Journal of Colloid and Interface Science 602 (2021) 822–833

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Journal of Colloid and Interface Science

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

Regular Article

Soft j-carrageenan microgels stabilized pickering emulsion gels:

Compact interfacial layer construction and particle-dominated emulsion
gelation
Qinbo Jiang, Shaoyang Li, Liyang Du, Yuanfa Liu, Zong Meng ⇑
State Key Laboratory of Food Science and Technology, School of Food Science and Technology, Jiangnan University, 1800 Lihu Road, Wuxi 214122, Jiangsu, People’s Republic of China

g r a p h i c a l a b s t r a c t

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

Article history: Hypothesis: The well-known gelling ability of j-carrageenan can make aqueous solutions into soft
Received 26 April 2021 materials, which are crisp and can be mechanically treated into the nano-sized microgel particle (MP)
Revised 11 June 2021 as the building block for constructing the Pickering emulsion gel (PEG). MPs are expected to adhere
Accepted 11 June 2021
and further create the network structure in PEGs due to their viscoelastic texture. Herein, properties of
Available online 13 June 2021
PEGs should be possibly altered by using MPs with different pH and ionic strength.
Experiments: MPs were prepared by shearing and gelling j-carrageenan solutions simultaneously. Effects
Keywords:
of pH and ionic strength on MPs were formulated, and physical properties of PEGs prepared from corre-
j-carrageenan microgel
Pickering emulsion gel
sponding MPs were investigated. The interaction between j-carrageenan molecules was analyzed by
Viscosity interfacial layer FTIR, and the formation process of the interfacial layer was traced by the interfacial rheological technique.
Saturated fat substitution Findings: The moderate K+ could increase the flocculation and hardness of MPs to improve the viscoelas-
ticity of PEGs. Prepared MPs were more favorable for forming PEGs when pH was 8 and 9. The oil fraction
impacted physical properties of PEGs slightly. MPs constantly moved to the interface from the continuous
phase, forming the compact adsorption layer due to the extrusion of MPs.
Ó 2021 Elsevier Inc. All rights reserved.

⇑ Corresponding author.
E-mail address: mengzong@jiangnan.edu.cn (Z. Meng).

https://doi.org/10.1016/j.jcis.2021.06.070
0021-9797/Ó 2021 Elsevier Inc. All rights reserved.
Q. Jiang, S. Li, L. Du et al.
1. Introduction
Structured oils, especially emulsions, have counted for many
applications in the colloid material field with their predominant
functionalities [1,2]. Gelled emulsions, which have the excellent
performance to solidify emulsion droplets, are essential for
developing novel oil–water hybrid systems [3]. The Pickering
emulsion gel (PEG) has facilitated the development of structured
oils in many areas due to the unique interfacial kinetic stabiliza-
tion mechanism and the restrictive gel network, covering the
material science, food, pharmaceutical, and chemical industry
[4–8]. Inorganic hard Pickering particles with a nano-scale or
micro-scale, like the silica and polystyrene, always had the high
interfacial adsorption obstruction and poor gelling ability. How-
ever, soft particles could adsorb at the water–oil interface more
facilely and more likely to assemble different types of the inter-
facial layer structure [9]. Thus, soft solid particles had begun to,
for a while, draw people’s raised concerns for the specific tex-
ture, advantageous gelling ability, and structural functionality,
being roles as stabilizers of Pickering emulsions and foams,
bioactive constituent microcapsules, and target deliverers, etc.
[10–13].
Microgel particle (MP) is a nano/micro-sized soft matter formed
in the presence of gelators and can work as Pickering particles [14].
As discussed in the former literature, protein-based MPs were still
in the majority in preparing MP-based Pickering emulsions. For
instance, whey protein MPs had a better manifestation in stabiliz-
ing emulsions than solely using the whey protein isolate [15], and
MPs generated by the peanut protein isolate could form various MP
aggregations to fabricate Pickering emulsions [16]. However, MPs
prepared by some familiar easily-gelled polysaccharides (agar,
curdlan, and gellan gum) were used to perform as Pickering parti-
cles by bottom-up and top-down approaches [17]. Unmodified
hydrophobic cellulose-based MPs, which were fabricated by a
regeneration pathway, could emulsify water-in-oil (W/O) Pickering
emulsions and hold the system steady for more than several weeks
[18]. Moreover, a Pickering foam system was established by apply-
ing electrostatic complexes of j-carrageenan MPs (negatively
charged) and a cationic surfactant (positively charged) [19]. j-
carrageenan is the hydrophilic colloid with an excellent cold-
inducing gelling capacity, and it is very susceptible to cations,
especially the K+. The j-carrageenan hydrocolloid is viscoelastic
and brittle, which was beneficial to reduce the size of hydrogels
for making MPs [20]. So far, few studies had focused on the inter-
facial behavior of polysaccharide-based soft MPs and the soft MP-
based gelling performance of PEGs.
In this article, j-carrageenan was chosen to fabricate nano-
sized MPs as Pickering particles and ulteriorly created a PEG sys-
tem. The simple physical approach smashed large bulk j-
carrageenan hydrocolloids finally into a nano-scale, which could
subsequently emulsify the oil–water mixed system for preparing
oil-in-water (O/W) PEGs. K+ and pH-adjusted j-carrageenan MPs
and corresponding PEGs were investigated to study effects of K+
and pH on the emulsifying capacity of MPs and physical properties
of PEGs. Besides, physical properties of PEGs prepared with differ-
ent oil fractions were also studied. The formation process of the
MP-formed interfacial layer was traced by the interfacial rheolog-
ical analysis for characterizing the interfacial behavior of j-
carrageenan MPs. Most importantly, the MP interfacial behavior,
the impact of the oil fraction, and physical properties of MPs and
PEGs were discussed synthetically to put forward a possible inter-
facial adsorption process of j-carrageenan MPs and the gelling
mechanism in PEGs. With the green and straightforward treatment
method, j-carrageenan MP-based PEGs would provide broad and
eco-friendly development prospects as sustainable soft materials,
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Journal of Colloid and Interface Science 602 (2021) 822–833
harmless and low-carbon substitutes for edible solid oils (such as
hydrogenated oils and animal fats).
2. Materials and methods
2.1. Materials
j-carrageenan was offered by Fujian Lvqi Food Colloid (Fujian,
China). Soybean oils, which were refined, bleached, and deodor-
ized, were obtained from a supermarket. Nile Red, Nile Blue, and
other reagents for chemical experiments were offered by Sigma-
Aldrich, Ruichu Biotechnology, and Sinopharm (Shanghai, China),
respectively.
2.2. Preparation of j-carrageenan microgel particle suspensions
j-carrageenan powders (2 wt%) were dissolved in the KCl solu-
tion at 75 °C with physical stirring at 400 rpm and pH adjusting
using 1% KOH and 1% HCl solutions that could be negligible to
the effect of the ionic strength. Formulas for preparing j-
carrageenan MPs are listed in Table 1. When j-carrageenan was
completely dissolved at 75 °C, the solution was immediately trans-
ferred to an ice-water bath and stirred by a digital magnetic stirrer
(RW20, IKA Guangzhou, China) at 550 rpm to disturb the gelation
process for generating coarse gel fragments rather than a large
bulk gel. Solutions with the corresponding ionic strength and pH
(Table 1) were added into coarse gel fragments in the mass ratio
of 3:1 to prepare 25 wt% gel suspensions. Then coarse gel frag-
ments in suspensions were broken down into nano-sized by the
high-speed shearer (Ultra-Turrax T25, IKA Guangzhou, China) at
15000 rpm for 2 min to gain 25 wt% MP suspensions.
2.3. Preparation of Pickering emulsion gels
The MP suspension was mixed with the soybean oil in proportion
(formulas are showed in Table 2), then the high-speed homogenizer
was conducted to emulsify the mixture at 15000 rpm for 2 min. The
ice-water bath was used to cool the mixture during the emulsifica-
tion. The extra water phase added for the emulsification was the
solution with the corresponding ionic strength and pH value.
2.4. Measurements of three-phase contact angle and dynamic
interfacial tension
OCA15EC optical contact angle measuring device (Dataphysics,
Germany) was used to test the three-phase contact angle and
dynamic interfacial tension. MP suspensions were dripped on a
coverslip and entirely covered the coverslip. Then the coverslip
was put into a vacuum drying oven (DP63C, Yamato, Japan) and
subjected to the vacuum drying at 25 °C for 24 h to obtain a thin
Table 1
The pH value and KCl concentration for the preparation of j-carrageenan MPs and
suspensions.
MP types pH KCl (mM)
C-5–62.5 5 62.5
C-6–62.5 6 62.5
C-7–62.5 7 62.5
C-8–62.5 8 62.5
C-9–62.5 9 62.5
C-9–0 9 0
C-9–25 9 25
C-9–125 9 125
C-9–250 9 250
e.g. C-5–62.6 means j-carrageenan MPs and corresponding suspensions prepared
at pH 5 with 62.5 mM of KCl.
Q. Jiang, S. Li, L. Du et al. Journal of Colloid and Interface Science 602 (2021) 822–833

Table 2 2.7. Cold field emission scanning electron microscopy (FE-SEM)

Formulas of j-carrageenan MP-based PEGs.

PEG types MP types 25 wt% MP suspensions Oils Appearances of j-carrageenan MPs were observed by a cold
field emission scanning electron microscope (SU8100, HITACHI,
(wt%) (wt%) Japan). The n-hexane was instead of soybean oils to prepare PEGs
E-5–62.5 C-5–62.5 70 30 [23]. PEGs were freeze-dried by a vacuum freeze-dryer (DC801,
E-6–62.5 C-6–62.5 70 30 Yamato, Japan) for 24 h, and a thin conductive powder layer was
E-7–62.5 C-7–62.5 70 30
E-8–62.5 C-8–62.5 70 30
sprayed on the surface of the dried PEG before observing using
E-9–62.5 C-9–62.5 70 30 the FE-SEM. The acceleration voltage of the FE-SEM was 5.0 kV,
E-9–0 C-9–0 70 30 and the resolution was 0.8 nm.
E-9–25 C-9–25 70 30
E-9–125 C-9–125 70 30
2.8. Rheology of Pickering emulsion gels
E-9–250 C-9–250 70 30
E-10 C-9–62.5 50 10
E-20 C-9–62.5 50 20 Rheological properties of PEGs were confirmed using the DHR-3
E-30 C-9–62.5 50 30 rheometer (TA, USA) equipped with the 40 mm steel flat plate. The
E-40 C-9–62.5 50 40 performed measurement included four sweeps: the logarithmic
E-50 C-9–62.5 50 50
sweep pattern was used from 0.01 to 100% strain for the oscillation
e.g. E-5–62.5 means PEGs prepared by the C-5–62; E-10 means PEGs prepared with amplitude sweep at 1 Hz frequency and 25 °C; the logarithmic
the 10 wt% oil fraction. sweep pattern was applied from 0.1 to 10 Hz for the oscillation fre-
quency sweep at 0.1% strain and 25 °C; the oscillation time sweep
and dry particle layer. After that, the MP-loading coverslip was
was performed at 25 °C and 1 Hz frequency for three stages, which
immersed into a quartz glass container contained soybean oils.
had 300 s duration for per stage, and the first and third stages kept
The sessile drop method was used to measure the three-phase con-
0.1% strain while it was 10% in the second stage; the oscillation
tact angle. The measurement of the dynamic interfacial tension
temperature sweep was performed from 5 °C to 50 °C with 0.1%
was performed via the pendant drop method. The C-9–62.5 sus-
strain and 1 Hz frequency. The soak time before testing was
pension with different MP concentrations (0, 1, 2, 3, 4 wt%) was
180 s for all measurements. The testing gap and trimming gap off-
squeezed out by a needle to record the dynamic interfacial tension
set were 2000 and 50 lm, respectively.
in 10000 s. The temperature for all measurements was controlled
at 25 °C.
2.9. Interfacial rheology of microgel particle-based interfacial layer
2.5. Adsorption kinetic of microgel particles
The DHR-3 rotational rheometer, which was equipped with a
double-wall ring, was adopted to measure interfacial rheological
The interfacial adsorption of MPs at the interface was elabo-
properties using the oscillation amplitude sweep. MP suspensions
rated by an adsorption kinetic model (Eq. (1)) [21].
and soybean oils were added into the groove of the base slowly and
rffiffiffi! !  
t t successively. The double-wall ring stayed on the interface of the oil
Dr ¼ A  EXP  þ B  EXP  ð1Þ
a ss and water all the time during the measurement. The sweep fre-
quency was 1 Hz, and the strain was 0.1% at 25 °C for a 4000 s con-
tinuously scanning.
Dr ¼ rt  re ð2Þ

1 2.10. Optical microscopy measurement of Pickering emulsion gels

k¼
ss
where rt and re are the dynamic interfacial tension at time t
and equilibrium time, respectively, A and B are amplitudes of the
attenuation equation, ss is the kinetic relaxation time, k is the rate
constant, and a is a diffusion-related coefficient.
2.6. Measurements of size distribution and zeta-potential
The size distribution and zeta-potential of j-carrageenan MPs
were measured using the dynamic light scattering technique of
the nanometer laser particle size analyzer (ZEN3700, Malvern Pana-
lytical, British). The refractive index and absorption of the j-
carrageenan MP were set as 1.45 and 0.001, respectively. The size
distribution of emulsion droplets was analyzed via the laser diffrac-
tion technique of the laser particle size analyzer (S3500, Microtrac,
USA), and the refractive index of emulsion droplets was set as 1.1.
Results of the size distribution were reported as the Z-average and
d3,2 for MPs and emulsion droplets, respectively. The polydispersity
of particles and emulsion droplets was represented by the polymer
dispersity index (PDI) and the span ((D90–D10)/D50), respectively. The
d3,2 was calculated by the equation [22]:
P 3
ni di
d3;2 ¼ P 2
ni di
ð3Þ
Optical micrographs of PEGs were captured by a light micro-
scope (DM2700M, Leica, Germany), and the used magnification
was 200 and 500 times, respectively. Micrographs were captured
immediately after the preparation by a bright-field mode at 25 °C.
2.11. Confocal laser scanning microscopy (CLSM)
CLSM micrographs of PEGs were taken by the high-resolution
confocal laser scanning microscope (LSM-880, ZEISS, Germany)
that was equipped with Argon (458, 488, 514 nm) and Helium/
Neon (633 nm) lasers. PEGs were observed immediately after the
preparation. The soybean oil was dyed with the Nile Red (0.1 wt
%), while j-carrageenan was dyed with the Nile Blue (0.1 wt%).
The fluorescence of the Nile Red and Nile Blue was stimulated at
514 and 633 nm, respectively, and was detected by two PMT detec-
tors with 521–600 nm and 600–720 nm of the detecting wave-
length, respectively.
2.12. Analysis of Fourier transform infrared spectroscopy (FTIR)
FTIR results of dried MPs were obtained via the Fourier trans-
form infrared spectrometer (OMNIC iS-10, Nicolet, USA). Firstly,
ð4Þ MP suspensions were freeze-dried in a vacuum freeze-dryer
(DC801, Yamato, Japan) for 24 h. The attenuated total reflection
(ATR) accessory of the spectrometer was adopted to detect dried
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Q. Jiang, S. Li, L. Du et al.
MPs and j-carrageenan powders. Spectral information was col-
lected from 4000 cm1 to 500 cm1 of wavenumbers.
2.13. Apparent stability of Pickering emulsion gels
The apparent stability of PEGs was recorded using a digital cam-
era. PEGs were prepared according to formulas in Table 2. Appear-
ances of PEGs loaded in transparent glass bottles were recorded at
0, 1, 2, 14, 30 days after the preparation, respectively.
2.14. Statistical analysis
The experimental repetition was  3. Data that appeared in this
article were shown as mean ± standard deviation, and differences
of means were judged by the least significant difference test
(P < 0.05). The data processing was accomplished with GraphPad
Prism 8 (GraphPad Software, USA), Origin 2019 (OriginLab, USA),
and SPSS Statistics 19 (IBM, USA).
3. Results and discussion
3.1. Formation process of j-carrageenan microgel particles
As shown in Fig. 1A, the pH (5–9) used to prepare MPs would
significantly affect the particle size and zeta-potential of j-
carrageenan MPs. Because j-carrageenan was always negatively
charged due to abundant sulfate hemiester groups, the zeta-
potential would keep negative and gradually rise following the
increment of the pH [24]. The zeta-potential of j-carrageenan
MPs was the lowest (–33.7 mV) at pH 5, while it was the highest
(–43.7 mV) at pH 9. The particle size would decrease gradually
(560.5 to 212.5 nm) when the pH increased from 5 to 8, and the
size increased to 443.7 nm when the pH was up to 9 from 8 due
Fig. 1. The Z-average size and Zeta-potential of j-carrageenan MPs prepared with different pH (A) and ionic strength (B); the d3,2 of PEGs fabricated by pH-changing (C) and
K+-changing (D) MPs; the d3,2 of PEGs made with 10, 20, 30, 40, and 50 wt% oil fractions (E).
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Journal of Colloid and Interface Science 602 (2021) 822–833
to mechanical properties of j-carrageenan hydrogels changed.
The pH influenced the size of j-carrageenan MPs mainly by adjust-
ing the gel strength and controlling the hydrolysis during the
preparation, which the hydrolysis might decrease the brittleness
of j-carrageenan hydrogels and make MPs difficult to be smaller
by shearing [25]. Moreover, cations such as Na+, K+, and Ca2+ could
dramatically impact the gel strength due to the cationic sensitivity
of j-carrageenan [26,27]. With the presence of the K+, the con-
struction of j-carrageenan molecules would undergo three varia-
tions during the gelation process (Fig. 8), which had been
reported: firstly, disordered molecules formed a chiral single helix
structure; secondly, the single-helix gradually transformed into a
double helix; finally, the double helix further entangled with each
other to create a super helix structure [28]. The low K+ concentra-
tion could facilitate the gel strength and cohesiveness of j-
carrageenan hydrocolloids [29]. The MP size, as shown in Fig. 1B,
was close to 440 nm for a low K+ concentration (0, 25, and
62.5 mM), whereas the size would be greatly enlarged (greater
than550 nm) when the K+ concentration continued to increase to
125, 250 mM. The zeta-potential of MPs constantly declined due
to the increase of the K+ would weaken the electrostatic repulsion
between MPs and enhance the flocculation effect, leading to the
enlargement of MPs. The effect of the K+ on the zeta-potential of
MPs could be explained that the charge screening of K+ on anionic
groups of j-carrageenan resulted in the electronegative of MPs
decreased.
FE-SEM micrographs of freeze-dried PEGs prepared by j-
carrageenan MPs are presented in Fig. 2. After freeze-drying, the
water and n-hexane in PEGs sublimated so that the FE-SEM could
observe MPs in the droplet surface and the continuous phase. MPs
appeared in all shapes as displayed as irregular aggregations
(Fig. 2B) and the tiled granule layer (Fig. 2C), and these various par-
ticles resulted in that the PDI of particles always was higher than
Q. Jiang, S. Li, L. Du et al.
Fig. 2. FE-SEM micrographs of freeze-dried PEGs prepared using n-hexane and j-carrageenan MPs (C-9–62.5). Scale bars: 1 lm (A, B, and C) and 400 nm (D).
0.5 (Fig. 1A and 1B), meaning the size of particles was very uneven.
Therefore, it could be speculated that some MPs, which did not
adsorb at the interface, were very likely to gather together in the
continuous phase forming some aggregated structures, and then
MPs further created an MP-based network in PEGs. Moreover,
MPs in the continuous phase would interact with those MPs cov-
ered at the droplet surface to construct the PEG network together
[30]. Interestingly, shapes of MPs that formed the granule layer
were complementary (Fig. 2D). It seemed that these MPs had been
suffered the mutual extrusion due to the soft texture of j-
carrageenan hydrogels. Hence, soft MPs were likely to adsorb at
the surface of emulsion droplets in the form of complementary
multilateral bodies for constructing a compact, soft, and viscoelas-
tic layer structure around emulsion droplets. The stabilization
mechanism of this elastic protective layer seemed to be different
from that of the interfacial layer formed by traditional hard Picker-
ing particles because this MP-based layer was sealed and complete,
so the capillary pressure between Pickering particles was few
[14,31–34].
FTIR spectra of freeze-dried MPs and j-carrageenan powders
are presented in Fig. S1. FTIR spectra of j-carrageenan MPs and
powders both revealed that a broad characteristic absorption peak
appeared at around 3400 cm1, representing the stretching vibra-
tion of OAH groups. Peaks in the fingerprint region at 1226, 1064,
925, and 843 cm1 meant the sulfate ester, glycosidic bond, D-3,6-
anhydrogalactose, and D-4-sulfate-galactose, respectively [35]. The
OAH stretching vibration in j-carrageenan powders was at
3422 cm1 (Fig. S1B), which was higher than that in j-
carrageenan MPs (<3380 cm1), suggesting that the red-shift of
the OAH characteristic peak happened in j-carrageenan MPs.
The red-shift often proved the presence of hydrogen bonds [36],
which indicated that the formation of j-carrageenan MPs was pro-
moted by intermolecular and intramolecular hydrogen bonds.
Comparing wavenumbers of the OAH stretching vibration in j-
carrageenan MPs fabricated at different pH values (five lines above
in Fig. S1A), the red-shift degree was approximate (about 3370–
3380 cm1), illustrating there was no significant difference in the
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Journal of Colloid and Interface Science 602 (2021) 822–833
strength of the hydrogen bonding among these MPs. The red-
shift degree was, as well, similar (about 3365–3375 cm1) among
j-carrageenan MPs containing the K+ concentration of 0, 25,
62.5, and 125 mM, respectively, while a high K+ concentration
(250 mM) reduced the absorption wavenumber of the OAH
stretching vibration considerably to 3357 cm1. The stronger
hydrogen bonding would cause the greater red-shift in j-
carrageenan [37], and the spectrum of C-9–250 showed the great-
est red-shift with 65 cm1 compared with the peak of j-
carrageenan powders, indicating that the hydrogen bonding of C-
9–250 was the strongest and would make the aggregation of j-
carrageenan molecules more serious. Hence, the significant
increase in the MP size of the C-9–250 could be explained that
MPs quickly aggregated to be larger particles due to the K+-
resulted growth of the adhesiveness.
3.2. Interfacial behaviors of j-carrageenan microgel particles
Physical properties of Pickering particles are critical for prepar-
ing Pickering emulsions, as Pickering particles can decide the type
of Pickering emulsions (O/W or W/O) by different interfacial attri-
butes, adjust the emulsion stability, and be functionalized to meet
special requirements such as the interfacial catalysis and material
cleaning [16,38–40]. Three-phase contact angles of j-carrageenan
MPs and the dynamic interfacial tension of C-9–62.5 at the oil–wa-
ter interface are shown in Fig. 3 and Fig. 4, respectively. As the pH
increased from 5 to 9, as shown, the contact angle approached
gradually to 90° from 60°, meaning that the hydrophilicity of
MPs was weakened and the lipophilicity was enhanced. It was
because more hydrophobic groups in j-carrageenan molecules
were exposed from the region within j-carrageenan molecules
when the environmental pH increased. The adsorption kinetic
model was used to analyze the dynamic interfacial tension for
studying the MP adsorption process. Fitting results are listed in
Table S1. The interfacial tension in four systems with different
MP concentrations finally reached around 20 mN/m according to
fitted equilibrium interfacial tensions (re). Moreover, Table 3
Q. Jiang, S. Li, L. Du et al. Journal of Colloid and Interface Science 602 (2021) 822–833

Fig. 3. Three-phase contact angles of j-carrageenan MPs prepared with different formulas.

Fig. 4. Experimental results (A) and corresponding fitting results (B) of dynamic interfacial tensions of the ultrapure water and j-carrageenan MP (C-9–62.5); MPs were 1, 2,
3, and 4 wt% in suspensions, respectively.

Table 3 drove MPs to diffuse to the oil–water interface by elevating the dif-
The interfacial tension and desorption energy of different MPs. ferential concentration of MPs between the aqueous phase and
MP types Interfacial tension (mN/m) DG (kT)
interface. On the other, the increased viscosity resulted from the
a
higher MP concentration obstructed diffusion. Hence, according
C-5–62.5 20.32 ± 0.08 3.07  106
a to these diffusion-related coefficients, the MP concentration pre-
C-6–62.5 20.00 ± 0.12 1.45  106
C-7–62.5 20.02 ± 0.10 a
5.20  105 dominated the diffusion process only when the concentration
C-8–62.5 20.22 ± 0.18 a
1.18  105 was more than 2 wt%, while the diffusion rate would reduce as
a
C-9–62.5 20.12 ± 0.32 2.35  105 the MP concentration increased under 2 wt%. The further investi-
a
C-9–0 20.37 ± 0.35 4.68  104
a
gation, which was on the stability of Pickering emulsion droplets,
C-9–25 19.96 ± 0.16 2.56  106
C-9–125 20.07 ± 0.06 a
4.47  106
was carried out by the interfacial desorption energy analysis of
C-9–250 19.93 ± 0.12 a
6.17  105 MPs. The desorption energy (DG) when the j-carrageenan MP
detached from the interface and entranced the continuous phase
is calculated by Eq. (5) [41].
shows that different types of MPs also created interfacial tensions
near 20 mN/m. That was to say, once the intact interfacial layer DG ¼ pR2 cOW ð1  coshÞ2 ð5Þ
was created, the interfacial tension was independent of the MP where R, cOW, and h are the radius, interfacial tension of the oil
concentration and type. The kinetic relaxation time (ss) and rate and water, and three-phase contact angle of MPs, respectively. The
constant (k) represented the rate to achieve the adsorption equilib- oil–water interfacial tension and radius were from the dynamic
rium of MPs. As the MP concentration grew up, a less kinetic relax- interfacial tension measurement and particle size analysis, respec-
ation time was required to balance the oil–water interface, and the tively. The difference in the desorption energy and energy of the
rate constant improved. The diffusion-related coefficient (a) thermal motion determined stability of particles at the interface
showed the diffusion rate of MPs from the aqueous phase to the [40].
oil–water interface. The diffusion-related coefficient of 2 wt% The calculated DG value of MPs was shown in Table 3. The mag-
MPs was the lowest (227.24 ± 1.87 s1), and the coefficient nitude of the desorption energy of MPs far outweighed the thermal
increased when the MP concentration was both more than motion energy and could lead to the strong adsorption of MPs at
or<2 wt%, inferring that not only the MP concentration controlled the interface. The desorption energy of MPs with different pH val-
the diffusion, but the viscosity of gel suspensions might impact ues was lower in pH 8 (1.18  105 kT) and pH 9 (2.35  105 kT) that
the diffusion. Concretely, the increase of MPs, on the one hand, meant MPs in the alkaline environment more easily adsorbed at
827
Q. Jiang, S. Li, L. Du et al.
the interface. The effect of the ionic strength on the desorption
energy seemed to be irregular.
The formation process of the interfacial layer based on j-
carrageenan MPs was traced by the interfacial rheological analysis.
The whole process had been divided into three stages highlighted
in Fig. 5. In the first stage, the interfacial loss modulus (G’’) was
always higher than the slowly growing storage modulus (G’), illus-
trating that the interfacial layer had not been formed and was
liquid-like with the good mobility. In the second stage, the G’
quickly surpassed the G’’, so the interfacial layer slowly trans-
formed from the liquid-like state to the viscoelastic-like state. In
the third stage, both the G’ and G’’ tended to be steady, which
meant that the viscoelastic layer (G’ > G’’) had been formed.
According to the variation of the interfacial modulus in three
stages and the morphological appearance of MPs provided in
SEM micrographs, hence, the possible interfacial adsorption behav-
ior of j-carrageenan MPs was inferred: in the beginning, MPs con-
tinually moved to the interface, though the low-coverage rate of
MPs mildly weakened the interfacial mobility and resulted in the
slight increase of G’, and the interfacial layer still exhibited the
liquid-like appearance (G’’ > G’); then, MPs covered the whole
interface gradually and tended to squeeze with each other for
forming a viscoelastic film, resulting in the rapid growth of the
G’ and G’’; finally, the interaction between MPs squeezed and
deformed MPs at the interface to form a complementary structure,
leading to the generation of the viscoelastic and closed MP layer at
the interface. The schematic diagram of the interfacial adsorption
behavior of MPs is shown in Fig. 5. In sum, the tremendous desorp-
tion energy bound MPs at the oil–water interface, and viscoelastic
MPs interacted with each other to form a compact and viscoelastic
layer, effectively protecting emulsion droplets.
3.3. Physical properties of Pickering emulsion gels
Physical properties of PEGs prepared by different oil fractions
and j-carrageenan MPs were investigated. Fig. 1 (C-E) records size
results of emulsion droplets. Emulsion droplet sizes were 15.7,
15.2, 14.3, 6.5, and 9.7 lm for pH 5–9, respectively, and the small-
est droplet presented at pH 8. No sharp variation on the droplet
size occurred when the K+ concentration was<62.5 mM, and dro-
plet sizes were 8.9, 8.2, and 9.7 lm at the K+ concentration of 0,
25, and 62.5 mM, individually. However, emulsion droplets were
much larger in the high K+ environment (125 and 250 mM) that
the d3,2 was 75.2 and 122.3 lm, respectively. When the pH and
ionic strength changed, the size of emulsion droplets changed fol-
lowing trends of MPs. The emulsion droplet size was vulnerable to
Fig. 5. Three stages of the interfacial rheology and the simulated adsorption
illustration for the adsorption process of j-carrageenan MPs (2 wt% C-9–62.5).
828
Journal of Colloid and Interface Science 602 (2021) 822–833
the size of Pickering particles that, to a great extent, the average
size of emulsion droplets more easily increased with larger parti-
cles [42,43]. Emulsion droplet sizes were steadily enlarged as the
oil fraction increased that the d3,2 was 19.6, 30.0, 37.0, 44.6, and
62.1 lm for the oil fraction of 10, 20, 30, 40, and 50 wt%, respec-
tively. However, the span of emulsion droplets was always higher
than 0.8, illustrating that the size of these emulsion droplets was
uneven. It could be considered that the concentration of Pickering
particles determined the maximum area of the stable oil–water
interface. Therefore, for the low oil fraction system, the droplet size
could be reduced to maximize the stable interfacial area, namely
the higher fractal dimension represented the larger interfacial area,
while it was opposite in the high oil fraction system [44].
CLSM and optical micrographs of PEGs are shown in Figs. 6 and
S2, respectively. As Fig. 6A demonstrates, emulsion droplets of the
PEG with 62.5 mM of K+ partially merged and formed bigger dro-
plets when the environmental pH value was 5, 6, and 7, respec-
tively. With the increase of the pH, emulsion droplets remained
steady and dispersive at pH 8 and 9, respectively. Fig. S2A, like-
wise, shows the coalescence of emulsion droplets at pH 5, 6, and
7, respectively, and more dispersive emulsion droplets appeared
at pH 8 and 9, respectively. The destabilization of emulsion dro-
plets also presented when the K+ grew to 125 and 250 mM
(Fig. 6B and S2B), in which emulsion droplets merged seriously,
although the desorption energy of different MPs was all high.
The destabilization of Pickering emulsion droplets was always
chiefly blamed on the improper three-phase contact angle and size
of Pickering particles [9]. However, the stability of PEGs stabilized
by the soft viscoelastic microgel-based particles was special that
physical properties of MPs, such as the viscoelasticity, would
mainly affect the stability of the emulsion droplet and the gel net-
work. As pH was 9, emulsion droplets possessed the better stability
at the low K+ concentration (0, 25, and 62.5 mM), as shown in
Fig. 6A, 6B, S2A, and S2B, respectively. When K+ increased to more
than 125 mM, the cohesiveness of j-carrageenan hydrocolloids
would reduce quickly to soften j-carrageenan MPs, so the strength
of the j-carrageenan MP-based interfacial layer decreased, result-
ing in the breakage of the interfacial layer and the coalescence of
emulsion droplets. Hence the K+-adjusted cohesiveness of j-
carrageenan MPs, as well, was very influential to the stabilization
of PEGs. Fig. 6C and S2C, respectively, suggest CLSM and optical
micrographs of PEGs made with different oil fractions (10, 20, 30,
40, and 50 wt%). The dispersion of emulsion droplets was good
due to the light coalescence when the oil fraction was<40 wt%,
whereas the demulsification phenomenon was found in the PEG
made with the 50 wt% oil fraction because the 50 wt% MP suspen-
sion was insufficient to emulsify the oil–water system. The
observed droplet size was gradually increased as the oil fraction
increased from 10 to 50 wt%, keeping in line with the size analysis
above. Fluorescent images of the j-carrageenan MP-based interfa-
cial layer are illustrated in Fig. 6D and 6E. The environment around
the droplet was diverse that a single emulsion droplet might be
dispersed in the continuous phase (first picture in Fig. 6E) or
adhere to some large MPs (second picture in Fig. 6E), even aggre-
gate with other emulsion droplets (third picture in Fig. 6E). The lat-
ter two cases were more likely to occur in the PEG system due to
the presence of the gel network. The last picture in Fig. 6E was
the fluorescent image of the emulsion droplet in which the oil
(red) and MP layer (green) were dyed using Nile Red and Nile Blue,
respectively. Rather than gelling the continuous phase with pure
gelators [30], the MP-based gelling mechanism of PEGs was more
complex. The gel network in j-carrageenan MP-based PEGs, as
shown in Fig. 8, contained the aggregation of emulsion droplets,
cementation of MPs and emulsion droplets, and the network linked
by free MPs. The rheological test was performed further to investi-
gate macro-physical characteristics of PEGs.
Q. Jiang, S. Li, L. Du et al. Journal of Colloid and Interface Science 602 (2021) 822–833

Fig. 6. CLSM micrographs of j-carrageenan MP-based PEGs. The Pickering emulsion droplets (red) were stabilized using (A) pH-changing (from 5 to 9) MPs, (B) K+-changing
(from 0 to 250 mM) MPs, and (C) different oil fractions (from 10 to 50 wt%). The oil was strained by Nile Red, and (D and E) j-carrageenan MPs (green) were strained by Nile
Blue. Scale bars: 50 lm (A, B, and C), 10 lm (D), and 1 lm (E). (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of
this article.)

Influences of j-carrageenan MPs and oil fractions on rheological
properties of PEGs are shown in Fig. S3. For the amplitude sweep,
the G’ of PEGs made by pH-changing MPs was in the order of E-8–
62.5 > E-9–62.5 > E-5–62.5 > E-6–62.5 > E-7–62.5 in the linear vis-
coelastic region, and the G’ was always bigger than the G’’ at the
strain between 0.01 and 10% (Fig. S3A-1). Additionally, as the K+
concentration rose from 0 to 250 mM (Fig. S3A-2), the G’ was the
largest when the K+ in PEGs was 125 mM and followed by 62.5,
25, 250, and 0 mM, successively. The oil fraction was a common
factor to impact the rheological property of emulsions [45]. How-
ever, the effect of the oil fraction on rheological properties of the
MP-based PEG was unremarkable (Fig. S3A-3) that the increment
of the oil fraction (10–40 wt%) slightly increased the G’ and G’’.
As the oil fraction was overmuch (50 wt%) and surpassed the emul-
sifying capacity of MPs, emulsion droplets and gel structures in
PEGs were destroyed, leading to the decrease of the G’ and G’’. In
the oscillation amplitude sweep, the G‘‘ would gradually surpass
the G’ in all PEGs when the strain was more than 10%, which
showed the semi-solid structure of the j-carrageenan MP-based
PEG had been changed into the liquid. These results indicated that
the pH and K+ concentration could alter rheological properties of
PEGs obviously, illustrating properties of j-carrageenan MPs were
the dominating foundation of physical properties of PEGs. Com-
pared with many other familiar Pickering emulsions significantly
impacted by the oil fraction [46], the influence of the oil fraction
on rheological properties of j-carrageenan MP-based PEGs was

829
Q. Jiang, S. Li, L. Du et al.
little. Therefore, whether the gel network formed by emulsion dro-
plets or free MPs in the PEG was based on MPs as connecting units
of gel networks, and the gelling effect of MPs was insusceptible
when the size and amount of emulsion droplets changed (the oil
fraction changed). To sum up, the pH and ionic strength could
directly alter properties of j-carrageenan MPs and further affect
physical properties of PEGs due to the predominant role of
adsorbed and unadsorbed MPs in gelling the Pickering emulsion,
while the variation of the oil fraction impacted less. Because of
the protection of the gel structure in PEGs, the G’ was higher than
the G’’ in all PEGs in the frequency (0.1–10 Hz) sweep (Fig. S3B), so
the elasticity was the dominating property in PEGs.
The structural recovery capacity and temperature sensitivity of
PEGs were investigated by the oscillation time sweep (Figs. S3C-1
and S3C-2) and temperature sweep (Fig. S3C-3). In the first 300 s,
all PEGs kept viscoelastic (G’ > G’’) at the 0.1% strain, and then
the rapid increase of the strain to 10% destroyed gel structures in
PEGs (G’’ > G’) for 300 s. As the oscillation strain dropped to 0.1%
again for 300 s, the G’ recovered more than 70% and exceeded
the G’’ again, meaning viscoelastic PEGs had a good structural
Fig. 7. Appearances of PEGs made by different j-carrageenan MPs and oil fractions; photographs were taken after 0, 1, 2, 14, and 30 days from the preparation, respectively.
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Journal of Colloid and Interface Science 602 (2021) 822–833
recovery capacity and the thixotropy. Herein, the interaction
between MPs was reversible because the viscous surface of MPs
resulted from physical factors (such as the reversible hydrogen
bonding and Van der Waals forces) could cohere MPs again to form
the MP-based gel network. The G’ and G’’ measured during the
heating (5 to 50 °C) represented the temperature-sensitivity of
PEGs. The G’’ showed a continuous slight decline from 5 to 50 °C,
whereas the G’ was sharply reduced when the temperature was
over 35 °C. The reversible j-carrageenan hydrogel would turn to
the sol as the temperature was above the gelling temperature,
and former reports proved that the K+ increased the gelling tem-
perature of the j-carrageenan [29,47]. Hence, the G’ started getting
below the G’’ as the temperature was more than 45 °C. Once the
gelled j-carrageenan dissolved again, the gel structure in MPs
would turn to the sol, and MPs would melt and lose the function
as Pickering particles, resulting in the collapse of gel structures
and emulsion droplets of PEGs.
The stability of PEGs is an imperative parameter for most applica-
tions. The apparent stability of PEGs in 30 days of the storage is
issued in Fig. 7. As shown, different degrees of creaming-like phe-
Q. Jiang, S. Li, L. Du et al.
nomena came out during the storage of PEGs. Unlike the common
gravity-inducing creaming phenomenon in conventional emulsion
systems [48], j-carrageenan MP-based PEGs were the stable vis-
coelastic matter that emulsion droplets were fixed in the MP-
linking gel network, so the gravity-inducing creaming in the PEG
should be very weak. Herein, the creaming-like phenomenon in j-
carrageenan MP-based PEGs was caused mainly by the shrinkage
of j-carrageenan MPs, leading to that the water leaked from the
hydrogel matrix and settled under the PEG. Appearances of PEGs
made by pH-changing MPs was similar and showed a small portion
of the water leakage after 30 days. As for ionic strength-changing
MPs, prepared PEGs exhibited a significant difference that the water
leakage was the most inconspicuous in the PEG without adding the
K+ (E-9–0), and the leakage was almost the same in PEGs made using
MPs with 25, 62.5, and 125 mM of the K+. The redundantly increased
K+ (250 mM) caused the poor stability of the PEG (E-9–250) in which
droplets quickly swelled, floated up, and was separated from the MP
suspension, and then the upper layer became a continuous oil phase
after 14 days. Notably, after 30 days of the storage, a three-decker
situation was observed in the E-9–250, including the upper oil
phase, the mid MP aggregation, and the nether water layer. The
water leakage phenomenon also appeared in the wholly demulsified
oil–water system, further certifying that the creaming-like phe-
nomenon in j-carrageenan MP-based PEGs was caused by the water
leakage rather than the emulsion droplets creaming. The increased
oil fraction weakened the water leakage because the higher oil frac-
tion reduced the content of waters. Due to the K+-inducing improve-
ment of the hardness and shrinkage of j-carrageenan hydrogels
[49], the water leakage of K+-sensitive j-carrageenan hydrogels
greatly obstructed the apparent storage stability of PEGs. Hence, a
low K+ concentration was preferred to enhance the apparent stabil-
ity of PEGs. Moreover, a moderately increased oil fraction was also
conducive to the PEG stability.
3.4. Formation mechanism of Pickering emulsion gels
Based on the experimental analysis and discussion, a schematic
diagram of the possible formation mechanism of j-carrageenan
MPs and the possible stabilization mechanism of the j-
carrageenan MP-based PEG was conducted in Fig. 8. Besides, the
formability of PEGs, the gel network in PEGs, and the appearance
of emulsion droplets were exhibited by the appearance picture,
Fig. 8. Schematic representations of the preparation process of j-carrageenan MPs and the possible stabilization mechanism of j-carrageenan MP-based medium internal
phase PEGs.
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Journal of Colloid and Interface Science 602 (2021) 822–833
the sketch of the gel network, and the simulated diagram of the dro-
plet, respectively. j-carrageenan powders dissolved in the heated
water (75 °C), and molecules physically interacted mainly by hydro-
gen bonds to form the helix, double helix, and super helix structure,
successively, and then coarse hydrogel fragments were gradually
generated by quick cooling and stirring. After several times mechan-
ical destructions, including high-speed shearing, coarse hydrogel
fragments were broken into hundreds of nano-scale, which could
finally act as Pickering particles and the primary element of the gel
network of PEGs. MPs adsorbed at the oil–water interface from the
MP suspension while the high-speed homogenization was used to
treat the oil–water-MP system, and the strong desorption energy
made j-carrageenan MPs solidly attach at the interface. MPs would
extrude and interact with each other to form a compact and vis-
coelastic interfacial layer, protecting emulsion droplets from the
coalescence. j-carrageenan MPs, both in the continuous phase and
at the interface, were critical units of the gel network and ulteriorly
physically adhered together, forming the complex gel structure in
PEGs. Emulsion droplets were fixed to the gel network, so the oil
fraction of PEGs had a slight effect on the strength of the gel network.
Because the interaction between MPs was reversible, the PEG pos-
sessed a structural recovery capacity to rebuild the gel network
structure after being damaged. However, when the temperature
was higher than 40 °C, MPs would turn to the sol, then disintegrate
PEGs. Therefore, the preparation of j-carrageenan MP-based PEGs
had a specific temperature limit. The K+ and pH concentration were
essential factors to alter properties of j-carrageenan MPs, which
were highly associated with physical properties of PEGs. As the K+
was low (<62.5 mM), the increased K+ was suitable for hardening
j-carrageenan MPs in order to endow the obtained PEG with the
better elasticity, but j-carrageenan MPs would lose the ability for
emulsification when the K+ was more than 125 mM. j-
carrageenan MPs prepared at pH greater than 7 were more favorable
to generate stable PEGs. Hence, according to particular requirements
of applying PEGs, the performance of j-carrageenan MPs could be
adjusted by changing the ion strength and pH to prepare customized
and functionalized PEGs.
4. Conclusions
The suitable K+ (0–62.5 mM) could enhance the semi-solid tex-
ture of Pickering emulsion gels (PEGs) by altering attributes of j-
Q. Jiang, S. Li, L. Du et al.
carrageenan microgel particles (MPs). The hydrogen bonding was
significantly reinforced, and the Zeta-potential was greatly
decreased as the K+ increased to 250 mM, leading to the serious
aggregation and shrinkage of MPs that caused the poor stability
of PEGs. These MPs were more suitable for acting as Pickering par-
ticles at the alkaline environment because of the acid hydrolysis. In
the past, the mechanism of preparing PEGs based on polysaccha-
ride MPs was rarely described [17,18]. Therefore, our findings pro-
vided an innovative way to understand the formation of soft MP-
based PEGs: (1) MPs moved to the interface from the continuous
phase, forming the unsaturated adsorption layer; (2) MPs gradually
covered the entire interface and began to interact with each other;
(3) the adsorption was saturated, and MPs squeezed to form a com-
pact and viscoelastic interfacial layer; (4) both adsorbed and unad-
sorbed MPs were further connected to create the gel network in
PEGs and decided physical properties of PEGs, fixing emulsion dro-
plets and endowing PEGs with the viscoelastic semi-solid texture.
According to the hypothesis, changing MP properties by ionic
strength and pH was the key to adjust physical properties of PEGs
rather than altering the oil fraction of PEGs. These PEGs, which
were different from PEGs gelled mainly by the high oil fraction
[16], could offer same functions at a low oil fraction (<50%) as high
internal phase emulsions, greatly lowering the consumption of oils
in applications. The creaming in PEGs prepared by lots of hard par-
ticles (such as starch particles) or protein-based colloid particles
could only be relieved by increasing the oil phase or adding some
thickeners [50,51], but the network structure solely formed by j-
carrageenan MPs could greatly impede the creaming and improve
the PEG stability. Further research is being carried out to use this
low-oil PEG in meat products and functional foods to improve
the diet.
CRediT authorship contribution statement
Qinbo Jiang: Investigation, Data curation, Formal analysis,
Writing - original draft. Shaoyang Li: Software, Methodology.
Liyang Du: Software, Methodology. Yuanfa Liu: Resources. Zong
Meng: Conceptualization, Writing - review & editing, Supervision,
Project administration, Funding acquisition.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgements
This research was supported by the National Natural Science
Foundation of China (31772008), the National Natural Science
Foundation of China (31972112), the National Key Research and
Development Program of China (2016YFD0401404), and also sup-
ported by Jiangsu Province Science and Technology Plan Project
(BE2018379), Jiangsu Province Science and Technology Plan Pro-
ject (BE2019369).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.jcis.2021.06.070.
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