Carbohydrate Polymers 224 (2019) 115202

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Carbohydrate Polymers
journal homepage: www.elsevier.com/locate/carbpol

Transparent and strong polymer nanocomposites generated from Pickering T

emulsion gels stabilized by cellulose nanofibrils
⁎
Xinyue Liua, Xiaojun Qia, Yupeng Guana, Yingying Hea, Shuai Lia, Hongxia Liua, , Li Zhoua,
⁎
Chun Weia, Chuanbai Yua, Yunhua Chenb,
a
College of Material Science & Engineering, Guilin University of Technology, Guilin 541004, China
b
School of Materials Science and Engineering, South China University of Technology, Guangzhou 510640, China

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

Keywords: We report here the development of transparent and strong polymer composites reinforced by unmodified cel-
Cellulose nanofibrils lulose nanofibrils (CNFs) with a Pickering emulsion gelation strategy. The CNFs entangle and firmly stabilize on
Pickering emulsion the surface of emulsion droplets containing polymethyl methacrylate (PMMA) solution, leading to the gelation of
Polymer nanocomposite the emulsions. CNFs/PMMA composites were generated via vacuum filtration and solvent washing of the gel and
PMMA
a subsequent two-step hot pressing. The composites contained a unique self-assembled two-tier hierarchy of
Three-dimensional network
CNFs networks and demonstrate promising transparency, tensile strength, flexibility, and an extremely low
thermal expansion. Remarkably, these properties are highly tunable with varying the concentration of CNFs and
the volume ratio of the water to oil phase. This work offers a facile route to realize the well dispersion of
unmodified CNFs in hydrophobic polymer matrix and achieve high performance of polymeric materials re-
inforced by CNFs.

1. Introduction
Cellulose nanofibrils (CNFs) are typically a fibrous component of
cellulose fibers that have nanoscale (< 100 nm) diameter and lengths
of up to several micrometers (Kiziltas, Kiziltas, Bollin, & Gardner, 2015;
Stelte & Sanadi, 2009). CNFs, which provide structural support to plant
bodies in nature, are characterized by biodegradability, high surface
area, high aspect ratio, low density (˜1.5 g/cm3) (Ahmadi, Behzad,
Bagheri, Ghiaci, & Sain, 2017), high strength (2–6 GPa) (Saito,
Kuramae, Wohlert, Berglund, & Isogai, 2013; Wu, Moon, & Martini,
2014), high elastic moduli (130–150 GPa) (Iwamoto, Kai, Isogai, &
Iwata, 2009; Sakurada, Nukushina, & Ito, 1962; Sturcova, Davies, &
Eichhorn, 2005), and low thermal expansion coefficients (4–6 ppm K-1)
(Diaz, Wu, Martini, Youngblood, & Moon, 2013; Horii & Wada, 2005).
These unique properties have been exploited for the development of
CNFs as a reinforcing filler in polymer nanocomposite materials (Azizi
Samir, Alloin, & Dufresne, 2005; Eichhorn et al., 2010; Sakakibara,
Moriki, Yano, & Tsujii, 2017; Alidadi-Shamsabadi, Behzad, Bagheri, &
Nari-Nasrabadi, 2014; Sato et al., 2016; Cai et al., 2016; Ballner et al.,
2016; Stone & Korley, 2010; Jahed, Khaledabad, Almasi, & Hasanzadeh,
2017; Ljungberg et al., 2005).
Due to the hydrophilic nature of cellulose, CNFs can be generally
dispersed in most polar or hydrophilic polymers (Qing, Sabo, Cai, &
Wu, 2013; Xiao, Gao, Gao, & Li, 2016；Nordqvist et al., 2007). How-
ever, at low concentrations of CNFs suspension, CNFs have a gel-like
structure due to their high agglomeration, which leads to poor disper-
sion in non-polar or hydrophobic polymer matrix (Ahmadi et al., 2017).
Incompatibility with hydrophobic polymers represents a critical issue
during the development of these composites. Many methods have been
attempted in an effort to increase the compatibility and interaction
between CNFs and the hydrophobic polymer matrix. These include
solvent exchange (Kiziltas et al., 2015), surface modification of CNFs
(Soeta, Fujisawa, Saito, Berglund, & Isogai, 2015; Soman, Chacko, &
Prasad, 2017), addition of compatibilizing agents (Volk, He, & Magniez,
2015), and in situ polymerization (Sain, Ray, & Mukhopadhyay, 2014).
Although these methods can improve the dispersion of CNFs in the
polymeric matrix and the subsequent mechanical properties of the
composites, complex chemical reactions and expensive reagents or
additional latexes are required. Meanwhile, the transparency of the
nanocomposite (especially when transparent polymers such as PMMA
are used) could be significantly affected by this process (Kiziltas et al.,
2015). In addition, mixing some waterborne latexes, such as polyvinyl
acetate (PVAc), polylactide (PLA), nature rubber (NR) and so on, with
to prepare nanocomposites was also used to solve the aggregation of the

⁎
Corresponding authors.
E-mail addresses: aozihx@foxmail.com (H. Liu), msyhchen@scut.edu.cn (Y. Chen).

https://doi.org/10.1016/j.carbpol.2019.115202
Received 2 June 2019; Received in revised form 30 July 2019; Accepted 12 August 2019
Available online 13 August 2019
0144-8617/ © 2019 Elsevier Ltd. All rights reserved.
X. Liu, et al.
hydrophilic CNFs in hydrophobic polymer matrix (LópLez-Suevos,
Eyholzer, Bordeanu, & Richter, 2010; Larsson, Berglund, Ankerfors, &
Lindström, 2012; Chaabouni & Boufi, 2017; Nechyporchuk, Pignon,
Maria, & Belgacem, 2016; Silva et al., 2014; Abraham et al., 2013).
Stable aqueous dispersions and homogeneous composites were pre-
pared when using latex with anionic surfactant and CNFs, while non-
homogeneous distribution of CNFs within the matrix was resulted from
mixing negatively charged CNFs and positively charged matrix
(Nechyporchuk et al., 2016). Moreover, the aggregation of CNFs was
more pronounce with CNFs percentage increased in NR matrix
(Abraham et al., 2013). Therefore, realizing the improvements in the
dispersion of CNFs in a hydrophobic transparent polymer matrix re-
mains a challenge.
Alternatively, the Pickering emulsion strategy, which refers to an
emulsion stabilized by solid particles rather than organic surfactants
(Pickering, 1907), offers potential to address this issue. Depended on
diversity of the solid particles, the Pickering emulsion has great ad-
vantages in building different functional and structural materials, and
even acting as microreactors (Liu, Geng, Xu, Wei, & Zhou, 2016, 2017;
Liu et al., 2019; Tang et al., 2019; Wang et al., 2019). Especially,
Pickering emulsions stabilized by CNFs have been used to build CNFs/
polymer microcapsules or microspheres, and even CNFs/polymer
composites. For example, a Pickering emulsion co-stabilized by cellu-
lose nanocrystals (CNCs) and cellulose nanofibers (CNFs) was used to
fabricate CNCs/CNFs reinforced polyurethane PU microcapsules
(Svagan et al., 2014). Our group also reported a straightforward
method of fabricating multifunctional model drug methyl red-loaded
polymethylmethacrylate (PMMA)/CNFs composite microspheres from a
Pickering emulsion system co-stabilized by CNFs and upconversion
nanoparticles (Liu et al., 2016). More interestedly, Fujisawa et al. re-
ported a facile aqueous preparation process that yields nanostructured
polystyrene (PS)/CNFs composites via the formation of a CNFs-stabi-
lized styrene/Water Pickering emulsion and subsequent polymerization
(Fujisawa, Togawa, & Kuroda, 2017). Also, the PS/CNFs composite was
easily collected via filtration, and subsequent melt pressing allowed the
preparation of a transparent PS/CNFs composite film. The film ex-
hibited high optical transparency, strength, and thermal dimensional
stability, owing to the reinforcement provided by the homogeneously
distributed CNFs. Pickering emulsification approach combined with a
curing reaction was also reported to fabricate hierarchical composites
of immiscible acrylic polymer and cellulose or chitin nanofibers
(Biswas, Sano, Shams, & Yano, 2017; Shams & Yano, 2015). Ad-
ditionally, an oil-in-water Pickering emulsion of PLA/methylene
chloride was firstly stabilized by regenerated cellulose (RC), and uni-
formly dispersed RC/PLA microspheres was obtained through eva-
poration of methylene chloride and vacuum filtration. The subsequent
hot pressing of the microspheres allowed the preparation of a RC/PLA
composite film (Zhang et al., 2018). However, there are some dis-
advantages for the preparation of the CNFs-reinforced polymer in these
studies. The evaporation of organic solvents could give rise to de-
mulsification which possibly led cellulose to desorb from the surface of
emulsion droplets and affect the dispersion of cellulose in polymer
matrix. Additional polymerization or resin-curing process and pur-
ification processes were involved in many cases.
Herein, we developed a CNFs-stabilized Pickering emulsion gel
strategy for building a large panel of CNFs/polymer nanocomposites. A
Facile route for obtaining a good dispersion of CNFs in a hydrophobic
polymer matrix was designed. In contrast to the aforementioned stu-
dies, our work is aimed at obtaining a Pickering emulsion gel resulting
from the entanglement of CNFs stabilized on the surface of emulsion
droplets containing organic solvents of certain polymers. After the va-
cuum filtration and solvent washing of the emulsion gel, hot pressing
was performed to generate the CNFs/polymer nanocomposites. We can
easily adjust the CNFs content of the resulting composites by control-
ling the concentration of CNFs in the water phase and the volume ratio
of water and oil phase. Poly (methyl methacrylate) (PMMA) was served
2
Carbohydrate Polymers 224 (2019) 115202
as the polymeric matrix and effectively reinforced by a multiple scale
network of CNFs. Highly transparent composites with tensile strength
twice higher than that of pure PMMA were realized even at a very high
CNFs content (i.e., 47 wt%).
2. Experimental
2.1. Materials
Sisal fibers were gifted by Guangxi Sisal Fiber Group. 1, 2-di-
chloroethane (DCE), hydrochloric acid, sodium hydroxide, Na2S·9H2O,
sodium chlorite, chloroacetic acid, acetic acid, sodium carbonate, so-
dium bicarbonate, epichlorohydrin, ammonium hydroxide (29.4%),
fluorescein isothiocyanate (FITC), and ethanol were purchased from
Aladdin Chemistry Co. Ltd. (Shanghai, China) and used directly.
Polymethyl methacrylate (PMMA) with n of 70 000 was purchased from
Chi Mei Industrial Factory (Taiwan).
2.2. Fabrication of CNFs from sisal fiber
Fabrication of sisal fiber pulp: As-received sisal fibers were pre-
conditioned prior to cellulose extraction. The fibers were repeatedly
washed with distilled water, dried in an oven at 80 °C for 12 h, and then
chopped to an approximate length of 5 cm. Approximately 10 g of the
fibers were treated under moderate conditions (1 m M HCl, 100 mL,
165 °C) with 42 min of hydrolysis time. After hydrolysis, the fibers were
washed with distilled water until a colorless filtrate was obtained. The
drained sisal fibers, 4 g of NaOH, 4 g of Na2S·9H2O, and 100 mL of
distilled water were then mixed in a hydrothermal synthesis reaction
kettle, which was kept in an oven at 170 °C for 2 h. The following wash
was performed with distilled water in some cases. Subsequently, the
filtrated preproduct was treated with an acetic acid aqueous solution of
sodium chlorite (Msodium chlorite : Macetic acid : Mwater = 1.34 : 1.30 : 1) at
75 °C for 2 h. The final sisal fiber pulp (SFP) was obtained after repeated
washing and then drying in an oven at 75 °C.
Chemical pretreatment: First, the dried sisal fiber pulp was well-
dispersed in a water/ethanol solution of NaOH and stirred for 30 min
under 30 °C. The chloroacetic acid was then added and the reaction was
performed at 70 °C. After the reaction, the excess carboxylmethyl cel-
lulose was removed via multiple immersion and washing with distilled
water. The sisal fiber pulp modified with carboxyl groups was obtained
after filtration.
Fibrillation of sisal fiber pulp: Approximately 1 g of the sisal fiber
pulp modified with the obtained carboxyl group was immersed in
250 mL of water with a pH of 10–11 adjusted by NaOH for 4 h. The
system was then stirred for 6 min under about 32000 × g using a high-
speed shear blender such as a household bean juice maker (AOKE WMS-
PB108, China). Afterward, the viscous fluid was diluted to 400 mL and
centrifuged for 10 min at 14900 × g using a refrigerated centrifuge
(Dynamica V18R, Australia), with the upper layer corresponding to the
aqueous dispersion of CNFs. A desired concentration of CNFs aqueous
dispersion could then be prepared from the obtained dispersion.
Meanwhile, the carboxymethylation degree of the final CNFs was de-
termination by conductimetric titration. The detailed process has been
presented in Supporting Information part, and the titration curve was
exemplified in Fig.S1. The result showed that the carboxyl content of
the CNFs was 1.48 mmol g−1, equivalent to about 0.24 C arboxyl group
per anhydroglucose units. The definition of the degree of substitution
(DS) is the ratio of reacted carboxyl groups per anhydroglucose units, so
the DS of the final CNFs was 0.24. According to what Eyholzer; et al
have stated in the reference (Eyholzer et al., 2010), the DS of 0.24 for
CNFs is reasonable.
Furthermore, in preparation for confocal laser scanning microscopy
(CLSM), CNFs were labeled by Fluorescein isothiocyanate (FITC) in
accordance with a previously described method (Dong & Roman, 2007).
The detailed process has been presented in Supporting Information
X. Liu, et al. Carbohydrate Polymers 224 (2019) 115202

Fig. 1. The schematic fabrication process of CNFs/PMMA composites based on Pickering emulsions stabilized by CNFs.

part, and a FITC content of 0.016 mmol/g of cellulose was calculated,
equivalent to 1 FITC moieties per 400 anhydroglucose units.
2.3. Fabrication of CNFs/PMMA composites
Our design strategy for the fabrication of CNFs/PMMA composites is
shown in Fig. 1. A certain concentration of DCE solution with polymer
(PMMA) as the oil phase was prepared by dissolving polymer in DCE. A
certain concentration of CNFs aqueous dispersion as the water phase
was mixed with the oil phase in a cylindrical glass container. Afterward,
the O/W Pickering emulsion stabilized by CNFs was obtained by
emulsifying the above mixture on a sonicator (KQ-400KDE) under
400 W (6 cycles of intermittent sonication with 5 min at each cycle were
employed). The CNFs-stabilized emulsion formed a gel after being left
undisturbed for 24 h. The specific experimental schemes are shown in
Table 1. These Pickering emulsion gels are referred to as G-CNFs/
PMMA-x, where x represents the mass percent content of CNFs in the
dispersed solid phase of the emulsion calculated based on the feed ratio.
Subsequently, the Pickering emulsion gel was vacuum filtered for ˜3 h
using a micropore filter (diameter: 50 mm), which was padded with a
layer of polyterafluoroethylene organic filter membrane (pore size: 0.22
μm). The filtration process was extended to 24 h by dropping the mix-
ture solution of DCE and ethanol (VDCE : Vethanol = 9 : 1) into the gel to
eliminate the residual water, and finally an organic gel mat yielded. An
incompletely dried mat, which was formed by drying the above organic
gel mat at 50 °C in a mold to volatilize most of the solvent, was used to
generate CNFs/PMMA composites using a two-step hot-pressing
method. The first step was performed at 70 °C and 1.5 MPa for 15 min
and second step was performed at 120 °C and 75 MPa for 20 min. The
resulting composites with a multiple scale three-dimensional (3D)
network of CNFs are referred to as C-CNFs/PMMA-x, where x denotes
the mass percent content of CNFs in the composites. Note that there is
some mass loss of both nanosized CNFs and dissolved PMMA when the
Pickering emulsion was filtrated into the organic gel mat. So, the x was
determined by TGA analysis according to the following formula.
R composite − Rpmma
x= × 100%
R cnfs − Rpmma
Here, x is the finial content of CNFs in C-CNFs/PMMA composites, and
Rcomposite, Rpmma and Rcnfs are respectively the residue mass of the C-
CNFs/PMMA composites, pure PMMA and pure CNFs. As a result, this
loss was ˜22–32% and the denoted value (x) ranged from 68 to 78% of
the initial CNFs content.
2.4. Characterization
The crystal structure of CNFs was characterized by X-Ray dif-
fractometor (PANalytical B.V., X’Pert PRO, Netherlands) which used
Cu-K target at 40 kV 300 mA, λ = 1.542 Å. Samples were scanned in 2θ
ranges varying from 5° to 40° (1° min−1).
Fourier transform infrared (FT-IR) spectra of samples were mea-
sured as KBr pallets by a NICOLETNEXUS 470 infra-red spectrometer
(America) operating in transmission mode for wavenumbers ranging
from 400 to 4000 cm-1 (resolution: 2 cm-1).
The morphology and structure of the samples were characterized
via field emission scanning electron microscopy (FE-SEM, Hitachi S-

Table 1
Experimental recipe of preparing Pickering emulsion gels stabilized by CNFs and the resulted composites.
Sample name Concentration of CNFs in water Concentration of PMMA in DCE Volume of water phase Volume of oil phase
(%) (w W−1) (mL) (mL)
Pickering emulsion gel Composites

G-CNFs/PMMA-17 C-CNFs/PMMA-13 0.3 4% 12 m L 4 mL

G-CNFs/PMMA-30 C-CNFs/PMMA-20 0.4 4% 12 m L 3 mL
G-CNFs/PMMA-47 C-CNFs/PMMA-37 0.4 2% 12 m L 4 mL
G-CNFs/PMMA-62 C-CNFs/PMMA-42 0.4 2% 12 m L 3 mL

3
X. Liu, et al.
4800, Japan) where each sample was gold-sputtered, polarizing mi-
croscopy (POM, Leica DM PxP, Germany), confocal laser scanning mi-
croscopy (CLSM, Leica Tcs Spe, Germany) where the samples of the gels
or films were put on a glass slide with a coverslip and observed under
100 × or 200 × magnification., and transmission electron microscopy
(TEM, JEM-2100 F, JEOL, Japan) performed at 200 kV. For the TEM
imaging of CNFs, a drop of 0.001 wt% CNFs aqueous suspension was
deposited on Cu grids and then stained with 2% uranyl acetate prior to
complete drying.
The optical transmittance of samples was measured at wavelengths
from 300 to 800 nm using an ultraviolet − visible light spectro-
photometer (UV-3600, Shimadzu). Transmission spectra were mea-
sured using air as a reference.
The practical amount of CNFs in the resulting composite was esti-
mated and the thermal degradation profile was assessed by means of
thermogravimetric analysis (TGA). A 3 mg portion of sample was
measured (heating rate: 10 °C min−1) in a flowing nitrogen (N2) at-
mosphere (flow rate: 60 mL min−1) on a thermal analyzer instrument
(Netzsch STA-449, Germany). Each measurement was performed on 3
individual samples for obtaining a mean data.
Differential scanning calorimetry (DSC) was measured with a
Netzsch DSC-204 instrument using indium standards for calibration
with a heating rate of 10 °C min−1from 20 °C to 200 °C. N2
(20 mL min−1) was employed as the purging gas for the sample and
reference cells. Heating, cooling, and reheating cycle were performed
and second heating cycle was studied. Samples were heated from 20 °C
to 200 °C, held at 200 °C for 5 min to eliminate thermal history in the
first heating cycle. The measurements were performed on 3 individual
samples for obtaining a mean data.
The mechanical properties of neat PMMA and C-CNFs/PMMA
composite films were studied with a dynamic mechanical analyzer
(DMA, TA Instruments Model Q800) in tensile mode. The
stress − strain measurements of these materials were performed in a
strain rate of 1% min−1at 25 °C. The storage modulus and tan δ of the
pure PMMA and C-CNFs/PMMA composites were performed at a con-
stant frequency (1 Hz), amplitude of 15 μm, a temperature range from
30 to 110 °C, and with a heating rate of 3 °C min−1. For these experi-
ments, rectangular composite films with a length of 10 mm a width of
3 mm and a thickness of 0.10 mm were used, and the measurements
were performed on 3 individual samples.
The thermal dimensional stability of the samples was evaluated
using a thermomechanical analyzer (TMA Q400, TA Instruments, New
castle, PA, USA). The linear coefficient of thermal expansion (CTE) of
the film was determined using a 0.05 N load cell where samples were
heated from 0 to 170 °C (heating rate: 5 °C min-1) under a N2 atmo-
sphere.
Rheological measurements were conducted on TA ARES-RFS strain-
controlled rheometer at 25 ℃. A flat-plate geometry with diameter of
25 mm was used. Samples were placed in the plate. Silicone oil was
applied on the edge of the sample to prevent water evaporation. The
linear viscoelastic of samples were preliminarily obtained from an
amplitude sweep using a constant angular frequency of 1.0 s-1 with
strain amplitude varying from 0.01% to 100%. Complex viscosity,
storage modulus (G’), and loss storages (G’’) were measured as a
function of the angular frequency using oscillatory measurements in the
range 0. 1 s-1 −100 s-1 with fixed strain amplitude of 0.8%.
3. Results and discussion
The method employed in this work differs from the TEMPO method
described by Saito et al. (Tanaka, Saito, & Isogai, 2012). In the present
work, chloroacetic acid was used to convert the hydroxyl groups of
cellulose molecule to carboxylates, thereby resulting in negatively
charged SFP. The repulsive effect of these charges contributed sig-
nificantly to the separation of SFP into nanofibrils. After a high-speed
shear treatment, individualized CNFs with high aspect ratios were
4
Carbohydrate Polymers 224 (2019) 115202
produced. A TEM image of the obtained CNFs (see Fig. S3) revealed that
the crossed CNFs are dispersed in the copper mesh and have a diameter
of 4.8 ± 0.6 nm calculated by a Nano Measurer 1.2 software. The
diameter of 4.8 ± 0.6 nm was much smaller than that of 20–50 nm and
5–20 nm respectively produced by grinding (Iwamoto, Nakagaito, &
Yano, 2007) and TEMPO oxidization (Besbes, Alila, & Boufi, 2011;
Besbes, Rei Vilar, & Boufi, 2011). Their length ranges from hundred
namometers even to several micrometers. So the CNFs have very high
aspect ratio. The long and entangled CNFs can form a strong network,
owing to their fibrillar morphology and strong mutual hydrogen bonds.
The obtained CNFs were well dispersed in water, owing to their aqu-
eous dispersion (see Fig. S4a). The appearance of light and dark stripes
after adding polarizing film indicated the liquid crystalline nature of
CNFs (see Fig. S4b). In addition, the crystal structure was characterized
via X-ray diffraction of CNFs (see Fig. S5). The lack of a doublet in the
intensity of the main peak (θ = 22.6°) indicates that the CNFs obtained
was present in the form of cellulose I, rather than cellulose II (Morán,
Alvarez, Cyras, & Vázquez, 2008).
CNFs as solid particles for stabilizing a Pickering emulsion have
been reported in our previous work (Liu et al., 2016). In the present
work, we focus on the fact that a CNFs-stabilized Pickering emulsion
can form a gel through the entanglement of the long CNFs. By inversion
experiments we investigated the conditions promoting gelation of the
CNFs aqueous dispersion, and found that gelation occurs only at CNFs-
suspension concentrations of > 0.3 wt% (see Fig. S6a). In order to
further prove that the gels formed, we perform rheology of the 0.4 wt%
CNFs aqueous dispersion and G-CNFs/PMMA-47 after ultrasonication.
The results shown in Fig. S6b presented that the storage modulus (G’)
and loss modulus (G’’) of the both samples had platform zones. And also
the higher G’ than G’’ proved the formation of crosslinked network
structure.
Therefore, in the subsequent experiment, we employed concentra-
tions of 0.3 wt% and 0.4 wt% for the suspension. A digital photo, POM,
and CLSM image of the obtained Pickering emulsion gel of G-CNFs/
PMMA-17 are shown in Fig. 2a, c, and e, respectively. This CNFs-sta-
bilized emulsion was fixed in the bottom of an inverted vial, where the
Pickering emulsion gel was formed. In the gel, the emulsion droplets
consisted of DCE solution of PMMA stably dispersed in a water con-
tinuous phase (see Fig. 2c). In the CLSM image of the sample, the green
water phase (shown in Fig. 2e) shows that CNFs in the emulsion gel
were still present in the continuous water phase and on the surface of
droplets (black dispersion phase). The entangled CNFs led to gelation of
the water phase and subsequent formation of the emulsion gel. The
gelation of the CNFs-stabilized Pickering emulsion is important for the
subsequent filtration and solvent washing process, which yields an or-
ganic gel with PMMA incorporated into a 3D interconnected CNFs
network. Note that if the emulsion was filtrated directly, demulsifica-
tion occurred and most of the PMMA and CNFs were mixed in the filter
liquid. However, upon gelation of this emulsion, the emulsion droplets
could still be retained after filtration.
A digital photo, POM, and CLSM image of the obtained organic gel
mat with PMMA incorporated into the 3D interconnected CNFs network
are shown in Fig. 2b, d and f, respectively. The digital photo shows that,
after filtration and solvent washing, the obtained mat became a thin
membrane and seemed harder than the previous emulsion gel. From
Fig. 2d, we can see that there were many closely packed emulsion
droplets in the mat. The droplets diameter decreased significantly after
filtration and solvent washing. The diameter distribution of these dro-
plets before and after filtration and solvent washing was investigated.
The results were shown in Fig. S7. The diameter of the droplets in G-
CNFs/PMMA-17 was felt in the several micrometers to three hundred
micrometers range, and the diameter distribution was fairly wide and
the mean diameter was about 50 μm. While, after filtration and solvent
washing the diameter distribution of the droplets in the organic gel mat
with a mean diameter of about 14 μm became obviously narrow be-
tween several micrometers and forty micrometers. A similar result is
X. Liu, et al.
Fig. 2. Digital images (a, b), POM (c, d) and CLSM images (e, f) of the obtained Pickering emulsion gel of G-CNFs/PMMA-17 (a, c, e) and the corresponding organic
gel (b, d, f), and SEM images of the surface (g) and fracture (h) of the fully dried organic gel. The scale bars are 50 μm.
shown in Fig. 2f, where the smaller and closely packed emulsion dro-
plets (black spherical area) are dispersed in the interconnected CNFs
network (continuous green area). This may have resulted from the fact
that (i) on the one hand, the network structure in the emulsion gel can
fix and protect the emulsion droplets, but (ii) on the other hand, can
reduce the efflux rate of the water and solvent during filtration and
solvent washing. With the removal of the water phase and solvent
washing, the DCE solution of PMMA in the droplets could slowly exude
from the inside to the outside. This resulted in the larger droplets be-
coming unstable and even demulsified or transforming to more stable
smaller droplets, whereas the initially smaller droplets were perfectly
preserved. The structure of the obtained organic gel mat was further
investigated via scanning electronic microscopy (SEM; see Fig. 2g and h
for SEM images of the surface and fracture, respectively, of the fully
dried mat). Many circular particles, i.e., PMMA droplets, were packed
on the surface of the mat. However, the image of the fracture (Fig. 2h)
revealed flat circular (deformed during vacuum filtration) PMMA dro-
plets inlayed in the continuous CNFs network, where initial individual
CNFs eventually evolved into 2D-sheet-like structures during the drying
process, owing to the intensive hydrogen bonding interaction between
CNFs.
The C-CNFs/PMMA composites were generated by hot pressing the
gel mats. Hot pressing was performed in two steps: 1) low temperature
and pressure (at 70 °C and 1.5 MPa for 20 min, deflation at intervals of
5 min), 2) high temperature and pressure (at 120 °C and 75 MPa for
20 min). In our experiment, we found that the first step played an im-
portant role in the formation of high-transparency C-CNFs/PMMA
composites. The appearance of the composites obtained through one-
step hot pressing (under high temperature and pressure) and two-step
hot pressing is shown in Fig. 3a and b, respectively. A highly trans-
parent composite was obtained through two-step hot pressing, while an
opaque composite was obtained through one-step hot pressing. The
POM images (Fig. 3c and d) of the two composites further disclosed that
many PMMA droplets were still obviously dispersed in the composites
obtained via one-step hot pressing, but the surface of the composite
obtained via two-step hot pressing was smooth and clean. Obviously,
the two-step hot pressing can facilitate to improve interface in-
compatibility the PMMA droplets and CNFs. The possible reason is the
slow exudation of a portion of PMMA from the droplets into CNFs
network during the first step of the two-step hot pressing. It allowed
further slow volatilization of the trace residue DCE solvent in the in-
completely dried gel mat, accompanied with which PMMA (surrounded
by close-packed CNFs) Facilely exudated from the droplets and pene-
trated into the interconnected CNFs network. The following second step
5
Carbohydrate Polymers 224 (2019) 115202
allowed flow of the melted PMMA and completed blending of the
PMMA with the interconnected CNFs network under high temperature
and pressure. However, with only one-step hot pressing, the rapid
evaporation of DCE solvent ineffectively promoted the exudation of
PMMA from the droplets and complete penetration into the network,
which led to form obvious boundary between PMMA droplets and
CNFs. The CLSM image (Fig. 3e) of the composites obtained via one-
step hot pressing revealed individual PMMA droplets (marked by white
dotted circle in the figure). These droplets were characterized by a clear
boundary which represented phase separation occurred between these
droplets and interconnected CNFs network (green area). On the con-
trary, although these droplets still existed, the boundary of two phases
was ambiguous in the composites obtained via two-step hot pressing
(Fig. 3f). It can be concluded that the interfacial compatibility of PMMA
droplets and the interpenetrated CNFs network was improved during
two-step hot pressing.
To clarify the interface difference between the CNFs and PMMA
droplets in the composites produced by one-step and two-step hot
pressing, the cross-sectioned fractures of the composites were in-
vestigated by SEM imaging. For the composite subjected to one-step hot
pressing, Fig. 4a shows clear gaps between the oval PMMA droplets
(marked by white solid arrows) and the CNFs network where initial
individual CNFs eventually evolved into sheet-like structures (marked
by white dotted arrows), demonstrating relatively loose connections
between the two phases. However, for the composites obtained through
two-step hot pressing, oblate PMMA droplets (marked by white solid
arrows) were compactly embedded in a continuous micrometer-sized
network (marked by white dotted), as shown in Fig. 4b and c, indicating
the condense inner morphology of the composites. So, the composites
contained a unique self-assembled two-tier hierarchy of CNFs networks,
one being the micrometer-sized network around the droplets and an-
other being the interconnecting bulk network throughout the compo-
site.
The FT-IR spectra of PMMA, the CNFs and C-CNFs/PMMA-37
composite films were shown in Fig. S9. From the spectrum of CNFs, we
can see that the stretching vibrations of the ‒OH and C = O groups are
respectively observed at 3350 cm−1 and 1620 cm−1. While in spectrum
of the C-CNFs/PMMA-37 composite film, along with the above-men-
tioned characteristic peaks of CNFs, there were distinct characteristic
sharp peaks at 1723 cm-1 and 2990 cm-1 respectively corresponding to
the stretching vibrations of ester carbonyl and C-H groups, which were
characteristic peaks of PMMA. So, the results convincingly proved the
successful production of the C-CNFs/PMMA composite films.
Fig. 5a shows digital photos of the neat PMMA and C-CNFs/PMMA
X. Liu, et al.
Fig. 3. Digital images (a, b), POM (c, d) and CLSM (e, f) images of the obtained composite respectively through one-step hot pressing (a, c, e) and two-step hot
pressing (b, d, f).
composite sheets with different mass percent content of CNFs. The
patterns and letters in the background indicate that the C-CNFs/PMMA
composite sheets are all transparent despite the high CNFs mass percent
content (i.e., 42%), which is significantly higher than that reported by
Littunen and Kiziltas (Kiziltas et al., 2015; Littunen, Hippi, Saarinen, &
Seppälä, 2013). This result indicated that the light transmittance was
only moderately affected by the CNFs at the present loading levels,
owing to the nanosize and homogenous dispersion of the CNFs (Liu, Liu,
Yao, & Wu, 2010). Here, the high transparency of the C-CNFs/PMMA
composites, despite the high CNFs content, resulted from the unique
self-assembled two-tier hierarchy of CNFs networks within the PMMA
matrix.
Fig. 5b shows the quantitatively measured profiles of light trans-
mittance versus the wavelength of visible light for the neat PMMA and
C-CNFs/PMMA composite sheets examined via UV–vis spectroscopy
performed over a visible wavelength range of 300–800 nm. The percent
transmittances at 400, 600, and 800 nm are tabulated in Table 2. The
neat PMMA and CNFs sheets transmitted ˜92% and 90%, respectively,
of the incident light. The C-CNFs/PMMA composites with 13 wt.%,
20 wt.%, 37 wt.%, and 42 wt.% of CNFs resulted in 85%, 84%, 87%,
and 85% light transmittance, respectively, at a wavelength of 600 nm.
The light transmittance of the C-CNFs/PMMA composites decreased
only slightly compared with that of the neat PMMA, and was in-
dependent of the CNFs loading content. This trend differed completely
from the results of previous studies where, with increasing cellulose-
nanomaterial loading level, the composites became increasingly
opaque, owing to CNFs agglomeration in the polymer matrix (Littunen
Fig. 4. SEM images of the fracture of the composite C-CNFs/PMMA-42 obtained through one-step hot pressing (a) and two-step hot pressing (b, c).
6
Carbohydrate Polymers 224 (2019) 115202
et al., 2013; Liu et al., 2010). Moreover, the light transmittance of the
C-CNFs/PMMA composite fabricated via our design strategy is higher
than that of the previously reported transmittance (Kiziltas et al., 2015;
Littunen et al., 2013). This may have resulted from the successful
construction of the 3D interconnected network structure of CNFs in the
PMMA matrix.
The thermal properties of the C-CNFs/PMMA composites were also
investigated. Fig. 6a and b show the TGA and DTG curves of the com-
posites, PMMA, and CNFs (the corresponding data are listed in Table 3).
The initial CNFs weight loss occurring at temperatures below 200 °C
(see Fig. 6a) is attributed to the removal of moisture from the cellulose.
The thermal degradation occurring at temperatures of 200–380 °C is
attributed to the depolymerization of hemicellulose and cleavage of
glycosidic cellulose linkages for CNFs (Lee et al., 2012). Thermal de-
gradation of the PMMA began at 300 °C, i.e., the onset decomposition
temperature, and the maximum weight loss occurred at 368 °C. How-
ever, the thermal degradation of the C-CNFs/PMMA composites can be
divided into two processes, which are attributed to the decomposition
of CNFs and PMMA, respectively. During the first process, the compo-
sites began to degrade at a temperature considerably lower and slightly
higher than the temperatures associated with PMMA and CNFs, re-
spectively (see Table 3). The maximum weight loss of the C-CNFs/
PMMA composites at temperatures of up to 313 °C was slightly higher
than that of CNFs. The possible reason is that the addition of PMMA
inhibited the degradation of CNFs and increased the decomposition
temperature of the composites. During the second process, the onset
and maximum decomposition temperatures of the C-CNFs/PMMA
X. Liu, et al. Carbohydrate Polymers 224 (2019) 115202

compositions. Tg values of 110 °C and 98–105 °C were measured for

PMMA and the C-CNFs/PMMA composites, respectively. The lowered
Tg phenomenon has also been reported for PMMA/CNC composites (Liu
et al., 2010) and PMMA/NFC (nanofibrillated cellulose) composites
(Littunen et al., 2013). The decrease of Tg value of C-CNFs/PMMA
composites is probably resulted from the plasticization of the residual
solvent which was not completely volatilized during the hot-pressing
process. However, the gradually increased Tg values from 98 °C to
105 °C were also found with the increasing content of CNFs in these C-
CNFs/PMMA composites. The increase of Tg value is probably resulted
from the hydrogen bonding interactions between PMMA and CNFs. So,
though the Tg of the C-CNFs/PMMA composites was affected by the
probable residual solvent, the interaction between PMMA and CNFs
was still improved by the formation of hydrogen bonding.
Moreover, as revealed by the thermal expansion behavior (Fig. 6d),
the thermal dimensional stability of the C-CNFs/PMMA composite was
superior to that of the neat PMMA. The thermal expansion of the
composite was considerably lower than that of PMMA. The coefficient
of thermal expansion (CTE) of the C-CNFs/PMMA-42 Composite
(12.7 ppm K-1, comparable to that of glass (7–10 ppm K-1)) was sig-
nificantly lower than that (149.2 ppm K-1, below the glass transition
region) of PMMA (Ashby, 1992). Therefore, the inclusion of CNFs
yielded considerable reduction (˜12 times) in the thermal expansion of
the PMMA.
The tensile properties of neat PMMA and C-CNFs/PMMA composites
are shown in Fig. 7. As the figure shows, the tensile properties of all the
C-CNFs/PMMA composites were superior to those of the neat PMMA.
The tensile stress at break of the composites increased gradually with
increasing CNFs content. The optimum tensile stress (59 MPa) and the
maximum elongation at break (4.3%) achieved at a CNFs loading of
42%, which represented both ˜200% improvement, compared with
those of the neat PMMA. The C-CNFs/PMMA composites exhibited
Fig. 5. Digital photos (a) and profiles of light transmittance versus the wave-
length of visible light (b) of the neat PMMA and C-CNFs/PMMA composite
higher stiffness and toughness than the neat PMMA. The improvement
sheets with different mass contents of CNFs. of tensile strength indicates that CNFs acted as reinforcement in the
PMMA matrix by transferring load from the polymer matrix to the
CNFs. In our C-CNFs/PMMA composites, the multiple scale inter-
Table 2
connected network structure of CNFs carried the load, and stress dis-
UV-vis transmittances of the neat PMMA and C-CNFs/PMMA composite sheets
sipation could occur at the interfaces of the CNFs network/PMMA
at 400 nm, 600 nm, 800 nm.
droplets through mutual sliding. This dissipation could also occur in the
Sample name Transmittance(%) CNFs network itself, where the soft PMMA is penetrated in associated
with volatilization of DCE during solvent washing and two-step hot
400 nm 600 nm 800 nm
pressing. Moreover, the maximum elongation at break was improved
Neat PMMA 91 92 92 with the CNFs content in composites increased, which is different from
CNFs 88 90 90 that reported by Huang et al (Huang, Kuboyama, Fukuzumi, &
C-CNFs/PMMA-13 81 85 85
Ougizawa, 2018). The difference maybe resulted from the unique self-
C-CNFs/PMMA-20 80 84 85
C-CNFs/PMMA-37 83 87 87 assembled two-tier hierarchy of CNFs networks in the C-CNFs/PMMA
C-CNFs/PMMA-42 81 85 86 composites. The micrometer-sized network around PMMA droplets can
be deformed and allow larger deformation to take place along the di-
rection of the stress loaded.
(337 °C and 377 °C, respectively) were both significantly higher than Meanwhile, the temperature dependency of the storage modulus
those of PMMA and dependent on the CNFs content. Similar results and tan δ of the pure PMMA and C-CNFs/PMMA composites were in-
were observed for PMMA/CNC (cellulose nanocrystal) composites with vestigated via DMA to explain the mechanical behavior of the compo-
loading levels of 2 wt.% –10 wt.% (Liu et al., 2010). This could be at- sites with change in temperature, especially in the plastic region of
tributed to hydrogen bonding interactions between CNC hydroxyl materials. The C-CNFs/PMMA-20 composites showed much greater
groups and carbonyl groups on the PMMA matrix (Dong et al., 2012; storage modulus throughout the temperature range tested (Fig. S10a).
Kuo, 2008), where hydrogen bonding had a significant effect on the Though with changing from a glassy state to a rubbery state, a drop in
thermal properties of the polymer blends. Moreover, owing to the high the storage modulus was observed for both the pure PMMA and C-
char yield (27.8%) of CNFs at 700 °C, the char yield of the C-CNFs/ CNFs/PMMA composites, the decrease for the C-CNFs/PMMA compo-
PMMA composites also increased from 1.9% to 12.7% with increasing sites was slighter than that of the pure PMMA. Seen from Fig. S10b and
CNFs content of the composites. So, we can conclude that the thermal c, tan delta tan δ peak position the C-CNFs/PMMA-20 composites was
property of the C-CNFs/PMMA composites was poorer than the pure shifted to the right and towards the higher temperature regions com-
PMMA during the beginning decomposition process, but the subsequent pared with that of the pure PMMA, which suggested that CNFs hindered
maximum temperature of the C-CNFs/PMMA composites was inversely the movement of molecular chain segments in the PMMA matrix.
increased with the addition of CNFs. Additionally, the intensity of the tan δ peak obviously decreased com-
The glass transition temperatures in Fig. 6c show that the addition pared to pure PMMA. This indicates that The C-CNFs/PMMA-20 com-
of CNFs lowered the glass transition temperature (Tg) of PMMA at all posites had the better elasticity and probable crosslinking structure,

7
X. Liu, et al. Carbohydrate Polymers 224 (2019) 115202

Fig. 6. TGA (a), DTG (b) and glass transition temperatures (c) curves of the PMMA, CNFs and C-CNFs/PMMA composites with different mass contents of CNFs, and
(d) thermal expansion behaviors of PMMA and C-CNFs/PMMA-42 Composite.

which maybe resulted from the self-assembled two-tier hierarchy of
CNFs networks dispersed in the PMMA matrix. Therefore, the self-as-
sembled two-tier hierarchy of CNFs networks endows the C-CNFs/
PMMA composites with the unique mechanical property.
4. Conclusions
We have developed a simple CNFs-stabilized Pickering emulsion gel
pathway for fabricating a CNFs/PMMA composite. The obtained com-
posites featured a unique multiple scale 3D network structure of CNFs.
The CNFs/PMMA composite layer resulted from the exudation of
PMMA in emulsion drops into the outer original interconnected CNFs
network formed in the Pickering emulsion gel. This exudation occurred
when DCE effused and volatilized from the inner region of the drops
during vacuum filtration, solvent washing, and two-step hot pressing.
The multiple scale 3D network structure of CNFs synergistically led to a
desirable combination of high tensile strength (60 MPa) and strain
(2%), which are four and two times higher than those of neat polymer,
respectively. The composites also exhibited a high optical transparency
(87%), high flexibility, excellent thermal properties, and low CTE si-
milar to that of glass (12.7 ppm K-1, 1/12th that of the neat polymer),
owing to the well-dispersed CNFs. Consequently, the results of this
work can be applied to various polymers where reinforcement by CNFs
is possible and can provide a Facile route for realizing a good dispersion
of CNFs in a hydrophobic polymer matrix.
Acknowledgment
The authors gratefully acknowledge the financial support of the
National Natural Science Foundation of China (21664006, and
21604025) and Natural Science Foundation of Guangxi Province (No.
2016GXNSFAA380004 and 2015GXNSFAA139256).

Table 3
TG analysis of the CNFs, PMMA and C-CNFs/PMMA composites.
Sample First cycle Second cycle TEnd (oC) Char yield (%)

TOnset (oC) TMax (oC) TOnset (oC) TMax (oC)

CNFs 209.5 302.1 – – 327.8 27.8

PMMA – – 300.9 368.6 413.8 1.9
C-CNFs/PMMA-13 245.2 300.5 332.5 368.6 410.5 5.2
C-CNFs/PMMA-20 248.5 301.3 333.9 376.4 411.8 6.2
C-CNFs/PMMA-37 251.9 310.4 335.2 376.5 412.5 11.4
C-CNFs/PMMA-42 254.6 313.0 337.9 377.2 413.2 12.7

TOnset means the onset temperature; TMax means the maximum degradation temperature; TEnd means the ending degradation temperature.

8
X. Liu, et al.
Fig. 7. Tensile properties of neat PMMA and C-CNFs/PMMA composites with
different mass content of CNFs.
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