Carbohydrate Polymers 265 (2021) 118014

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

Preparation of a novel double crosslinked chitin aerogel via etherification

with high strength
Jintian Wang a, Zhiqiang Chen a, b, Hani E. Naguib c, *
a
Department of Mechanical and Industrial Engineering, University of Toronto, 5 King’s College Street, Toronto, Ontario, Canada
b
State Key Lab for Strength and Vibration of Mechanical Structures, Department of Engineering Mechanics, Xi’an Jiaotong University, Xi’an, 710049, China
c
Department of Mechanical and Industrial Engineering, Department of Materials Science and Engineering, Institute of Biomaterials and Biomedical Engineering,
University of Toronto, 5 King’s College Street, Toronto, Ontario, Canada

A R T I C L E I N F O A B S T R A C T

Keywords: In this study, we introduced a novel double crosslinked chitin aerogel via etherification with EGDE for me­
Chitin aerogels chanical reinforcement. Samples with different EGDE: chitin weight ratios from 0 to 1.5:1 were fabricated
Poly(ethylene glycol) diglycidyl ether (EGDE) through chitin dissolution in KOH/urea aqueous solution, ethanol neutralization and washing, and supercritical
Double crosslinking
CO2 drying. Both the physical and chemical crosslinking maintained the high porosity and light weight of chitin
Etherification
Reinforcement
aerogels. The morphology under SEM has shown the close-ended and denser fibrils alignment for EGDE cross­
linked aerogels and the mesoporous and macroporous structure induced by emulsion effect from excessive EGDE.
FTIR characterization was conducted for chemical structure analysis. Compressive testing showed an increase of
247 % compressive strength at 10 % strain and 243 % modulus could be achieved at 1.0 EGDE samples. TGA
results revealed a delayed thermal degradation for the chemically crosslinked samples. This study demonstrates
EGDE an effective chemical crosslinker for reinforced chitin aerogels.

1. Introduction
Biopolymer aerogels research has entered a rapid acceleration stage
in recent years as the sustainability concern grows all over the world.
Biopolymer aerogels have not only maintained the unique characteris­
tics of conventional aerogels including high porosity, lightweight and
high interfacial area, but also inherited superior properties from the
bioresources such as biocompatibility, biodegradability, non-toxicity,
and ease of functionalization. With the expectation and the effort to
compile those superior properties, a wide variety of materials system has
been developed while the majority of which is composed of cellulose,
alginate, chitosan, pectin, starch and chitin (Escudero et al., 2009; Heath
et al., 2013; Kenar et al., 2014; Mi et al., 2016; Rinki et al., 2011; Tkalec
et al., 2015; Wang et al., 2020; Zhang et al., 2017). Innovative methods
to manufacture those biopolymer aerogels have been created in order to
meet the requirement of different applications in thermal insulation,
filtration, adsorption, flame retardancy, catalysis, drug delivery and
food industry (Chaudhary et al., 2014; Escudero et al., 2009; Liu et al.,
2017; Pettignano et al., 2015; Qin et al., 2020; Selmer et al., 2015;
Veronovski et al., 2013; Zhao et al., 2017). However, among those
popular biopolymers, chitin is the least studied one.
Chitin is the second most abundant biopolymer in the world with
billions of tons of production from crustacean shells and other resources.
Owning the linear polysaccharide structure composed of pairs of N-
acetyl-glucosamine units, chitin is recalcitrant to most organic solvents
due to strong inter and intramolecular hydrogen bonds (Zhao et al.,
2018). Before the discovery of alkali/urea aqueous and ionic liquids
system, chitin can only be dissolved in limited and highly toxic solvents
such as DMAc/LiCl and HFIP (Hu et al., 2007; Min et al., 2004; Poirier &
Charlet, 2002; Qin et al., 2010). As the aerogels construction are heavily
dependent on the nanostructure processing of the polymers, current
chitin aerogels have been produced via either thorough dissolution of
chitin or uniform dispersion of chitin nanocrystals followed by the
sol-gel process, supercritical CO2 or freeze drying method (Ding et al.,
2012; Silva et al., 2011; Suenaga & Osada, 2019; Tsioptsias et al., 2009;
Tsutsumi et al., 2014; Wu & Meredith, 2014; Yan et al., 2020).
Compared with aerogels made of other biopolymers, one of the draw­
backs of the chitin aerogels is the mechanical strength. For example, the
chemically crosslinked anisotropic carboxymethyl cellulose aerogels
incorporating cellulose nanofibril prepared by Gong’s group exhibited a
compressive strength of 1 MPa at 10 % strain and a compressive
modulus up to 10 MPa while the chitin aerogels directly dried from

* Corresponding author.
E-mail addresses: jintian.wang@mail.utoronto.ca (J. Wang), zq.chen@mail.utoronto.ca (Z. Chen), naguib@mie.utoronto.ca (H.E. Naguib).

https://doi.org/10.1016/j.carbpol.2021.118014
Received 30 November 2020; Received in revised form 25 March 2021; Accepted 27 March 2021
Available online 2 April 2021
0144-8617/© 2021 Elsevier Ltd. All rights reserved.
J. Wang et al.
various alkali hydroxide/urea solutions prepared by Cai’s group showed
a 10 % strain compressive strength up to 0.3 MPa and a compressive
strength up to 4.1 MPa (Chen et al., 2016; Ding et al., 2016). Therefore,
more sophisticated, and advanced processing techniques are still chal­
lenging for chitin aerogels in order to obtain mechanical strength and
toughness.
On the other hand, many methods have been developed for aerogels
made of polymers other than chitin to deal with the lack of mechanical
strength. For instance, a self-reinforcing silica aerogel designed with the
support of electrospun SiO2 nanofibers was made by Yu’s group,
exploiting the strong and compatible interfacial interaction between
SiO2 fibers and silica solution to achieve tunable mechanical properties
(Huang et al., 2020). Another example comes from Zhang’s group where
a polyimide aerogel was prepared with the addition of silicon carbide
whiskers (SiCw) which functioned as shrinkage inhibitor and reinforcing
fillers in the aerogels, resulting high compressive strength and enhanced
thermal stability (Hou et al., 2020). Besides, utilizing crosslinkers is
another way for strengthened aerogels including polyimide aerogels
crosslinked with octa (aminophenyl) silsesquioxane (OAPS) in Guo’s
group (Guo et al., 2011) and chitosan aerogels crosslinked with form­
aldehyde in Takeshita’s group (Takeshita & Yoda, 2015). Furthermore,
as epichlorohydrin (ECH) crosslinked chitin hydrogels, a precursor of
chitin aerogels, has shown tremendous improvement on mechanical
properties in Zhang’s group (Xu et al., 2016), suggesting a chemically
crosslinked chitin aerogels one of the solutions for reinforcement. In this
study, both physically crosslinked and double crosslinked chitin aero­
gels were obtained from the potassium hydroxide/urea aqueous solution
with the addition of poly(ethylene glycol) diglycidyl ether (EGDE) as a
crosslinker. EGDE has been proved to be an effective chemical cross­
linker for polysaccharide polymers including cellulose and chitosan by
etherification. As chitin is one of the polysaccharides with similar
functional groups, EGDE was chosen for the chemical crosslinking.
(AZLAN et al., 2009; Kono et al., 2016). In addition, the hydrophilicity
and water solubility of EGDE made it compatible to the KOH/urea
aqueous chitin solution and ease of functionalization. Therefore, we
hypothesized that the EGDE would be an effective chemical crosslinkers
for chitin and the crosslinked chitin aerogels generated would have
significant improvement on the mechanical properties. The aerogels
were characterized for their porosity, mechanical properties, and cor­
responding internal morphology affected by EGDE. The reaction and
interaction mechanism portrait were finally proposed for specific
interpretation.
2. Materials and methods
2.1. Materials
The chitin powder from shrimp shells (Pandalus borealis) was pur­
chased from Sigma-Aldrich (St. Louis, Missouri, United States) in prac­
tical grade. The potassium hydroxide (KOH) was purchased from Sigma-
Aldrich (St. Louis, Missouri, United States) in ACS reagent grade (≥85
%) in the form of pellets. The urea was purchased from Bioshop Canada
Inc (Burlington, ON, CA) in molecular biology grade (purity ≥99.5 %).
The hydrochloric acid (HCl)was purchased from Bioshop Canada Inc
Scheme 1. Chemical structures of (a) chitin and (b) EGDE.
2
Carbohydrate Polymers 265 (2021) 118014
(Burlington, ON, CA) in ACS reagent grade (12 N normal) and used for
preparing 5 wt% HCl aqueous solution. The sodium hydroxide (NaOH)
pellets were purchased from Caledon Laboratories Ltd (Georgetown,
ON, CA) in ACS reagent grade (purity ≥97 %) and were dissolved to
prepare 5 wt% NaOH aqueous solution. The Poly(ethylene glycol)
diglycidyl ether (EGDE) (molecular weight 500) was purchased from
Sigma- Aldrich (St. Louis, Missouri, United States) in a liquid form. All
chemicals above were used as received unless otherwise specified.
Scheme 1 present the chemical structures of the chitin and EGDE
used in the present work.
2.2. Fabrication methodology
The chitin powder was further purified in 5 wt% NaOH aqueous
solution, then 5 wt% HCl aqueous solution and again 5 wt% NaOH
aqueous solution. In each round, the suspension was stirred for one day
and washed with water until neutral followed by filtration. The final
product was dried under 80 ◦ C for 3 days and grinded to fine powders for
future use. The degree of acetylation of chitin after purification was
calculated to be 89.2 % using the values of absorbance peaks from the
corresponding FTIR spectroscopy (Renata et al., 2012). 5 wt% chitin
solution was made by dissolving certain amount of purified chitin
powder in an aqueous 4.2 M KOH/0.72 M urea solution via freeze/­
thawing method that has been previously reported with some modifi­
cation (Huang et al., 2017). The transparent chitin solution was
obtained after one freeze/thawing cycle. Corresponding amount of
EGDE was added to the chitin solution for different weight ratio between
chitin and EGDE followed by vigorous stirring. The mixed solution was
then centrifuged to remove air bubbles and finally casted in petri-dish
molds. The solution was then heated at 80 ◦ C for 3 h for the sol-gel
process where both physical gelation (Ding et al., 2012) and chemical
crosslinking happened (Li & Bai, 2005). The reaction between chitin
chains and EGDE was induced by the etherification between the epoxide
groups from EGDE and the hydroxyl groups from chitin as similar re­
actions between EGDE, chitosan and cellulose have already been
examined in some literature (AZLAN et al., 2009; Li & Bai, 2005;
Rodríguez et al., 2003; Shen et al., 2015). The detail of the reaction is
presented in Scheme 2, showing a ring opening of epoxide groups and
the formation of covalent bonding between the epoxide and hydroxyl
groups and by which chitin chains connect with each other in an intra
and intermolecular way. After that, the chitin hydrogels were thor­
oughly washed in ethanol bath where alcogels were formed with
neutralization and further physical gelation (Huang et al., 2017). The
alcogels were finally dried under supercritical CO2 to become aerogels.
The neat chitin aerogels without chemical crosslinking were obtained
with same procedures but skipping the addition of EGDE. The efficient
amount of the crosslinker EGDE was determined by the molar ratio
between chitin molecules with two N-acetyl-D-glucosamine units
(C16H28N2O11, 424 g/mol) and EGDE molecules (C8H14O4, 174 g/mol)
to balance the stochiometric ratio of the hydroxyl and epoxide func­
tional groups so that the complete crosslinking was achieved theoreti­
cally with the minimum EGDE loading of 0.5:1 with respect to the mass
of chitin. Samples with weight ratio of 1:0, 1:0.5, 1:1, and 1:1.5 between
chitin and EGDE were named neat, 0.5 EGDE, 1.0 EGDE, and 1.5 EGDE,
J. Wang et al.
Scheme 2. (a) Etherification reaction mechanism and (b) crosslinking between
chitin molecules and EGDE.
respectively.
2.3. Porosity, density, and shrinkage measurement
The skeletal volumes of the aerogels were measured by a AccuPyc II
1340 gas pycnometer (Micromeritics Instrument Corporation, GA,
United States) under nitrogen condition. The diameter and the height of
the aerogels were measured by a caliper to calculate the bulk volumes of
the aerogels. The porosity, bulk density and the true density were
calculated using the measured weight, skeletal and bulk volumes. The
shrinkage of the aerogels was calculated by measuring the diameters of
the mold and the aerogels.
2.4. Aerogels morphology characterization
The effect of the chemical crosslinker EGDE on the morphologies of
the chitin aerogels were characterized by observing under the JEOL JSM
1000 SEM (JSM USA, Inc., Massachusetts, United States). The cross-
section of the aerogels was obtained by direct breaking. The samples
were loaded with carbon tapes and sputter coating before observation.
2.5. Chemical structure characterization
The chemical structures of the aerogels were characterized by the
infrared spectroscopy using a Platinum ATR spectrometer (Bruker Co.,
Massachusetts, USA). The absorbance spectra were measured in the
4000− 400 cm− 1 range.
2.6. Compressive testing
Compressive tests were carried out according to the ASTM standard
D695 using a Instron 5848 Universal Testing Machines (Instron, Mas­
sachusetts, United States). The samples were finely sanded with flat
surfaces and loaded in a cylinder form. The loading rate was set to
0.5 mm/min. The compressive strength was measured at 10 % strain and
the elastic modulus was measured from the initial slope of the stress-
strain curve.
3
Carbohydrate Polymers 265 (2021) 118014
2.7. Thermogravimetric analysis
The thermal stability of the aerogels was measure via the thermog­
ravimetric analysis TGA Q50 (TA Instruments, New Castle, United
States). Samples were cut to cubes less than 50 mg and loaded on a
platinum plate. The ramp testing had the temperature increased to
600 ◦ C at the rate of 20 ◦ C/min with nitrogen gas flow.
3. Results and discussion
3.1. Shrinkage, porosity, and density verification of aerogels
The properties summary including the shrinkage, porosity and the
density were listed in the Table 1 for clarification. The porosity of the
neat chitin aerogels has reached 96 % while that of the chemically
crosslinked chitin-EGDE aerogels are about 93 %. As research results
from other groups have shown a porosity range of 84.1 %–97 % for
chitin aerogels fabricated via different methods (Ding et al., 2012, 2016;
Heath et al., 2013; Silva et al., 2011; Tsioptsias et al., 2009; Tsutsumi
et al., 2014; Wu & Meredith, 2014), the chemically crosslinked chitin
aerogels has shown adequate porosity with limited reduction from that
of neat chitin aerogels. The bulk density was increased for chitin-EGDE
aerogels from 0.5 to 1.5 EGDE samples compared with the neat refer­
ence, suggesting a closer packed chitin polymer chains shown up after
chemical crosslinking. The relative drop of the bulk density with the
increased amount of EGDE from 0.5 to 1.0 EGDE samples was ascribed to
the relative decreased composition of chitin as weaker intermolecular
association and less chain entanglement happened due to less chitin
concentration (Ding et al., 2012). The unusual drop of density for 1.5
EGDE samples will be discussed in later section. Fig. 1 has shown the
appearance transition of chitin aerogels in different stage of fabrication.
It can be observed that the chitin solution and that with EGDE occupied
comparable volume when casted in petri-dish molds although the
transparent solution has become opaque when mixed with EGDE. The
physical chitin hydrogel and chemically crosslinked chitin -EGDE
hydrogels obtained from heat treatment and sol-gel process both showed
yellowish color and the major shrinkage occurred in this stage as the
volumes of the hydrogels, alcogels obtained from ethanol washing, and
the supercritical dried aerogels were comparable shown in Fig. 1(c).
Compared with samples without chemical crosslinking, it can be seen
that the etherification reaction between chitin and EGDE would not only
crosslink the chitin polymer chains but also supplement equal amount of
hydroxyl groups consumed, inducing more intermolecular association
and physical entanglement in between chitin chains, thus the overall
shrinkage was increased. Furthermore, although the density of 1.0 EGDE
samples dropped compared with 0.5 EGDE samples, the shrinkage
slightly increased as the amount of hydrophilic functional groups and
the corresponding water holding capability were diminished with the
relative decreased chitin composition. The drop of the shrinkage at 1.5
EGDE samples was related to the excessive amount of EGDE which
would be discussed in detail in later parts.
Table 1
Physical properties summary of the aerogels.
Samples Porosity (%) Bulk Density (g/ True Density Shrinkage
cm^3) (g/cm^3) (%)
Neat 96.05 ± 0.35 0.14 ± 0.0033 3.67 ± 0.19 20.50 ± 0.45
0.5 93.25 ± 0.49 0.34 ± 0.0570 4.86 ± 0.05 32.91 ± 1.29
EGDE
1.0 93.40 ± 0.14 0.25 ± 0.0051 3.81 ± 0.18 34.39 ± 0.16
EGDE
1.5 93.30 ± 0.20 0.22 ± 0.0053 3.24 ± 0.14 23.64 ± 1.99
EGDE
J. Wang et al.
Fig. 1. The appearance the (a) neat chitin solution, (b) chitin solution with
EGDE added, and (c) the hydrogel after sol-gel process, the alcogel after thor­
ough ethanol washing and the aerogel from supercritical CO2 drying.
3.2. Internal morphology of aerogels
Fig. 2 has presented the scanning electron micrographs of the in­
ternal morphology of the neat chitin aerogels and the aerogels with
different amount of EGDE. The images are presented with the magnifi­
cation of x30k, x50k and x75k, and the scale bars of 5 μm and 2 μm
accordingly for comparison. The porous network structure of all samples
exhibiting high portion of open cell volumes has confirmed the structure
retaining after supercritical CO2 drying and matched the porosity
resulted mentioned above. The microstructure also suggested the ho­
mogenous dissolution of chitin in the KOH/urea aqueous solution.
However, it can be clearly observed that the addition of EGDE has
completely affected the morphology and the pore structure. The neat
samples in Fig. 2(a–c) with sole physical gelation from heating and
ethanol coagulation have maintained the porous structure with open-
ended homogenous nano-sized chitin fibrils. Loosely stacked chitin fi­
brils could be detected intertwining with each other suggesting effective
intermolecular association and entanglement during physical gelation.
Compared with physically crosslinked samples, chemically crosslinked
samples have exhibited a comparable size of chitin fibrils. More spe­
cifically, the chemically crosslinked chitin fibrils in samples 0.5 and 1.0
EGDE in Fig. 2(d–i), have displayed a close-end structure with twisted
and angled fibrils alignment, resulting in a denser construction. Besides
the end-to-end polymer chain connection, the etherification occurred
uniformly throughout the entire aerogel has led to the interconnected
fibrils and network microstructure as well. The morphology of 1.5 EGDE
samples in Fig. 2(j–l) has suggested that the weight ratio of 1:1.5 be­
tween chitin and EGDE have included excessive amount of EGDE for
effective chemical crosslinking to happen. Although the end epoxide
groups of EGDE is polar and water soluble, extra EGDE left that could not
react with chitin in the aqueous solution formed droplets under mo­
lecular interaction such as hydrogen bonding, configuring a water-in-
water emulsion system. Such system has met the condition of
emulsion-templating technique that has been used for macroporous and
mesoporous manipulation in the fabrication process of various polymer
aerogels recently (Gui et al., 2020; Liu et al., 2020; Mawhinney & Jana,
2019; Teo et al., 2018; Tian et al., 2020). It can be inspected that
micro-scale sized pores with various diameter were left after extra EGDE
was washed out during the exchanging phase of water and ethanol. The
fibrils arrangement of 1.5 EGDE samples was comparable with that of
0.5 and 1.0 EGDE samples seeing through those macropores except that
4
Carbohydrate Polymers 265 (2021) 118014
at the edges of such macropores there were denser stacks of chitin fibrils
existing.
3.3. Chemical structure of aerogels
Fig. 3 provides the chemical structure analysis of the aerogels eval­
uated by FTIR spectroscopy. All aerogels samples have exhibited similar
spectra as shown in Fig. 3(a). Characteristic absorbance peaks of chitin
including the vibration of NH groups at 3263 cm^-1, vibration of the
amide I C–– O bonds in the region of 1660− 1624 cm^-1, the stretching of
C–O bonds in the region of 1080− 1020 cm^-1 were all presented
(Cárdenas et al., 2004) as all aerogels shared similar backbone chitin
molecules. The absence of peaks of epoxide rings including
ring-stretching weak band in the region of 1280− 1230 cm^-1, asym­
metric ring deformation strong band in the region of 950− 815 cm^-1 and
the symmetric ring deformation with showing strong band in the region
of 880− 750 cm^-1 has shown the complete reaction and residual
removal of EGDE after ethanol washing and supercritical drying (Chi­
niwalla et al., 2003). One of the characteristic peaks of EGDE showing
the stretching of ether C–O bonds as well as the C–C bonds around
1100 cm^-1 could not be distinguished for EGDE crosslinked aerogels as
the chitin molecule would generate the same stretching peaks in the neat
samples spectrum (Van Wagner et al., 2011). However, the weakened
peak at 1028 cm^-1 in Fig. 3(b) could be viewed as a C–O–H defor­
mation of chitin molecules and a signal of etherification reaction be­
tween EGDE and chitin (Duerkop, 2008).
3.4. Mechanical properties of aerogels
Fig. 4 displayed the mechanical properties in the aspect of
compression for the aerogels obtained with different amount of EGDE
crosslinkers. The statistic comparison of the compressive properties
including compressive strength at 10 % strain and the elastic modulus is
presented in Table 2 with specific values and standard deviation. All
samples have exhibited typical aerogels compressive stress-strain curves
with an initial elastic part of the whole aerogels, followed by a plateau
resulting from the rapid pressing out of air content, and finally a pre­
cipitous rise due to the direct compressing of aerogels bulk materials in
Fig. 4(a). Compared with neat chitin aerogels, chemically crosslinked
EGDE chitin aerogels have shown the maximum at 1.0 EGDE samples
with the increase of 247 % on compressive strength at 10 % strain in
Fig. 4(b) and the increase of 243 % on elastic modulus in Fig. 4(c). In
comparison with the chitin aerogels fabricated in the similar KOH/urea
aqueous system at same concentration of 5 wt% (compressive strength
at 10 % strain: 0.2 MPa and modulus: 2.6 MPa), the neat samples in this
study has shown comparable compressive strength at 10 % strain
(0.21 MPa) and elastic modulus (2.54 MPa) (Ding et al., 2016). The
addition of appropriate portion of chemical crosslinker EGDE in samples
0.5 EGDE and 1.0 EGDE has significantly increased both the compressive
strength and the modulus. The reinforcement was mainly attributed to
the intermolecular strong bonding between chitin fibrils induced by the
etherification, matching with the close-ended chitin fibrils observed at
the internal morphology of the aerogels. The other reason that may have
contributed to such significant improvement is the stronger inter and
intramolecular bonding caused by the supplemented hydroxyl groups
generated as the by products of the etherification. The fibrils arrange­
ment mentioned above has clearly indicated a denser structure, sug­
gesting the occurrence of extra inter and intramolecular forces in
samples 0.5 and 1.0 EGDE compared with that of neat chitin aerogels
samples. Therefore, EGDE could be confirmed as an effective chemical
crosslinkers for chitin in the aspects of aerogels reinforcement. On the
other hand, the 1.5 EGDE samples, though tougher than the neat sam­
ples, had a drastic drop of properties from 1.0 EGDE samples. The main
cause of such property drop could be ascribed to the macroporous in­
ternal structure of the aerogels resulting from the excessive EGDE. As
indicated by the internal morphology of 1.5 EGDE samples above, when
J. Wang et al.
Fig. 2. SEM images of the internal morphologies of the aerogels: (a-c) neat samples, (d-f) 0.5 EGDE, (g-i) 1.0 EGDE, and (j-l) 1.5 EGDE in which scale bars are 5 μm
and 2 μm respectively.
too much EGDE has been added, emulsion would happen inside the
aerogels with EGDE droplets left from reaction. It can be concluded that
both the lack of homogenous porous structure for effective load transfer
and the flaws role acted by those emulsion caused macropores lead to a
drastic drop of the compressive mechanical properties of the aerogels.
3.5. Thermal properties of aerogels
Fig. 5 provides the thermal characteristics of the aerogels in the
aspect of thermal degradation under a temperature ramp condition.
There has been an initial weight loss around 10 wt% for all samples
before 200 ◦ C suggesting an evaporation and detachment of the volatile
content trapped in the aerogels (Wang, Chen et al., 2020). It can be
observed from the TGA ramp curves that neat chitin aerogel samples
have the major weight loss in the region of 200 ◦ C–400 ◦ C while all
chemically crosslinked aerogel samples have endured phased weight
5
Carbohydrate Polymers 265 (2021) 118014
drop in such temperature range. In accordance with the morphology and
mechanical properties analysis results, the optimal 1.0 EGDE samples
have shown the least weight drop in the first phase compared with 0.5
and 1.5 EGDE samples. After a continuous weight drop between 300 ◦ C
and 350 ◦ C, the 1.0 and 0.5 EGDE samples have reached similar weight
residual with 0.5 EGDE samples. The plateau right after 350 ◦ C for all
crosslinked samples marks the end of the phased thermal degradation
that could be attributed to the chemical bonds breaking and the initia­
tion of the degradation of polymer backbones. In addition, compared
with neat samples, crosslinked aerogel samples have a little improve­
ment in the thermal degradation onset temperature shown in Fig. 5(b),
increased from 199 ◦ C to maximum of 210 ◦ C listed in Table 2. The
subtle increase of the degradation onset may have suggested a delay of
weight loss and thermal degradation experienced by the crosslinked
aerogels. The optimal 1.0 EGDE samples have delayed the polymer
backbone degradation the most with the slowest weight loss under
J. Wang et al. Carbohydrate Polymers 265 (2021) 118014

Fig. 3. FTIR analysis of the aerogels: (a) the complete spectra (b) peaks highlighted in the wavenumber range of 1080–1020 cm− 1.

Fig. 4. Compressive properties: (a) compressive stress-strain curve, (b) compressive strength at 10 % strain, and (c) elastic modulus.

6
J. Wang et al. Carbohydrate Polymers 265 (2021) 118014

Table 2 intramolecular forces from abundant remaining hydroxyl end groups.

Mechanical and thermal properties summary of the aerogels. However, when excessive amount of crosslinker was added, those
Samples Compressive strength Elastic modulus Degradation unreacted EGDE molecules will be surrounded and trapped by those
(MPa) (MPa) temperature (◦ C) crosslinked chitin network as shown in Fig. 6. The caused emulsion ef­
Neat 0.21 ± 0.05 2.54 ± 0.23 199.43 ± 3.74 fect will generate macropores after extra EGDE washed out by the
0.5 0.62 ± 0.18 7.39 ± 1.40 206.58 ± 2.06 ethanol and let the aerogels have the mesoporous and macroporous
EGDE structure. The altered morphology and bonding have been reflected in
1.0 0.73 ± 0.11 8.70 ± 1.50 203.53 ± 1.63 the compressive mechanical properties of the aerogels. The optimal 1.0
EGDE
1.5 0.26 ± 0.04 3.58 ± 0.62 209.87 ± 0.66
EGDE samples have shown a significant increase of both compressive
EGDE strength at 10 % strain and the elastic modulus to the extent of 250 %
while the 1.5 EGDE samples with excessive crosslinkers have presented a
rapid property drop. Finally, the addition of EGDE could not be clearly
elevating temperature. reflected on the FTIR spectra of the aerogels and has limited effect on the
thermal degradation onset but just showing some delayed decomposi­
3.6. Discussion tion of the aerogels.

The experimental data obtained in this study has demonstrated the
poly(ethylene glycol) diglycidyl ether (EGDE) is an effective chemical
crosslinker of chitin aerogels for significant enhancement of mechanical
properties. First of all, the incorporation of different loading amount of
EGDE has maintained the high porosity and light weight of the chitin
aerogels. Then the chemical crosslinking has induced enormous change
of the internal morphology of the aerogels in the aspect of fibrils
arrangement and porous structure revealed in the internal morphology
of the aerogels. Fig. 6 proposes an interaction mechanism between chitin
and EGDE during aerogel construction. It suggests that physical aerogels
have only induced chitin fibrils entanglement and intermolecular
interaction during the gelation process while aerogels with appropriate
amount of EGDE added have generated both physical and chemically
crosslinked domains to form gels. The chemical crosslinking from
etherification between chitin and EGDE results in the close-ended fibrils
and a denser fibril structure via stronger covalent bonding, inter and
4. Conclusion
The research of chitin aerogels remains at a preliminary stage
compared with that of another biopolymer cellulose. While cellulose
aerogels have already utilized various techniques such as chemical
functionalization and chemical crosslinking for mechanically strong
aerogels, the processing and fabrication of chitin aerogels are still
dependent on the direct sol-gel and drying process leading to inadequate
strength. This study first time applied the EGDE chemical crosslinker to
the chitin aerogels showing significant improvement on the compressive
properties. This study has demonstrated EGDE an effective chemical
crosslinkers for chitin via etherification, resulting in interconnected and
denser fibrils arrangement inside the aerogels for reinforcement. Thus,
other chitin materials could also apply EGDE as a crosslinker for various
applications. Furthermore, emulsion effect induced by excessive EGDE
caused a mesoporous and macroporous structure of the aerogels

Fig. 5. Thermal stability of the aerogels: (a) TGA ramp curves, and (b) thermal degradation onset temperature.

Fig. 6. Interaction mechanism of physical and chemical crosslinked aerogels.

7
J. Wang et al. Carbohydrate Polymers 265 (2021) 118014

suggesting a morphology tuning capability of EGDE for chitin aerogels sodium palmitate. Green Chemistry, 16(4), 1921–1930. https://doi.org/10.1039/
c3gc41895b
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analysis. Hani E. Naguib: Conceptualization, Methodology, Writing - ie050145k
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Declaration of Competing Interest aerogels for water treatment by organic liquid removal and solar vapor generation.
ChemSusChem, 13(4), 749–755. https://doi.org/10.1002/cssc.201902970
The authors report no declarations of interest. Mawhinney, K., & Jana, S. C. (2019). Design of emulsion-templated
mesoporous–macroporous polyurea gels and aerogels. ACS Applied Polymer Materials,
1(11), 3115–3129. https://doi.org/10.1021/acsapm.9b00762
Acknowledgments Mi, Q. Y., Ma, S. R., Yu, J., He, J. S., & Zhang, J. (2016). Flexible and transparent
cellulose aerogels with uniform nanoporous structure by a controlled regeneration
process. ACS Sustainable Chemistry and Engineering, 4(3), 656–660. https://doi.org/
The authors of this work would like to acknowledge the support from 10.1021/acssuschemeng.5b01079
Mitacs Accelerate program (Grant number: IT17342). Zhiqiang Chen Min, B. M., Lee, S. W., Lim, J. N., You, Y., Lee, T. S., Kang, P. H., & Park, W. H. (2004).
acknowledges the support from the China Scholarship Council (No. Chitin and chitosan nanofibers: Electrospinning of chitin and deacetylation of chitin
nanofibers. Polymer, 45(21), 7137–7142. https://doi.org/10.1016/j.
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