European Polymer Journal xxx (xxxx) xxxx

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European Polymer Journal

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

In-situ modified cellulose nanocrystals as water droplet stabilizer in

polystyrene beads targeted for water expanded foam
⁎
Zahra Ajeloua, Nasser Nikfarjama, , Nader Taheri-Qazvinib,c
a
Department of Chemistry, Institute for Advanced Studies in Basic Sciences, Zanjan 45137-66731, Iran
b
Department of Chemical Engineering, University of South Carolina, Columbia, SC 29208, United States
c
Biomedical Engineering Program, University of South Carolina, Columbia, SC 29208, United States

A R T I C LE I N FO A B S T R A C T

Keywords: Synthesis of polystyrene beads containing well-dispersed water microdroplets via surfactant free Pickering
Cellulose nanocrystal emulsion polymerization in water-in-oil emulsion followed by suspension method. The water microdroplets with
In situ modification a diameter of 8–15 µm were stabilized using in situ modified cellulose nanocrystals (CNCs). The morphological
Inverse Pickering emulsion polymerization investigation revealed that the water droplets were surrounded by a dense layer of the modified CNCs. The
Water expanded polystyrene
thermogravimetric analysis confirmed two types of water inside the beads; free water and bound water with
release temperatures of 102 and 118 °C, respectively. The bound water was responsible for higher water pre-
servation ability and therefore long shelf-life of the beads, which over 75% of the initial entrapped water was
kept 7 months after synthesis. The beads can be expanded at an optimum temperature of 130 °C due to water
vapour pressure developed inside the beads. The best max expansion ratio of around 15 was found for the beads
included 5.45 wt% of water. During the expansion process, the CNCs were located in the cell wall to reinforce it
from rupturing. Eventually, we report a new type of water expanded polystyrene beads synthesized by the use of
CNCs, named CNCWEPS, with good expandability and extended shelf-life.

1. Introduction candidate to prepare Pickering emulsions used in food technology,

Solid particulate stabilized emulsions, commonly known as
Pickering emulsions, has gained more attention due to the superior
long-lasting stability against coalescence and the elimination of side
effects of surfactants in conventional emulsions [1]. In Pickering
emulsions, the solid particulate emulsifiers with intermediate wett-
ability are attached at the interfaces of two immiscible liquids to pro-
vide a steric hindrance against droplet coalescence phenomenon. The
main force of the stabilization process arising from the Gibbs free en-
ergy penalty caused by detaching of solid particles from the interface
[2–4]. Various particles with different shape and dimension ranging
from nanometer to micrometer have been used as particle emulsifier in
Pickering emulsions [1]. Among them, particles derived from natural
biopolymers such as protein [5], chitin [6], chitosan [7], casein [8], egg
yolk granules [9], soy glycinin [10], zein [11,12] and starch [13] have
recently drawn considerable attention due to the low-cost raw mate-
rials, safe application, broad range of chemical applications, biode-
gradability, non-toxic character, wide availability, renewability and
sustainability.
Cellulose, as the first abundant polysaccharide, is an excellent
cosmetic formulations, pharmaceutical products, and composite in-
dustry. Cellulose in different size and shape and also in different deri-
vative have been used as Pickering emulsion stabilizer such as re-
generated cellulose [14,15], hydrophobized bacterial cellulose [16],
quaternized cellulose hydrogel [17], stearoylated microcrystalline cel-
lulose [18], hydrophobized microfibrillated cellulose [19], cellulose
nanofiber [20], bacterial cellulose nanofiber [21–23], cellulose nano-
crystals [24–33], bacterial cellulose nanocrystals [23,34], cellulose
nanowhisker [35,36] and ethyl cellulose nanoparticle [37]. Moreover,
the nanoparticles from biopolymers can combine the advantageous
properties of biopolymers with the features of nanomaterials, which in
turn has broadened the spectrum of potential applications. It was found
that the size of particles had more effect than shape on emulsion sta-
bility, so that stabilized emulsion droplets by the smaller particles
showed better stability against coalescence and Ostwald ripening due to
their higher packing efficiency in forming a dense, uniform and
homogenous layer round the droplets [38–40]. Also, the native cellu-
lose base materials are highly hydrophilic and therefore are generally
not absorbing at the water-oil interface to stabilize emulsion droplets.
Hence in the most of the case, they should be chemically modified to

⁎
Corresponding author.
E-mail addresses: z.ajelu71@yahoo.com (Z. Ajelou), nikfarjam@iasbs.ac.ir (N. Nikfarjam), ntaheri@cec.sc.edu (N. Taheri-Qazvini).

https://doi.org/10.1016/j.eurpolymj.2019.109343
Received 17 July 2019; Received in revised form 22 October 2019; Accepted 31 October 2019
0014-3057/ © 2019 Elsevier Ltd. All rights reserved.

Please cite this article as: Zahra Ajelou, Nasser Nikfarjam and Nader Taheri-Qazvini, European Polymer Journal,
https://doi.org/10.1016/j.eurpolymj.2019.109343
Z. Ajelou, et al.
bring partially hydrophobicity to surface of these materials
[16,18,19,24,27,28,30,32,33,37].
In our previous works, we have reported the synthesis of poly-
styrene (PS) beads by the polymerization of styrene in the water-in-oil
emulsion followed by suspension polymerization, in which water mi-
crodroplets are stabilized by the crosslinked starch nanoparticles
(CSTNs) [41], and the cellulose nanofibrils (CNFs) [42]. Both of these
nanoparticles were in situ modified by the synthesis of styrene-maleic
anhydride (SMA) copolymer during the emulsification and poly-
merization. It was found that this strategy leads to a better attachment
of SMA onto the nanoparticle’s surface and modifies thier wettability
for absorbing at the the water-partially polymerized styrene interphase.
The formation of chemical and physical linkages occurs through
forming of esteric and hydrogen bonds between hydroxyl groups on the
surface of CNFs and CSTNs and maleic anhydride groups present in the
SMA chains [41,42]. The obtained PS beads containing water micro-
droplets can be expanded over 7–14 folds by immersing in a hot oil bath
at 130 °C [43,44]. In this case, water acts as an eco-friendly blowing
agent, to form water expanded polystyrene (WEPS) materials.
Despite this, the water-loss during expansion process and storage
period is still primary challenge to the commercialization of WEPS.
Therefore, with the aim of obtaining a higher expansion ratio, a more
efficient processing than can effectively avoid water permeation out
was developed in this study. The platelet shape along with the packed
and crystalline structure of CNCs encouraged us to utilize them in the
synthesis of new WEPS materials through Pickering emulsion poly-
merization. CNCs in this system act simultaneously as water absorbing
agent and particulate emulsifier to stabilizer water droplets inside the
polystyrene beads. Limited works have been published in the literature
on the use of CNCs in multi-emulsion systems. Cunha et. al., prepared
double emulsion of oil-in-water-in-oil (o/w/o) in which laurylated
CNCs and laurylated CNFs were used as stabilizer of oil-in-water and
water-in-oil emulsion, respectively [45]. And, Zhu et al., prepared
double emulsion of water-in-oil-water (w/o/w) in which oleic acid
coated magnetic nanoparticles and CNCs were used as stabilizer of
water-in-oil and oil-in-water emulsion, respectively [46]. As well, lo-
cating CNC particles inside the polymer matrix of WEPS materials is
expected to result in enhanced mechanical strength of polymer matrix
and act as an efficient barrier against water diffusing out of the PS
beads.
2. Experimental
2.1. Materials
The polystyrene with Mn = 100,000 g·mol−1 was supplied by Alfa
Aesar. Styrene, benzoyl peroxide with a half-life of 145 min at 90 °C,
maleic anhydride, toluene, sulfuric acid, and hydrochloric acid were
obtained from Merck. Hydroxyethyl cellulose (HEC, with average mo-
lecular weight of 250,000 g·mol−1) as suspension stabilizer was pur-
chased from Sigma-Aldrich and used as received. All reagents were used
without further purification. Distilled water was used for all experi-
ments.
2.2. Preparation of cellulose nanocrystals (CNCs)
CNCs were synthesized through acidic hydrolysis of Whatman paper
No.4. Briefly, 5 g of the chopped paper was added to 30 ml of sulfuric
acid 64% at 45 °C and continuously stirred for 90 min [47]. Next, the
solution was centrifuged at 11,000 rpm for 20 min and the resulting
precipitate was separated and redispersed in distilled water and again
centrifuged several times till pH > 5 was achieved. For further pur-
ification and also to achieve neutral pH, the resulting precipitate was
dialyzed against distilled water using dialysis tube for at least 3 days.
The final aqueous CNC dispersion was lyophilized and then stored at
4–6 °C. For each sample preparation, the CNCs powder was redispersed
2
European Polymer Journal xxx (xxxx) xxxx
Table 1
Suspension polymerization recipe.
Component Content (g)
Styrene 20-K
CNC# K
Polystyrene (18/100) × (20-K)
BPO# (0.5/100) × (20-K)
Maleic anhydride 1
Water (emulsified) (0.5/100) × (20-K)
Water (suspension) 60
HEC# 0.06
#
CNC: cellulose nanocrystals, BPO: benzoyl peroxide and
HEC: hydroxyethyl cellulose.
in water for at least 4 h and then homogenized with aide of ultrasound
waves (Qsonica, model Q-700, USA, with an intensity of 10% for 20 s)
before use.
2.3. Synthesis of polystyrene beads in w/o/w system
In the first step to synthesize polystyrene beads containing CNC-
stabilized water droplets, polystyrene along with benzoyl peroxide and
maleic anhydride were dissolved in inhibitor-free styrene according to
Table 1. After complete dissolution, the mixture was heated at 90 °C
under N2 atmosphere for 75 min to attain monomer conversion of
around 25%, determined by the gravimetric method. Afterward, an
aqueous dispersion of CNC was added to the partially polymerized
styrene mixture under stirring at 250 rpm and temperature of 90 °C for
2 min to create particulate stabilized inverse emulsion. It worth to
mention that the stirring more than 2 min was leading to emulsion
failure. To break the large droplets into the small ones and also obtain a
homogenous dispersion of water droplets, the mixture was sonicated for
80 s at 500 W. Then, the obtained inverse emulsion was transferred
quickly to a 250 ml three-neck glass reactor containing water and HEC
to form a water/oil/water system (Table 1). The reactor was equipped
with a mechanical stirrer, condenser and baffle to reduce the turbulence
of fluid flow. The suspension was heated for 20 h at 90 °C under N2
atmosphere while stirring at 350 rpm to complete the polymerization.
Finally, the suspension was cooled to room temperature, and the shiny
white spherical beads were obtained and washed with water several
times (Scheme 1). The yield of polystyrene beads was around 80% for
all samples.
2.4. Polystyrene beads fractionation
To confirm the in situ surface-modification of nanoparticles during
the polymerization-emulsification process, the grafted CNC was sepa-
rated from the polymer matrix using Soxhlet extractor. For this purpose,
8 g of the dried polystyrene beads were transferred into a cellulose
thimble and then placed in the extraction chamber of Soxhlet. To avoid
transfer of nanoparticles into the distillation flask, the thimble was
plugged and sealed with Whatman paper No.4. The extraction process
was performed for 72 h with toluene. The obtained surface-grafted
CNCs was dried in vacuum oven at 50 °C for 24 h and then character-
ized by FT-IR and contact angle analysis.
2.5. Expansion of WEPS beads
For all samples, beads with diameter of 4–5 mm were sieved and
used for expansion. The beads were expanded by exposure to the hot oil
bath (at an optimum temperature of 135 °C) followed by quenching by
cold water at a given time. The expansion ratio (ε) was calculated by
the following equation;
Ve d
ε= = e
V0 d0
Z. Ajelou, et al.
Scheme 1. Preparation of in situ modified CNC stabilized w/o emulsion (A) followed by polymerization of styrene in w/o/w system (B).
where, V0 , Ve , d 0 and de are the volume of a compact bead, the volume of
an expanded bead, the diameter of a compact bead and the diameter of
an expanded bead, respectively. The diameter of beads before and after
the expansion was measured by micrometer three times to determine
the average expansion ratio.
2.6. Characterization
2.6.1. Atomic force microscopy (AFM)
The morphology and size of CNCs were studied using AFM (Ara
Research Co., Iran) with a silicon tip operated in the tapping mode. For
sample preparation, a drop of a highly diluted aqueous dispersion of
CNCs was set on a clean mica surface and then dried in a vacuum oven
at 60 °C for 24 h. The size and shape were evaluated using SPIP 6.7.4
software.
2.6.2. Thermogravimetric analysis (TGA)
The incorporated water content stabilized by CNC particles inside
the as-synthesized WEPS beads was determined using a NETZSCH STA
409 PC/PG under N2 flow of 20 ml/min with the heating rate of 10 °C/
min from 30 to 600 °C. Also, the TGA measurements were performed
4.5 and 7 months after synthesis to study of water maintenance ability
of the final PS beads.
2.6.3. Fourier transform infrared spectroscopy (FT-IR)
The native CNCs and the surface-modified CNCs extracted from PS
beads were characterized by FT-IR spectroscopy using FT-IR spectro-
photometer (BRUKER, Vector 22, Germany) by preparing their KBr
pellets from 450 to 4000 cm−1. The samples were dried at 50 °C for 24 h
before characterization.
2.6.4. Contact angle
The extracted grafted-CNCs were pressed for 5 min at 74,000 bar
using stainless steel die-set hydraulic press into compact pellets 7 mm in
diameter. The contact angle was determined using deionized water
(5 µl), imaging by Canon SX230HS camera and calculating by Meazure
software. For more accuracy, three readings were taken. The pellets
were placed in a vacuum oven at 50 °C for 12 h before measurements.
3
European Polymer Journal xxx (xxxx) xxxx
2.6.5. Field emission scanning electron microscopy (FE-SEM)
The WEPS compact beads and the related expanded samples were
cut by a razor blade and then coated with a gold layer. Digital micro-
graphs from the cross-section of the samples were acquired using a
Hitachi S4160 field emission scanning electron microscope operating at
20 kV. The obtained micrographs were used to evaluate the mor-
phology and size of the water droplets in the unexpanded beads and the
foam cells in the expanded beads. The size of the water droplets and
foam cells were measured manually using JMicrovision 1.2.7 software.
At least 200 droplets and foam cells were characterized for each sample.
3. Result and discussion
3.1. Pickering emulsion polymerization of styrene in w/o/w system using
CNCs
Hydrophobization of particles derived from biopolymers is neces-
sary to act as an emulsion stabilizer for Pickering emulsions. However,
in-situ modification of particles during the emulsification and poly-
merization brings several advantageous including; (I) reduction of
processing steps, (II) shorter formulation cycle, (III) reduction or ex-
cluding of surfactants as well as organic solvents, (IV) well-dispersion of
particles in polymer matrix, (V) capability of upgrading to a continuous
polymerization process to make it easier to be industrialized. In this
study, the flake-like CNC particles with a length of 100–200 nm and a
thickness of 8 nm (Fig. 1) were utilized as solid particulate emulsifiers
to stabilize water droplets inside partially polymerized styrene in the
first stage, and to entrap the water droplets inside PS beads after
complete polymerization (Scheme 1). During the emulsification step
(Scheme 1A), an optimized viscosity of styrene/PS phase was required
to fixate the water droplets in styrene/PS phase and also break-down
the bigger CNC aggregates into the small aggregations and individual/
fresh particles to be efficiently acted as stabilizer. This required visc-
osity can also minimize the washing-out of CNCs from styrene/PS phase
to the suspension media. The optimized viscosity was attained by
adding 18 wt% of PS (Mn = 100,000 g·mol−1), relative to styrene con-
tent, and pre-polymerization of styrene up to 25% of monomer con-
version. To give suitable wettability to the CNCs acting as an efficient
emulsifier, an optimized content of maleic anhydride, 0.5 wt% related
to styrene content, was initially added to the styrene phase before
Z. Ajelou, et al.
Fig. 1. AFM micrographs of the prepared CNCs. Size evaluation revealed the thickness of approximately 8 nm and the length of 100–200 nm for CNCs.
polymerization. In the pre-polymerization step, both PS and styrene-
maleic anhydride (SMA) copolymer were obtained. The PS and SMA
chains modify the CNC's surface, and thus the hydrophilicity of CNC
was changed to partial hydrophobicity which is suitable for stabilizing
w/o emulsions (modification mechanisms will be discussed in the next
section). This surface modification also led to better compatibility of
CNCs with PS matrix which in turn prevented washing-out of CNCs
from PS bead to the suspension media during the final polymerization
step.
To characterize the internal morphology, the pearle like WEPS
beads were cut by a razor. The cross-section FE-SEM micrographs of the
PS beads showed that the water droplets were uniformly dispersed
throughout the bead (Fig. 2A–B). Fig. 2C–F show the morphology of the
internal wall of water droplets in more detail. The protruding spots on
the wall are related to the modified CNCs which form a wall around the
droplets and finally stabilize the water droplets. It seems that the par-
ticles can be arranged around the water droplets (Fig. 2E–F). This close-
packed form of particles around the droplets can be attributed to the
particle-particle interactions. Although SMA modified the CNCs during
the emulsification and polymerization, it is expected that there are still
some hydroxyl functional groups on the surface of CNCs.
It is worth to note that WEPS beads were prepared at different
content of maleic anhydride (0, 0.25, 0.5, 0.75, 1 and 2 wt% related to
the styrene content) and in agreement with previous findings
[41,42,48,49], the best results were obtained at 0.5 wt% of maleic
anhydride. In both higher and lower contents of maleic anhydride, non-
expandable PS beads were collected. Low maleic anhydride content
results in insufficient surface modification of CNCs with SMA and weak
anchoring strength of particles at the oil-water surface to stabilize water
droplets. On the other hand, at a high content of maleic anhydride,
because of the aggregation of SMA chains in the PS matrix, a phase
separation occurs which leads to the unstable emulsion and rough
morphology of the final PS beads.
3.2. In-situ modification of CNCs
Due to the hydrophilicity nature of CNC, it is immiscible with most
of the synthetic polymers. This immiscibility can lead to the phase se-
paration and agglomeration of CNCs in the PS matrix and therefore the
poor performance of the final products. Moreover, in the case of this
study, the hydrophobicity of CNCs can be a good reason to washing-out
from PS matrix to the media during the suspension polymerization. One
of the ways to cope with this problem is the introduction of polar
functional groups (carboxylic acid, anhydride, amine or epoxy) in the
PS chain. This partial manipulation of PS structure will lead to effective
interaction and hence good compatibility between the two components.
Among functional groups, the cyclic anhydride is expected to react
4
European Polymer Journal xxx (xxxx) xxxx
more quickly than the other ones. Consequently, in this work an opti-
mized content of maleic anhydride (0.5 wt% relative to the styrene
content) was added to the initial formulation. It is postulated that
maleic anhydride can compatibilize CNCs and polystyrene chains in
two ways; I) Grafting onto; styrene can copolymerize with maleic an-
hydride to produce styrene-maleic anhydride (SMA) copolymers in
different molecular weight and maleic anhydride content [49]. SMA
can be grafted on the CNC surfaces during the polymerization process
through the interaction (hydrogen bonding) and reaction (ester bond
formation) of the maleic anhydride groups in the copolymer with the
hydroxyl groups of the cellulose chains in CNCs. II) Grafting from;
absorbed maleic anhydride on the CNC surface through hydrogen
bonding can be copolymerize with styrene to produce SMA copolymers.
In both of these grafting mechanisms, formed radical sites by the in-
itiator or radical transfer from radical monomers on the CNC surfaces
can directly initiate co/homopolymerization of styrene from the CNC
surfaces. Both grafting mechanisms are illustrated in more details in the
supplementary data (Schemes S1 and S2).
To verify the in situ surface modification, the modified CNCs were
separated from the PS beads Soxhlet setup and investigated carefully.
AFM micrographs of the modified CNC showed a flake-like morphology
for the modified CNC (Fig. 3) similarly with the native CNCs (Fig. 1).
The surface evaluation revealed a rough surface for the modified CNC,
while the native CNC showed a smooth surface. Also, the size evalua-
tion disclosed an increase in thickness for the modified CNC in com-
parison with the native CNC (Fig. 3). The other evidence for surface
modification of CNCs can be obtained by FTIR. The FT-IR spectra of
neat polystyrene, maleic anhydride, CNC and modified CNC are com-
pared in Fig. 4. The native CNC shows some characteristic bands for
cellulose; CH2 bending at 1451 cm−1, CeOeC stretching in glycoside
ring at 1159, 1065 and 1082 cm−1, OeH bending of adsorbed water at
1635 cm−1, hydrogen bonded OeH stretching at 2900–3800 cm−1,
CeH stretching at 2850–2980 cm−1, S]O and SeO stretching of sul-
fate groups (existing sulfate at the surface of CNC) at 1204 and
715 cm−1, respectively (Fig. 4) [50]. While, the spectrum of SMA
grafted CNC shows that besides typical bands for CNC, additional bands
at 1157, 1451, 1491 and 1610 cm−1 are assigned to the aromatic ring
of styrene in SMA and bands at 1876 and 1781 cm−1 are assigned to the
cyclic anhydride group in SMA [51]. As well, the band at 1735 cm−1 is
assigned to C]O stretching of ester groups confirming the grafting of
SMA through the formation of ester group between anhydride groups in
SMA and hydroxyl groups in CNC surface.
The modified CNC was not soluble in water and therefore dispersed
in toluene after stirring at room temperature for a day. The affinity of
the native and modified CNC to water were evalute by measuring their
contact angles (θ) (Fig. S1). The measured values for the native and
modified CNC were 33 ± 1° and 92 ± 2°, respectively. One can be
Z. Ajelou, et al. European Polymer Journal xxx (xxxx) xxxx

Fig. 2. The cross-section FE-SEM micrographs (A–B) of prepared polystyrene beads (sample S-0.5-1). Cross-section FE-SEM micrographs of the water droplet and its
interior wall at different magnifications (C–F); The modified CNCs reside at the interface and physically stabilize the water droplets.

concluded that the modified CNC has less affinity to water than the droplets against coalescence phenomenon which in turn lead to a de-
native CNC and also it has suitable wettability to stabilize w/o emul- crease in the average droplet size and narrow size distribution [53].
sions. Furthermore, it has been proved that the energy needed to detach
a particle from the interface is the highest when θ is around 90° [52].
The high detaching energy is expected to give a robust and dense 3.3. Features of WEPS beads
particle network around the water droplets, resulting in high stability of
In order to find the best expansion ratio, two series of the PS beads

Fig. 3. AFM micrographs of the isolated in situ modified CNC. Size evaluation revealed that the modified CNC has a rougher surface than the native CNC confirming
surface modification by SMA and/or PS chains.

5
Z. Ajelou, et al. European Polymer Journal xxx (xxxx) xxxx

A B 1.0
1.02
Modified-CNC

Transmittacne

Transmittance

Transmittance
0.8
CNC 0.99

1876
1781

1491
1735

1157
0.6

1451
Maleic anhydride 0.96
CNC

1610
0.4 Modified CNC 0.93
Polystyrene

4000 3500 3000 2500 2000 1500 1000 500 2000 1800 1600 1400 1200 1000 800
-1 -1
Wavenumber, cm Wavenumber, cm
Fig. 4. FT-IR spectra of polystyrene, maleic anhydride, native CNC and SMA-modified CNC isolated from sample S-0.5-1 (A) and extended FT-IR spectra of CNC
before and after modification by SMA and/or PS chains.

Table 2
Characteristic of the prepared PS beads using the aqueous dispersion of CNC with different nanoparticle concentration and the emulsified water.
Series Sample* CNC/styrene ratio, wt.% Water content, wt.% Encapsulation efficiency, % Bead size, ± 0.1 mm Max expansion ratio, –

CNC content S-0.25-1 0.0125 4.24 84.8 3.2 5.6

S-0.5-1 0.025 5.45 109 5.8 14.6
S-1-1 0.05 3.45 69 3.5 4.6
Emulsified water S-1-0.5 0.025 1.14 44.2 3.9 3.8
S-0.5-1 0.025 5.45 109 5.8 14.6
S-0.25-2 0.025 6.31 63.1 6.0 8.1

* Sample Nomination: S-x-y, where x is the concentration of nanoparticle in water (wt.%) and y is the emulsified water (ml).

90
100 60
30
-dm/dt, %/min
Weight, wt.%

A 0 B
99 150 300 450

98
E-0.25-1 E-0.25-1
E-0.5-1 E-0.5-1
97 E-1-1 E-1-1 150 300 450

90 100 110 120 130 140 90 100 110 120 130 140 150
Temperature, °C Temperature , °C

100
100
50
0
-dm/dt, %/min
Weight, wt.%

98
150 300 450
C D
96

S-1-0.5 S-0.5-1
94 S-1-0.5
S-0.5-1
S-0.25-2 S-0.25-2
150 300 450
92
80 100 120 140 160 180 200 220 80 90 100 110 120 130 140 150
Temperature, C o Temperature, oC
Fig. 5. TGA and DTG thermograms of the prepared PS beads series CNC content (A, B) and water content (C, D).

were prepared by varying the CNC content and the initial emulsified
water (Table 2). Amount of the water content inside the PS beads was
obtained by TGA. The encapsulation efficiency (EE %) of the beads,
defined as the amount of internal aqueous phase preserved after
emulsification and polymerization, was calculated by dividing the total
incorporated water in the final bead to the initial water (CNC aqueous
dispersion) that used for emulsification.
The TGA and DTG results showed two profiles for water release at
around 102 and 118 °C for all beads (Fig. 5). The former one is attrib-
uted to free water or unbound water (behaves physically as pure water)

6
Z. Ajelou, et al. European Polymer Journal xxx (xxxx) xxxx

coalescence phenomenon [41,56,57]. But in the highest content of CNC

100 (S-1-1), we found the lowest water content (Table 2). This exception
E-0.5-1 As synthesized
E-0.5-1 After 4.5 months may be attributed to the CNC aggregation resulting in lack of effective
E-0.5-1 After 7 months available CNC particles to stabilize water droplets.
99 A
Weight, wt.%

The morphology of the PS beads (Sample S-0.5-1) was studied by

the FE-SEM (Fig. 2) and the related size distribution of water droplets
98
was obtained by manually counting droplet diameters (at least 200
droplets) by the use of JMicrovision 1.2.7 software. The measured
97
diameters for the micrographs were multiplied by a factor of 2/√3 to
have a better estimation of the real void (droplet) diameter [58]. This
96 statistical correction was applied in order to compensate for the un-
derestimation of values obtained by direct measurements from the
95 micrographs. The size distribution showed that the droplet size was in a
80 100 120 140 160 180 200
o
range of 5–35 µm centered at 10 and 20 µm (Fig. S2).
Temperature, C The water preservation ability during storage was determined by
calculating the encapsulation stability (ES %). The ES was obtained by
dividing the remained encapsulated water after storage into the original
encapsulated water. Therefore, the water content of the sample S-0.5-1
B was determined by TGA after 4.5 and 7 months and was compared with
-dm/dt, %/min

the as-synthesized sample (Fig. 6). It seems that the release rate of the
free water is higher than the bound water because the peak corre-
sponding to the free water was totally disappeared after 4.5 months,
while the bound water existed over 7 months (Fig. 6A–B). The calcu-
lated ES% for sample S-0.5-1 after 4.5 and 7 months after synthesis was
90.0 and 75.8% of the initial encapsulated water content, respectively
E-0.5-1 After synthesized
(Fig. 6C). Which in comparison with its analogous, i.e. polystyrene
E-0.5-1 After 4.5 months
beads containing water droplets stabilized by dioctyl sulfosuccinate
E-0.5-1 After 7 months
sodium salt (AOT) with ES of 2.63% [59] and polystyrene bead in-
80 100 120 140 160 180 cluded water droplets stabilized by AOT aid with sodium montmor-
o illonite platelet with ES of 27.1% [60], the prepared sample in this
Temperature, C
work showed the best encapsulation stability. This ability so crucial in
7
expansion ability which will discuss in the following section.
6
3.4. Expansion behavior of beads
90.0 %
Water content, wt.%

5
4 polystyrene (EPS) foam in which water is used as a physical blowing
3 agent instead of using volatile organic compounds (VOCs) like pentane.
27.1 %
2 CNCWEPS
1 C
2.6 %
0
0 1 2 3 4 5
Time, month
Fig. 6. TGA (A) and DTG (B) thermograms of sample S-0.5-1 as-synthesized and
over time. (C) Comparison of water preservation ability of S-0.5-1 (CNCWEPS)
with its analogous.
which is entrapped inside the water droplets. And, the latter one is
related to bound water which is associated chemically with the cellu-
lose chain existed in the CNC surfaces. Because of severely limited
motion of the bound water molecules, it is not released at the boiling
point of free water and therefore more energy, i.e., higher temperature,
needs to overcome these interactions [54,55]. These temperatures were
also reported in our previous works [43,44]. Obviously, the peak area
of the bound water is always higher than the free water (Fig. 5).
Moreover, the incorporated water content was increased with the CNC
content and the emulsified water (Table 2 and Fig. 5). This can be re-
lated to the abundance of available CNC particles to emulsifier of water
droplets and also sufficient water to be stabilized. Principally, the
plenty of effective available particles leads to small emulsion droplets
with narrow size distribution and also it can well prevent from
75.8 % Water expandable polystyrene (WEPS) is a new type of expanded
This can be a promising and eco-friendly product because, in its pro-
duction process, the flammable blowing agents and therefore their
(S-0.5-1) harmful environmental effects are avoided. Due to the complete im-
WEPSCN
miscibility of water and polystyrene, some specific methods have been
WEPS proposed to the synthesis of WEPS materials such as entrapping water
droplets through inversion emulsion followed by suspension poly-
6 7 8 merization [59,60] or introducing water using water absorbent mate-
rials during suspension polymerization of styrene [48]. One of the
biggest obstacles to the industrialization of WEPS materials is their low
expandability. During storage and expansion process, a substantial
fraction of water permeates out of the beads through polystyrene matrix
leading to a shortage of water as a blowing agent to expansion. In spite
of some attempts to put barriers against water diffusion-out [60–62],
the water loss and therefore low expandability are still the biggest
challenge for WEPS materials. Recently, our research group has pro-
posed Pickering emulsion polymerization technique to introduce and
stabilize water droplets inside the polystyrene beads using water ab-
sorbents solid particles such as crosslinked starch nanoparticles
(CSTNs) and cellulose nanofibers (CNFs) [43,44]. The prepared WEPS
materials in these two work were termed CSTNWEPS and CNFWEPS,
respectively. The higher ability of these nanoparticles to stabilize water
microdroplets along with their ability to preserve water inside the
polystyrene beads led to the expansion ratio of around 7 for CSTNWEPS
and around 14 for CNFWEPS which have not been reported before. In
the present work, we continue trying to reach more expansion ratio by
using cellulose nanocrystals (CNCs) with platelet-like morphology. The
CNCs were undertaken with the following aims; I) stabilizing water
microdroplets inside PS matrix, II) enhancing water maintainability of

7
Z. Ajelou, et al. European Polymer Journal xxx (xxxx) xxxx

Fig. 7. FE-SEM micrographs of foam morphology at maximum expansion for S-0.5-1 (CNCWEPS) 5.45 wt% of water at different magnifications (A, B, C, D). During
the expansion process, the softened polystyrene matrix along with the CNC particles are forced back to form polyhedral cells; thus, the CNC particles are located in
the cell wall (E and F).

Fig. 8. Expansion behavior of the S-0.5-1 (CNCWEPS) beads. (A) Cell size distribution of the obtained foam from CNCWEPS. Solid curve is Gaussian fit to the data.
(B) Three regimes in expanded polystyrene using water as blowing agent I; induction II; expansion III; collapse.

PS beads by water absorbing because of their nature of hydrophilicity processes the CNC particles were surface-modified with SMA copolymer
and III) placing individually in the PS matrix to cause tortuous pathway to be miscible with polystyrene matrix. Hence, it is not difficult to
against water molecules (barrier effect). As mentioned before in the in imagine that the modified CNCs are located at the water-in-oil interface
situ modification section, during the emulsification and polymerization and also in the PS matrix.

8
Z. Ajelou, et al.
When the S-0.5-1 sample beads included small and well-dispersed
water microdroplets are heated at an optimum temperature (~130 °C),
well above the glass transition temperature of the matrix, the rubbery
softened polystyrene matrix was expanded owing to the developed
water vapor pressure inside the beads. This results in a foam-like
structure with rather polyhedral cells (Fig. 7A–D) with cell size ranged
from 30 to 130 µm centered at around 75 µm (Fig. 8A). The beads were
exposed to hot oil and then quickly quenched in cold water bath. The
obtained expansion behavior for these beads is in agreement with the
results of other reports [43,44]. Generally, the WEPS materials show
three regimes during expansion; (I) induction, (II) expansion and (III)
cell collapsing. In the induction period, the applied heating is too low to
soften polystyrene matrix and make sufficient vapor pressure for ex-
pansion, however, during this period the content of water (blowing
agent) is lost due to water diffusion through polystyrene matrix. In the
expansion period, the sufficient water vapor pressure forces the well
softened polystyrene matrix and the beads were expanded quickly.
After the max expansion stage, the foam cells start to collapse from the
edge due to the lack of blowing agent, i.e. water (Fig. 8B). During the
expansion process, the polystyrene matrix along with the CNC particles
around the water microdroplets are forced back, consequently the CNC
particles located inside the cell walls (Fig. 7E–F). It is believed that the
presence of the modified CNCs at the cell wall with secure connection
with the polystyrene matrix through interaction and physical en-
tanglement, can improve the strength of the melted polystyrene around
the cell wall. This enhancing mechanism inhibits rupturing of the cell
wall and consequently, decreases the chance of premature escape of
water during the induction period and reduces water diffusion-out
during the expansion process. All these effects lead to higher expansion
ratios. The max expansion ratio of around 15 was obtained for S-0.5-1
(Fig. 8B). Since these materials are a new type of water expandable
polystyrene (WEPS) materials, therefore these materials obtained in
this work call CNCWEPS.
As mentioned before, the TGA results proved that the prepared
beads in this work have an excellent ability to preserve water inside the
beads over months (Fig. 6C). So, around 75% of initial water was re-
tained 7 months after the synthesis of the beads. This ability aids us to
overcome the problem of rapid water diffusion, which is the main
reason for low expandability in WEPS materials, and approach a higher
expansion ratio even after 4.5 and 7 months.
4. Conclusion
Polystyrene beads included monodispersed water microdroplets
were successfully synthesized through the water-in-oil Pickering
emulsion using cellulose nanocrystals (CNCs) followed by suspension
polymerization. The CNCs were in situ surface modified by poly
(styrene-co-maleic anhydride) (SMA) during emulsification and poly-
merization process to be compatibilized with polystyrene matrix. The
modified CNCs have suitable wettability to stabilize water droplets in-
side the styrene/polystyrene phase. It is believed that the grafting
mechanism occurs in two possible ways; forming ester bond and/or
forming hydrogen bonding between hydroxyl groups on CNC surfaces
and anhydride groups in SMA chains. The prepared polystyrene beads
containing CNC stabilized water droplets are a new type of water ex-
pandable polystyrene named as CNCWEPS materials. The CNCs not
only have a crucial role in particulate stabilization of water droplets
inside polystyrene beads but also can efficiently affect expansion be-
havior of the bead. First, the presence of the modified CNCs in the cell
wall reinforce the wall against rupture and consequently prevents the
premature escape of water as a blowing agent from the beads during the
expansion. Second, the modified CNCs enhance the melt strength of the
polystyrene matrix which in turn slows down the diffusion of water out
of the beads. Third, the presence of the modified CNCs with platelet-like
morphology inside the polystyrene matrix dictates a tortuous pathway
for water molecules to reduce the diffusion rate of water molecules to
9
European Polymer Journal xxx (xxxx) xxxx
out of the beads. Moreover, because of the significant amount of bound
water in the CNCs, the water preservation ability of the prepared
CNCWEPS beads was exceptionally enhanced. Specifically, 7 months
after synthesis of the beads, the residual water was around 75% of the
initial water. This water maintainability of these beads has positively
effect on expansion process. So, a max expansion ratio of about 15 was
found for the as-prepared CNCWEPS containing 5.45 wt% of water. As a
final conclusion, exploiting Pickering emulsion polymerization to re-
place pentane with water as blowing agent gives us an opportunity to
insert renewable hydrophilic compound into the expanded polystyrene
foam.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgement
The Institute for Advanced Studies in Basic Sciences (IASBS),
Zanjan, Iran are gratefully appreciated for financial support (with Grant
number of G2015IASBS32632). Also, the authors appreciate the assis-
tance of Kimia Nankali and Sara Naderizadeh in the preparing of na-
noparticles.
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.eurpolymj.2019.109343.
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