal caused by the
anticaking agents, which indicated a blocking mechanism for crystal growth [90,91].
(3) Simulation of caking behaviors. Wahl et al. simulated the two-dimensional particles loading of caked system with a
contact-dynamics model. A complete crystal bridge strength distribution of contact force network was analyzed [92].
Thakur et al. presented a numerical study of the packing, compression, and caking behavior of spray dried detergent based
on the DEM (discrete element modeling) using a three-dimensional elasto-plastic adhesive-frictional contact model [93].

Fig. 2. Illustration of relationship of molecular mobility, supra-molecular, and substance properties.

the surface, whereas crystals tend to form liquid bridge on the contact
points of particles instead of whole surface.
3.2. Amorphous caking
Amorphous caking is a unique caking mechanism of amorphous
powders, which is common in food industry. The studied substances
in literature include amorphous lactose, diary milk powder, onion pow-
der, fish protein hydrolyzates, juice powder, meat, fruit and vegetable
extract powders, etc. [52,62,84,96]. As a result of molecular mobility,
glass transition occurs and causes the change from glassy to rubbery
state in the Tg range, which is a potential motivation of amorphous
caking. Fig. 4 illustrates a typical amorphous caking process. Individual
powders in glassy state contact at first. With temperature increasing
and exceeding the Tg, molecule clusters start to set free and slip past
each other, which caused the change of free volume. The visco-elastic
properties of amorphous matrices therefore vary greatly. The contact
points become flatten due to elastic property, which leads to contact
area increasing. In additional the powders stick together as a result of
viscous property. Based on the changes of the powder system and an
effective contact time, a bonding between individual powders grows
called sintering. Eventually a decrease of temperature facilitates the
powder system back into glassy state and causes caking.
It should be noted that amorphous powder crystallization may occur
in an amorphous caking process. The change of compositions signifi-
cantly affects sintering bridge, e.g. kinetics of sintering, radius of bridge,
and mechanical strength of bridge. Yoshioka et al. reported crystalliza-
tion of indomethacin from the amorphous state in the temperature
range of 20 °C above and below its Tg. Samples' significant crystallization
to the most stable polymorphic form occurred over several days when
stored below Tg. At storage temperatures near to and above Tg the
rates of crystallization increased as expected but a second less thermo-
dynamically stable polymorph also appeared with the more stable
crystal form [97]. Schmitt et al. reported that amorphous lactose
appeared to give a mixed product consisting different crystal forms
due to nucleation and growth above Tg [98]. According to these reports,
crystallization of amorphous powders is a non-negligible issue. How-
ever, it would be much more complicated to study amorphous caking
considering this issue. In spite of it, it may be a necessary and challeng-
ing topic in further study.

3.3. Humidity caking

Humidity caking is facilitated by a liquid bridge caused by moisture

Fig. 3. Illustration of moisture sorption behavior of amorphous powder and crystal.
sorption. It is regarded as the one of most important caking processes in
the literatures [99]. Generally, liquid bridge is easier to be facilitated due
to the changes of ambient conditions, i.e. relative humidity, tempera-
ture, and stress. Besides, the capillary force caused by liquid bridges is
much higher than the van der Waals force between particles. Conse-
quently, particles show stronger tendency to bond each other. Hence,
the extent of caking caused by a humidity caking process is commonly
significant.
 M. Chen et al. / Chinese Journal of Chemical Engineering 27 (2019) 1429–1438
Fig. 4. Illustration of an amorphous caking process.
The typical humidity caking processes of amorphous powders and
crystals are summarized in Fig. 5. For amorphous humidity caking
(Fig. 5(a)), due to the continuous moisture sorption behavior, molecular
free volume, and macroscopic porosity, amorphous powders contain
more water content than crystalline ones. The condensed water forms
both liquid bridges between neighboring powders and diffusion into
molecular structures. It causes a decrease of viscosity and increase
of elastic property, which leads to a plastification and sintering on the
contact point. With the RH decreasing, a sintering bridge is generated
due to the glassy state. As to the crystals, two main caking processes
are presented based on their discontinuous moisture sorption behavior
(Fig. 3). Capillary condensation may occur when the RH is below the
deliquescence point. Water condenses on the contact point of crystals
only and forms a liquid bridge. It causes dissolution and capillary
force. Recrystallization facilitated by RH decreasing generates a crystal
bridge, which eventually causes caking (Fig. 5(b)). Fig. 5(c) shows
that large amount of water would condense on the crystal surfaces if
the RH exceeds the deliquescence point. A liquid bridge with a larger
diameter or even a liquid film around the crystals forms. The surfaces
of caked crystals may deform due to the severe recrystallization.
3.4. Factors of amorphous and humidity caking
It is of great importance to investigate the factors of caking processes
for the mechanism study and industrial control. The summary in
Section 2 has shown that most researchers focused on the factors of
Fig. 5. Illustrations for humidity caking processes of amorphous powders and crystals. a) Amorphous humidity caking. b) Crystalline humidity caking caused by capillary condensation.
C) Crystalline humidity caking caused by deliquescence.
1433
caking and tried to find the key factor of given substance. Theoretically,
caking phenomena are triggered by the changes of substance properties
caused by molecular mobility. Furthermore, the molecular mobility
depends on temperature and pressure [94]. It therefore could be con-
cluded that temperature and humidity are the key factors of caking
processes. In addition, according to the previous studies showed in
Section 2, the subsidiary factors include particle size distribution,
particle shape, consolidation time, stress, etc. (Fig. 6).
For amorphous powders, the ambient temperature and glass transi-
tion temperature determine the caking behavior. Amorphous caking
occurs when ambient temperature exceeds Tg. While a temperature
lower than Tg may facilitate humidity caking. RH has a great impact on
Tg [4,5,94]. The work of Aguilera et al. shows that an increase in the
water activity from 0 to 0.64 reduced the Tg of samples from 79.1 to
− 42.8 °C [96]. In an amorphous humidity caking process, humidity
determines the water content and consequently the sintering, which
plays a key role in sintering bridge formation. As to the subsidiary
factors, consolidation time and stress have relatively more impacts on
these two caking process. Because of the viscous and elastic properties,
necessary consolidation time should be provided for sintering and
higher stress leading to significant plastification and increase of contact
area which enhanced the caking processes.
For crystals, temperature and humidity determine two key
parameters, i.e. RH of capillary consideration and deliquescence, and
consequently two humidity caking processes. Although both caking
mechanisms are moisture sorption–dissolution–recrystallization, the
1434 M. Chen et al. / Chinese Journal of Chemical Engineering 27 (2019) 1429–1438

extents of caking and morphology of final agglomerates are significantly The contact time between amorphous particles required to develop
different. In general, crystals present smooth surfaces and hardness sufficient adhesion force to lead to caking could be calculated by Eq. (3)
structure against the stress and diffusion. As a result, the particle size [6]:
and distribution, and particle shape are relatively important factors. !
5X 2 π  r 2
Needle-like or plate-like fine crystals are preferable to cake. The reason
t¼ ηðT Þ ð3Þ
is the increase of contact area and moisture sorption due to radius of 4γXπ þ 2 F t X
meniscus.
The sufficient inter-particle adhesion force for ðXr Þ is assumed to be
4. Methods 0.1. η(T) could be calculated by Eq. (4) [103]:

Based on the discussion about factors of caking and history, glass ηðT Þ ¼ ηg 10½C ðT−T g Þ=½BþðT−T g Þ ð4Þ
transition and moisture sorption should be focused on in the caking
study. In the meantime, characterization of caking and caking tests are
the important technique that should be developed. With the aid of 4.2. Water vapor sorption
these methods, the caking behavior may be simulated and predicted
via simulation software. These five aspects for studying caking were Moisture sorption is the prerequisite of humidity caking, which
summarized in this section. plays a key role in the caking process. In Fig. 3, the critical value of
RH that causes the significant increase of moisture sorption is called
4.1. Glass transition deliquescence point. Below the point, capillary condensation occurs at
the contact points of crystals. The amount of water caused by capillary
The measured glass transition temperature Tg strongly depends on the bridges could be calculated by the Kelvin equation [48,104]:
method and the measurement parameters applied. As already mentioned,    
%RH γ ∙ Vm 1 1
glass transition occurs in a relative temperature interval. As a result, the ln ¼− ∙ − ð5Þ
100 R∙T s l
values also depend on the definition. Due to the influences of ambient
conditions, the humidity should be controlled during measurement.
In general, Tg is determined by DSC (differential scanning calorimeter) Deliquescence would dominate the moisture sorption when the RH
with a heating and cooling process [51,60,96,100,101]. It should be noted exceeds the deliquescence point. The thermodynamics of deliquescence
that the rate of heating and cooling has a non-negligible impact on the can be considered by Eq. (6) [64,105]:
result. A slower DSC temperature scanning determined a relatively
μ ¼ μ 0 þ RT ln p0 ð6Þ
lower Tg. Hence, the rate is a key factor that should be the same during
measurement. Tg could also be determined via NMR. Free volume of
amorphous powders changes during glass transition, which leads to an The kinetics of deliquescence equation can be simplified as follows
increase of average internuclear distance. The changes could be directly [105,106]:
measured with proton spin–lattice relaxation time analysis [34].  
RH
According to the Fox and Flory equation below, the glass transition W ¼ ðD þ F Þ ln ð7Þ
RH D
temperature of linear monodisperse homopolymers is proportional to
the inverse of their molecular weight M [102]:
Dynamic vapor sorption (DVS) is commonly utilized for the mea-
surement. According to the water sorption curve, the amorphous pow-
2N A ρθ

¼ α f T g;∞ −T g ð1Þ ders and crystals could be distinguished. For the crystals, the RH of
M
capillary condensation and deliquescence could be determined. Based
on the water sorption behavior, the kinetics of crystals caking could be
The relationship between Tg and moisture was described by Eq. (2) calculated with the Knudsen formula [73]. Compared with the curves
[94]: of pure samples, samples incorporated anti-caking agent, mixed sam-
ples, the effectiveness of anti-caking agent, phenomenon of deliques-
ð1−wÞafs T gs þ wafw T gw cence lowing, and proportion of amorphous and crystalline substances
Tg ¼ ð2Þ
ð1−wÞafs þ wafw could be analyzed [64,73,107].

Fig. 6. Factors of amorphous and humidity caking. RHc is the RH of capillary condensation, RHD the RH of deliquescence. Factors connected by solid line are considered to be relatively more
important than the ones connected by dotted line.
 M. Chen et al. / Chinese Journal of Chemical Engineering 27 (2019) 1429–1438
4.3. Quantitative methods characterizing caking
Caking phenomenon is commonly characterized by flowability,
microscopic attributes and extent of caking. A bin or funnel is utilized
to characterize flowability by discharging mass flow rate. Angle of
repose is also a method to reflect the flowability [4]. Microscopic
attributes are ratio of system porosity to initial system porosity, ratio
of interparticle bridge diameter to particle diameter, aspect ratio, circu-
larity, convexity, sphericity, bluntness, etc. They could be measured via
image analysis. Extent of caking could be described as caking intensity,
caking strength, caking ratio, compressibility, etc. Caking intensity is
used to characterize the force breaking the cake [53]. Apparatuses
showed in Fig. 7(a), (b), (c), and (e) are typical for characterization of
caking intensity. Shear testers (Fig. 7(a) and (b)) are preferable for
the research due to the easy operation and low investment [44,108–
110]. Micromanipulation particle tester (MPT, Fig. 7(c)) provides con-
trollable conditions of pressure, temperature, humidity, and compres-
sion forces, which was utilized to study influence of environmental
conditions on caking intensity [60]. The advantage of the device to
apply pressure on particles (DAPP, Fig. 7(e)) is the ability to control
two individual particles contact and apart. The details of caking pro-
cesses and caking intensity could be observed, measured, and analyzed
[92]. Compressibility describes the shrinkage of the specimen during
caking, and the pressure is related to the extent of powder caking
[111]. A penetration tester (Fig. 7(d)) could determine the value. Cake
strength is the force holding the particles together [112]. It could be de-
termined by the blow tester (Fig. 7(f)). Caking ratio is the percentage of
detached particle [113], which characterizes the degree of caking. It is
generally measured by sieving [12,78,79].
4.4. Accelerated caking tests
Caking experiments were first carried out on plant scale, which is
called bag-storage test [22]. In storage tests, powders were bagged in
multiwall paper bags with asphalt-laminated moisture barriers. They
Fig. 7. Apparatuses for characterizing extent of caking. a) Jenike shear cell. b) Ring shear tester. c) Micromanipulation particle tester. d) Penetration tester. e) The device to apply pressure
on particles. f) Blow tester.
1435
were stored in the lower positions of several bag stacks which provide
stress in an unheated building. Bags were inspected after several
months of storage. They were removed from the stacks and were
dropped four times from a height of 3 ft, once on each side and face.
This experiment is time-consuming with unstable ambient conditions
and large amount of samples. Accelerated caking tests are the experi-
ments carried out in lab scale that simulate the caking process with
a given setting of ambient conditions and stress [26]. An accelerated
caking tester usually contains a climate chamber to control the temper-
ature and humidity with constant values or desired recycles. A control-
lable loading force at bottom simulates the bag stacks. These tests
therefore accelerate the caking process and could also obtain relatively
more accurate results [12,26,28,35,93]. Recently, devices with camera
and force applying system that control the contact of two individual
particles were developed. Thus the double-particle system under spe-
cific temperature and humidity could be observed in situ [47,60,92]. In
addition, DVS could also be regarded as an accelerated caking tester
due to the climate chamber of humidity and temperature [73,77]. How-
ever, it should be noted that the stress could not be controlled in this
device.
4.5. Simulation of caking behaviors
The ultimate goal of caking study is to predict the caking behavior
under given conditions, e.g. temperature, humidity, stress, impurities,
particle size and distribution, particle shape, and amount of anti-
caking agent. The industrial production routine therefore could be
designed and the process control could be achieved. However, as
already mentioned, caking processes are affected by a number of factors.
It is complex and time-consuming to investigate via experiments. Thus
the simulation of caking behavior with common property data of sub-
stances is of great importance. It could be achieved with two aspects
of investigation: (1) particle packing simulation, and (2) basic thermo-
dynamics and kinetics of substances. For the aspect of simulation, a two-
dimensional simulation with a contact-dynamics model and a DEM
1436 M. Chen et al. / Chinese Journal of Chemical Engineering 27 (2019) 1429–1438

simulation with a three-dimensional elasto-plastic adhesive-frictional
contact mode have been reported [60,92]. As to the aspect of basic ther-
modynamics and kinetics of substances, heat & mass transfer model,
relationship between moisture sorption with temperature, relationship
between glass transition and water content, model for predicting the
onset of caking and caking extent are required for amorphous powders
[51], while heat & mass transfer model, relationship between moisture
sorption with temperature, solubility and metastable zone, nucleation
and growth models, model for predicting the onset of caking and caking
extent are required for crystals.
5. Prospects
The work in the past century has provided relatively a large amount
of study that shows macroscopic caking mechanisms and some micro-
scopic change of properties during caking, especially after the 2000s.
Based on the present mechanisms and models, some researchers have
started to simulate and predict caking behavior. Several suggestions
are proposed below for the further study:
Properties of amorphous powder and crystal, i.e. hygrocapacity,
hygrosensitivity, mechanical properties, and diffusion behavior, de-
pend on the molecular mobility. Based on the significant difference
from these properties, four basic formations of caking processes are
summarized: amorphous caking caused by glass transition, humidity
caking caused by sintering of amorphous powders, humidity caking
caused by capillary condensation of crystals, humidity caking caused by
deliquescence of crystals. The key factors of these processes are temper-
ature and humidity which determine the formation of glass transition,
capillary condensation and deliquescence. Other factors are particle
size and distribution, particle shape, stress, consolidation time, etc.
The thermodynamic and kinetic models of glass transition and mois-
ture sorption, characterization of caking (e.g. flowability, microscopic
attributes, and extent of caking), accelerated caking tests, simulation
of caking with two- and three-dimensional models are summarized
for the design of industrial production routine and the process control.
Caking of mixed particles, caking with phase transition or poly-
morph transition, non-homogenous caking, and simulation of caking
are considered to be the most potential aspects for further study.

Nomenclature
(1) Caking of mixed particles. Caking of crystalline–crystalline,
afw a coefficient describing temperature dependency of the free
crystalline–amorphous and amorphous–amorphous particle
volume of the solid
systems should be studied. Both amorphous caking and humidity
af a coefficient
caking may occur in a mixture system. In additional deliques-
B constant
cence lowing phenomenon may also be facilitated. The caking
C constant
behaviors would be more complex and interesting.
D contribute to heat transport
(2) Caking with phase transition or polymorph transition. A caking
F contribute to heat transport
process with these phenomena would change the moisture
Ft force applied, N
sorption and component of solid bridge. For amorphous caking,
fs the fractional volume of the solid
crystallization of amorphous powders is non-negligible. Charac-
fw arithmetic mean of the fractional volume of water
terizing the crystallinity of sintering bridge is the key that should
l azimuthal radius of a meniscus, m
be focused on. For humidity caking, different polymorph forms
M molar mass
may be generated in solid bridge. Crystallographic theories
NA Avogadro number, number of molecules per mol
should be adopted for this study.
p0 the vapor pressure of pure water, Pa
(3) Non-homogenous caking. In most instances, studies assume that
R Kelvin radius, m
caking is a steady state process whereby all the powder subjected
RH relative humidity
to atmospheric moisture over time will gain strength homoge-
RHD RH of deliquescence
neously, or have used testing methodologies which cannot
RHc RH of capillary condensation
differentiate the effects of non-homogeneity [1]. However, non-
r diameter of the sinter bridge, m
homogenous caking is common in industrial production or
s radius of meniscus, m
plant scale experiments. This phenomenon should be studied
T temperature, K
via relationship of stress distribution and particle packing struc-
Tg glass transition temperature, K
ture, kinetics of moisture sorption and migration, kinetics of
Tg,s glass transition temperature of the solid, K
solid bridge formation, etc.
Tg,w glass transition temperature of water, K
(4) Simulation of caking. Particle packing simulation should consider
Tg, ∞ glass transition temperature of a polymer with an infinite
the factor of particle shape [114,115]. Compared with models for
molecular weight, K
predicting the onset of caking and caking extent of amorphous
t time, s
caking, the ones of humidity caking still need to be studied, espe-
Vm molar volume of the liquid, m3·mol−1
cially the models for predicting the caking intensity via crystal
W the sorption rate
bridge.
w water content (wet-based)
X the diameter of the particle, m
6. Conclusions γ surface tension, N·m−1
ηg the viscosity in the glassy state, mPa∙s
History of caking research in the past century is summarized. The η(T) the viscosity of the material at temperature T, mPa∙s
research of caking started from the caking problems of salts, especially θ the additional free volume delivered by each chain end,
fertilizers. The original caking experiments and characterizations were mm3·mol−1
bag-storage tests and photograph analysis on plant scale. Nowadays, μ Chemical potential, J
accelerated caking tests with climate chamber and stress applying sys- μ0 the standard chemical potential, J
tem or individual particle controlling system on lab scale could simulate ρ density, kg·m−3
the caking processes precisely. The techniques, e.g. DSC, NMR, DVS, and
AFM have been adopted for studying the macroscopic and microscopic References
changes of powder surfaces and structure during caking. The thermody-
namic and kinetic models of liquid/solid bridge formation and moisture [1] T. Freeman, K. Brockbank, B. Armstrong, Measurement and quantification of caking
in powders, Procedia Eng. 102 (2015) 35–44.
sorption are proposed. Some simulations reported the prediction of [2] T.M. Lowry, F.C. Hemmings, Properties of powders. I. Caking of salts, London Sect.
caking behavior in recent years. Soc. Chem. Ind. Faraday Soc. 39 (1920) 101–110.
 M. Chen et al. / Chinese Journal of Chemical Engineering 27 (2019) 1429–1438
[3] J.R. Adams, A.R. Merz, Hygroscopicity of fertilizer materials and mixtures, Ind. Eng.
Chem. 21 (1929) 305–307.
[4] J. Aguilera, J.D. Valle, M. Karel, Caking phenomena in amorphous food powders,
Trends Food Sci. Technol. 6 (5) (1995) 149–155.
[5] M. Carpin, H. Bertelsen, J.K. Bech, R. Jeantet, J. Risbo, P. Schuck, Caking of lactose: A
critical review, Trends Food Sci. Technol. 53 (2016) 1–12.
[6] S. Palzer, The effect of glass transition on the desired and undesired agglomeration
of amorphous food powders, Chem. Eng. Sci. 60 (14) (2005) 3959–3968.
[7] D.I.W. Pietsch, Agglomeration Processes: Phenomena, Technologies, Equipment,
Wiley, Darmstadt, 2008.
[8] A.B. Khadilkar, P.L. Rozelle, S.V. Pisupati, A study on initiation of ash agglomeration
in fluidized bed gasification systems, Fuel 152 (2015) 48–57.
[9] L. Malafronte, L. Ahrné, F. Innings, A. Jongsma, A. Rasmuson, Prediction of regions of
coalescence and agglomeration along a spray dryer — Application to skim milk
powder, Chem. Eng. Res. Des. 104 (2015) 703–712.
[10] F. Thielmann, M. Naderi, M.A. Ansari, F. Stepanek, The effect of primary particle
surface energy on agglomeration rate in fluidised bed wet granulation, Powder
Technol. 181 (2) (2008) 160–168.
[11] E.M. Ålander, Åke C. Rasmuson, Agglomeration and adhesion free energy of
paracetamol crystals in organic solvents, AIChE J. 53 (10) (2007) 2590–2605.
[12] J. Cleaver, G. Karatzas, S. Louis, I. Hayati, Moisture-induced caking of boric acid
powder, Powder Technol. 146 (1–2) (2004) 93–101.
[13] U. Bröckel, M. Wahl, R. Kirsch, H.J. Feise, Formation and growth of crystal bridges in
bulk solids, Chem. Eng. Technol. 29 (6) (2006) 691–695.
[14] W. Pietsch, Agglomeration in Industry, Wiley, Darmstadt, 2004.
[15] L. Wang, Influencing factors on caking of compound fertilizer and their counter-
measures, Ningxia J. Agric. For. Sci. Technol. 54 (1) (2013) 44–46.
[16] Y. Tong, Influencing factors and experimental method of edible salt caking, J. Salt
Chem. Ind. 42 (5) (2013) 8–13.
[17] L. Liu, Aggregation of silica nanoparticles in an aqueous suspension, AIChE J. 61 (7)
(2015) 2136–2146.
[18] X. Tan, H. Fenniri, M.R. Gray, Water enhances the aggregation of model asphaltenes
in solution via hydrogen bonding, Energy Fuel 23 (7) (2009) 3687–3693.
[19] A.W. Pacek, P. Ding, A.T. Utomo, Effect of energy density, PH and temperature on
de-aggregation in nano-particles/water suspensions in high shear mixer, Powder
Technol. 173 (3) (2007) 203–210.
[20] W.R. Richmond, R.L. Jones, P.D. Fawell, The relationship between particle aggregation
and rheology in mixed silica–titania suspensions, Chem. Eng. J. 71 (1) (1998) 67–75.
[21] T.M. Lowry, E.E. Walker, The properties of potyders. Part II. Expansion and shrink-
age during caking of potassium carbonate, Faraday Soc (1922) 78–81.
[22] J. Silverberg, J.R. Lehr, G. H. Jr, Fertilizer caking, microscopic study of the mecha-
nism of caking and its prevention in some granular fertilizers, J. Agric. Food Chem.
6 (6) (1958) 442–448.
[23] W.A. Mitchell, An investigation into the caking of granular fertilizers, J. Sci. Food
Agric. 5 (9) (1954) 455–456.
[24] A.L. Whynes, T.P. Dee, The caking of granular fertilizers: An investigation on a lab-
oratory scale, J. Sci. Food Agric. 8 (8) (1957) 577–591.
[25] W.J. Tucker, Surfactants in fertilizers, effects of surface active agents on caking of
stored mixed fertilizer, J. Agric. Food Chem. 3 (8) (1955) 669–672.
[26] G.L. Tucker, L.F. Roy, Caking in ammonium phosphate fertilizers, J. Agric. Food Chem.
17 (6) (1969) 1279–1283.
[27] Y. Peleg, C.H. Mannheim, Caking of onion powder, J. Food Technol. 4 (2) (1969)
157–160.
[28] R.L. Gilbert, P.W. Knapp, Development of an accelerated caking test for urea,
J. Agric. Food Chem. 18 (3) (1970) 397–400.
[29] C. Sjolin, Mechanism of caking of ammonium nitrate (NH4NO3) prills, J. Agric. Food
Chem. 20 (4) (1972) 895–900.
[30] A. Lafci, K. Gürüz, H. Yücel, Investigation of factors affecting caking tendency of
calcium ammonium nitrate fertilizer and coating experiments, Nutr. Cycl. Agroecosyst.
18 (1) (1988) 63–70.
[31] O. Akinobu, S. Kazumi, D. Kazumi, S. Hisakazu, S. Yusaku, Caking of δ-D-
gluconolactone powder, Chem. Pharm. Bull. 23 (1975) 673–676.
[32] T. Tanaka, Evaluating the caking strength of powders, Ind. Eng. Chem. Prod. Res. Dev.
17 (3) (1978) 241–246.
[33] D.W. Rutland, Fertilizer caking: Mechanisms, influential factors, and methods of
prevention, Nutr. Cycl. Agroecosyst. 30 (1) (1991) 99–114.
[34] R.J. Lloyd, X.D. Chen, J.B. Hargreaves, Glass transition and caking of spray-dried
lactose, Int. J. Food Sci. Technol. 31 (4) (1996) 305–311.
[35] G.M. Walker, C. R. H., M.N. Ahmad, J. N. F., A.G. Kells, Granular fertilizer agglomer-
ation in accelerated caking tests, Ind. Eng. Chem. Res. 38 (10) (1999) 4100–4103.
[36] N. Wakiyama, A. Kusai, K. Nishimura, Mechanism of caking of granules containing
oily materials, Int. J. Pharm. 78 (2–3) (1992) 95–102.
[37] Y.L. Chen, J.Y. Chou, Selection of anti-caking agents through crystallization, Powder
Technol. 77 (1) (1993) 1–6.
[38] B. Rogé, M. Mathlouthi, Caking of white crystalline sugar, Int. Sugar J. 105 (1251)
(2003) 128–136.
[39] C.I. Beristain, E. Azuara, T.T. Tamayo, E.J. Vernoncarter, Effect of caking and stickiness
on the retention of spray-dried encapsulated orange peel oil, J. Sci. Food Agric. 83 (15)
(2003) 1613–1616.
[40] M. Mathlouthi, B. Rogé, Water vapour sorption isotherms and the caking of food
powders, Food Chem. 82 (1) (2003) 61–71.
[41] Y. Yokogawa, Y. Shiotsu, F. Nagata, M. Watanabe, Apatite hydrogel and its caking
behavior, Key Eng. Mater. 254-256 (2003) 63–66.
[42] Y.D. Listiohadi, J.A. Hourigan, R.W. Sleigh, R.J. Steele, Role of amorphous lactose in
the caking of α-lactose monohydrate powders, Aust. J. Dairy Technol. 60 (1)
(2005) 19–32.
1437
[43] Y.D. Listiohadi, J.A. Hourigan, R.W. Sleigh, R.J. Steele, Properties of lactose and its
caking behavior, Aust. J. Dairy Technol. 60 (1) (2005) 33–52.
[44] M. Röck, J. Schwedes, Investigations on the caking behaviour of bulk solids-
macroscale experiments, Powder Technol. 157 (1–3) (2005) 121–127.
[45] A.K. Salameh, L.S. Taylor, Deliquescence-induced caking in binary powder blends,
Pharm. Dev. Technol. 11 (4) (2006) 453–464.
[46] B. Weigl, Y. Pengiran, H.J. Feise, M. Röck, R. Janssen, Comparative testing of powder
caking, Chem. Eng. Technol. 29 (6) (2006) 686–690.
[47] M. Wahl, R. Kirsch, U. Bröckel, S. Trapp, M. Bottlinger, Caking of urea prills, Chem.
Eng. Technol. 29 (6) (2006) 674–678.
[48] S.W. Billings, J.E. Bronlund, A.H.J. Paterson, Effects of capillary condensation on the
caking of bulk sucrose, J. Food Eng. 77 (4) (2006) 887–895.
[49] M. Röck, M. Ostendorf, J. Schwedes, Development of an uniaxial caking tester,
Chem. Eng. Technol. 29 (6) (2006) 679–685.
[50] R. Ruan, Y.J. Choi, M.S. Chung, Caking in food powders, Food Sci. Biotechnol. 16 (3)
(2007) 329–336.
[51] J.J. Fitzpatrick, M. Hodnett, M. Twomey, P.S.M. Cerqueira, J. O'Flynn, Y.H. Roos, Glass
transition and the flowability and caking of powders containing amorphous lac-
tose, Powder Technol. 178 (2) (2007) 119–128.
[52] J.J. Fitzpatrick, E. O'Callaghan, J. O'Flynn, Application of a novel cake strength tester
for investigating caking of skim milk powder, Food Bioprod. Process. 86 (3) (2008)
198–203.
[53] Y. Listiohadi, J.A. Hourigan, R.W. Sleigh, R.J. Steele, Moisture sorption, com-
pressibility and caking of lactose polymorphs, Int. J. Pharm. 359 (1–2) (2008)
123–134.
[54] J.J. Fitzpatrick, N. Descamps, K. O'Meara, C. Jones, D. Walsh, M. Spitere, Comparing
the caking behaviours of skim milk powder, amorphous maltodextrin and crystal-
line common salt, Powder Technol. 204 (1) (2010) 131–137.
[55] M.E. Chávez, N.A. Santamaría, J.C. Gumy, P. Marchal, Moisture-induced caking of
beverage powder, J. Sci. Food Agric. 91 (14) (2011) 2582.
[56] D.M. Oliveira, E. Clemente, J.M.C.D. Costa, Hygroscopic behavior and degree of cak-
ing of grugru palm (Acrocomia aculeata) powder, J. Food Sci. Technol. 51 (10)
(2014) 2783–2789.
[57] K. Arp, K.E. Ileleji, R.L. Stroshine, Stress relaxation behavior of corn distillers dried
grains with solubles (DDGS) in relation to caking, Powder Technol. 235 (3)
(2013) 209–211.
[58] G. Calvert, N. Curcic, C. Redhead, H. Ahmadian, C. Owen, D. Beckett, A new environ-
mental bulk powder caking tester, Powder Technol. 249 (11) (2013) 323–329.
[59] N. Descamps, S. Palzer, Y.H. Roos, J.J. Fitzpatrick, Glass transition and flowability/
caking behaviour of maltodextrin DE 21, J. Food Eng. 119 (4) (2013) 809–813.
[60] C.I. Haider, M.J. Hounslow, A.D. Salman, T.O. Althaus, G. Niederreiter, S. Palzer,
Influence of environmental conditions on caking mechanisms in individual amor-
phous food particle contacts, AIChE J. 60 (8) (2014) 2774–2787.
[61] S. Baueregger, M. Perello, J. Plank, Influence of anti-caking agent kaolin on film
formation of ethylene–vinylacetate and carboxylated styrene–butadiene latex
polymers, Cem. Concr. Res. 58 (58) (2014) 112–120.
[62] A.H.J. Paterson, U. Bröckel, Caking development in lemon juice powder, Procedia
Eng. 102 (2015) 142–149.
[63] C. Modugno, A.H.J. Paterson, J. Mcleod, Lactose caking: Influence of the particle size
distribution and the water content, Procedia Eng. 102 (2015) 114–122.
[64] M. Dupas-Langlet, M. Benali, I. Pezron, K. Saleh, L. Metlas-Komunjer, The impact of
deliquescence lowering on the caking of powder mixtures, Powder Technol. 270
(2015) 502–509.
[65] M.F. Saleh, R.M. Dhenge, J.J. Cartwright, M.J. Hounslow, A.D. Salman, Twin screw
wet granulation: Effect of process and formulation variables on powder caking
during production, Int. J. Pharm. 496 (2) (2015) 571–582.
[66] K. Brockbank, B. Armstrong, Y. Chandorkar, T. Freeman, Understanding powder
caking as a consequence of a range of mechanisms by means of powder
rheometry, Part. Sci. Technol. 33 (1) (2014) 102–108 (7).
[67] T.W.Y. Tham, C. Wang, A.T.H. Yeoh, W. Zhou, Moisture sorption isotherm and
caking properties of infant formulas, J. Food Eng. 175 (2015) 117–126.
[68] A.B. Albadarin, T.D. Lewis, G.M. Walker, Granulated polyhalite fertilizer caking
propensity, Powder Technol. 308 (2017) 193–199.
[69] M. Carpin, H. Bertelsen, A. Dalberg, C. Roiland, J. Risbo, P. Schuck, Impurities
enhance caking in lactose powder, J. Food Eng. 198 (2017) 91–97.
[70] J. Petit, F. Michaux, C. Jacquot, E.C. Montes, J. Dupas, V. Girard, Storage-induced
caking of cocoa powder, J. Food Eng. 199 (2017) 42–53.
[71] T.W. Tham, X. Xu, A.T. Yeoh, W. Zhou, Investigation of caking by fat bridging in
aged infant formula, Food Chem. 218 (2017) 30–39.
[72] M.C. Leaper, M. Bradley, J. Cleaver, Constructing an engineering model for moisture
migration in bulk solids as a prelude to predicting moisture migration caking, Adv.
Powder Technol. 13 (4) (2002) 411–424.
[73] L. Komunjer, C. Affolter, Absorption–evaporation kinetics of water vapour on
highly hygroscopic powder: case of ammonium nitrate, Powder Technol. 157 (1)
(2005) 67–71.
[74] N. Christakis, J. Wang, M.K. Patel, M.S.A. Bradley, M.C. Leaper, M. Cross, Aggre-
gation and caking processes of granular materials: Continuum model and numer-
ical simulation with application to sugar, Adv. Powder Technol. 17 (5) (2006)
543–565.
[75] S.W. Billings, A.H.J. Paterson, Prediction of the onset of caking in sucrose from tem-
perature induced moisture movement, J. Food Eng. 88 (4) (2008) 466–473.
[76] M. Hartmann, S. Palzer, Caking of amorphous powders — Material aspects, model-
ling and applications, Powder Technol. 206 (1–2) (2011) 112–121.
[77] M. Langlet, M. Benali, I. Pezron, K. Saleh, P. Guigon, L. Metlas-Komunjer, Caking of
sodium chloride: Role of ambient relative humidity in dissolution and recrystalli-
zation process, Chem. Eng. Sci. 86 (5) (2013) 78–86.
1438 M. Chen et al. / Chinese Journal of Chemical Engineering 27 (2019) 1429–1438
[78] M. Chen, S. Wu, W. Tang, J. Gong, Caking and adhesion free energy of
maltitol: Studying of mechanism in adhesion process, Powder Technol. 272 (2015)
235–240.
[79] M. Chen, L. Lin, Y. Zhang, S. Wu, E. Liu, K. Wang, J. Wang, J. Gong, Mechanism and
inhibition of trisodium phosphate particle caking: effect of particle shape and
solubility, Particuology 253 (8) (2015) 115–121.
[80] Z. Afrassiabian, M. Leturia, M. Benali, M. Guessasma, K. Saleh, An overview of the
role of capillary condensation in wet caking of powders, Chem. Eng. Res. Des. 110
(2016) 245–254.
[81] R.A. Lipasek, J.C. Ortiz, L.S. Taylor, L.J. Mauer, Effects of anticaking agents and
storage conditions on the moisture sorption, caking, and flowability of deliques-
cent ingredients, Food Res. Int. 45 (1) (2012) 369–380.
[82] D. Wang, J. Chu, J. Li, T. Qi, W. Wang, Anti-caking in the production of titanium
dioxide using low-grade titanium slag via the NaOH molten salt method, Powder
Technol. 232 (4) (2012) 99–105.
[83] P. Ramachandran, M.N. Poojitha, N. Srividya, Influence of maltodextrin and nutri-
tive anti-caking agents on quality characteristics and storage stability of papaya
powder, Res. J. Pharm., Biol. Chem. Sci. 5 (2) (2014) 1108–1123.
[84] M.S. Chung, R.R. Ruan, P. Chen, S.H. Chung, T.H. Ahn, K.H. Lee, Study of caking in
powdered foods using nuclear magnetic resonance spectroscopy, J. Food Sci. 65
(1) (2000) 134–138.
[85] M.S. Chung, R. Ruan, P. Chen, Y.G. Lee, T.H. Ahn, C.K. Baik, Formulation of caking-
resistant powdered soups based on NMR analysis, J. Food Sci. 66 (8) (2001)
1147–1151.
[86] M.S. Chung, R. Ruan, P. Chen, J.H. Kim, T.H. Ahn, C.K. Baik, Predicting caking behav-
iors in powdered foods using a low-field nuclear magnetic resonance (NMR) tech-
nique, Food Sci. Technol. 36 (8) (2003) 751–761.
[87] C.I. Cheigh, H.W. Wee, M.S. Chung, Caking characteristics and sensory attributes of
ramen soup powder evaluated using a low-resolution proton NMR technique, Food
Res. Int. 44 (4) (2011) 1102–1107.
[88] Y.D. Listiohadi, J.A. Hourigan, R.W. Sleigh, R.J. Steele, An exploration of the caking of
lactose in whey and skim milk powders, Aust. J. Dairy Technol. 60 (3) (2005) 207–213.
[89] D.C. Prime, A.G.F. Stapley, C.D. Rielly, J.R. Jones, M.C. Leaper, Analysis of powder
caking in multicomponent powders using atomic force microscopy to examine
particle properties, Chem. Eng. Technol. 34 (1) (2011) 98–102.
[90] A.A.C. Bode, S. Jiang, J.A.M. Meijer, W.J.P.V. Enckevort, E. Vlieg, Growth inhibition of
sodium chloride crystals by anticaking agents: in situ observation of step pinning,
Cryst. Growth Des. 12 (12) (2012) 5889–5896.
[91] A.A.C. Bode, M. Verschuren, M. Jansen, S. Jiang, J.A.M. Meijer, W.J.P.V. Enckevort,
Influence of anticaking agents on the caking of sodium chloride at the powder
and two-crystal scale, Powder Technol. 277 (2015) 262–267.
[92] M. Wahl, U. Bröckel, L. Brendel, H.J. Feise, B. Weigl, M. Röck, Understanding powder
caking: predicting caking strength from individual particle contacts, Powder
Technol. 188 (2) (2008) 147–152.
[93] S.C. Thakur, H. Ahmadian, S. Jin, Y.O. Jin, An experimental and numerical study of
packing, compression, and caking behaviour of detergent powders, Particuology
12 (1) (2014) 2–12.
[94] P. St, The relation between material properties and supra-molecular structure of
water-soluble food solids, Trends Food Sci. Technol. 21 (1) (2010) 12–25.
[95] A.M. Stoklosa, R.A. Lipasek, L.S. Taylor, L.J. Mauer, Effects of storage condi-
tions, formulation, and particle size on moisture sorption and flowability of
powders: A study of deliquescent ingredient blends, Food Res. Int. 49 (2) (2012)
783–791.
[96] J.M. Aguilera, G. Levi, M. Karel, Effect of water content on the glass transition and
caking of fish protein hydrolyzates, Biotechnol. Prog. 9 (6) (1993) 651–654.
[97] M. Yoshioka, B.C. Hancock, G. Zografi, Crystallization of indomethacin from the
amorphous state below and above its glass transition temperature, J. Pharm. Sci.
83 (12) (1994) 1700–1705.
[98] E.A. Schmitt, D. Law, G.G.Z. Zhang, Nucleation and crystallization kinetics of
hydrated amorphous lactose above the glass transition temperature, J. Pharm. Sci.
88 (3) (1999) 291–296.
[99] D. Dopfer, S. Palzer, S. Heinrich, L. Fries, S. Antonyuk, C. Haider, Adhesion mecha-
nisms between water soluble particles, Powder Technol. 238 (2013) 35–49.
[100] L.E. Chuy, T.P. Labuza, Caking and stickiness of dairy-based food powders as related
to glass transition, J. Food Sci. 59 (1) (1994) 43–46.
[101] L.O. Figura, The physical modification of lactose and its thermoanalytical identifica-
tion, Thermochim. Acta 222 (2) (1993) 187–194.
[102] T.G. Fox, P.J. Flory, Second-order transition temperatures and related proper-
ties of polystyrene. I. Influence of molecular weight, J. Appl. Phys. 21 (6) (1950)
581–591.
[103] M.L. Williams, R.F. Landel, J.D. Ferry, The temperature dependence of relaxation
mechanisms in amorphous polymers and other glass-forming liquids, JACS 77
(14) (1955) 3701–3707.
[104] H.J. Butt, M. Kappl, Normal capillary forces, Adv. Colloid Interf. Sci. 146 (1–2) (2009)
48–60.
[105] J.A. Baird, R. Olayo-Valles, C. Rinaldi, L.S. Taylor, Effect of molecular weight, temper-
ature, and additives on the moisture sorption properties of polyethylene glycol,
J. Pharm. Sci. 99 (1) (2010) 154–168.
[106] L.J. Mauer, L.S. Taylor, Deliquescence of pharmaceutical systems, Pharm. Dev.
Technol. 15 (6) (2010) 582–594 (13).
[107] S. Sheokand, S.R. Modi, A.K. Bansal, Dynamic vapor sorption as a tool for character-
ization and quantification of amorphous content in predominantly crystalline
materials, J. Pharm. Sci. 103 (11) (2014) 3364–3376.
[108] A.W. Jenike, Gravity Flow of Bulk Solids, Bulletin No. 108, Utah State University, 1961.
[109] J.J. Fitzpatrick, K. Barry, C. Psm, T. Iqbal, J. O'Neill, Y.H. Roos, Effect of composition
and storage conditions on the flowability of dairy powders, Int. Dairy J. 17 (4)
(2007) 383–392.
[110] J. Schwedes, Review on testers for measuring flow properties of bulk solids, Granul.
Matter 5 (1) (2003) 1–43.
[111] A. Hassanpour, M. Ghadiri, Characterisation of flowability of loosely compacted
cohesive powders by indentation, Part. Part. Syst. Charact. 24 (2) (2007) 117–123.
[112] P. Pierrat, H.S. Caram, Tensile strength of wet granular materials, Powder Technol.
91 (2) (1997) 83–93.
[113] P.G.C. Petean, M.L. Aguiar, Determining the adhesion force between particles and
rough surfaces, Powder Technol. 274 (2015) 67–76.
[114] T. He, W. Zhong, B. Jin, Comparison of construction method for DEM simulation of
ellipsoidal particles, Chin. J. Chem. Eng. 21 (7) (2013) 800–807.
[115] J. Emmerich, Q. Tang, Y. Wang, P. Neubauer, S. Junne, S. Maaß, Optical inline anal-
ysis and monitoring of particle size and shape distributions for multiple applica-
tions: Scientific and industrial relevance, Chin. J. Chem. Eng. 27 (2) (2019) 257–277.