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Stabilizing alkenyl succinic anhydride (ASA) emulsions with starch

nanocrystals and fluorescent carbon dots

Article  in  Carbohydrate Polymers · February 2017

DOI: 10.1016/j.carbpol.2017.02.007

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 Carbohydrate Polymers 165 (2017) 13–21

Contents lists available at ScienceDirect

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

Stabilizing alkenyl succinic anhydride (ASA) emulsions with starch

nanocrystals and fluorescent carbon dots
Bei Gong, Wenxia Liu ∗ , Xueshuai Chen, Hua Tan, Xiuli Zhang, Huili Wang, Dehai Yu,
Guodong Li, Zhaoping Song
Key Laboratory of Pulp & Paper Science and Technology (Qilu University of Technology), Ministry of Education, Jinan, Shandong, 250353, China

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

Article history: Stabilizing alkenyl succinic anhydride (ASA) emulsions using fine particles instead of cationic starch have
Received 14 September 2016 attracted much attention in recent years. Herein, starch nanocrystals (SNCs) made from maize starch by
Received in revised form 25 January 2017 H2 SO4 hydrolysis were used to co-stabilize ASA emulsions with fluorescent carbon dots (CDs) made
Accepted 2 February 2017
hydrothermally from gelatin. The introduction of CDs can significantly enhance the stability and reduce
Available online 7 February 2017
the droplet size of SNC-stabilized ASA-in-water emulsions. Consequently, the sizing performance of the
SNC-stabilized ASA emulsion is significantly improved by increasing the CD-to-SNC mass ratio. SNC and
Chemical compounds studied in this article:
CD co-stabilized ASA emulsions show much better sizing performance than starch and CD co-stabilized
Corn starch (PubChem CID: 439341)
Cellulose (PubChem CID: 3084047)
ASA emulsions, achieving their best sizing performance at a CD-to-SNC mass ratio of 80%. Meanwhile,
Gelatin (PubChem CID: 441411) the morphology of SNC/starch and CD co-stabilized ASA emulsions can be traced under UV excitation.
Octadecenylsuccinic anhydride (PubChem © 2017 Elsevier Ltd. All rights reserved.
CID: 120045)
Aluminum sulfate (PubChem CID: 24850)
Sulfuric acid (PubChem CID:1118)

Keywords:
Starch nanocrystals
Alkenyl succinic anhydride
Emulsions
Carbon dots
Paper sizing

1. Introduction
Starch is a cheap, abundant, renewable and biodegradable
biopolymer. After being transformed into various derivatives,
starches can be used in the papermaking industry as dry strength
agents (Ghasemian, Ghaffari, & Ashori, 2012), surface sizing agents
(Brenner, Kiessler, Radosta, & Arndt, 2016), coating and paper-
board adhesives (García et al., 2012), emulsion stabilizers (Gess
& Rende, 2005), filler modifiers (Huang, Qian, Li, Lou, & Shen,
2015) and starch-based fillers (Shen, Song, Qian, & Ni, 2011). When
acting as the emulsion stabilizer in a paper sizing agent such as
alkenyl succinic anhydride (ASA), starch is generally functional-
ized by cationization and acid-hydrolysis and gelatinized before
use (Ghasemian et al., 2012). Because ASA is highly reactive to
∗ Corresponding author.
E-mail address: liuwenxia@qlu.edu.cn (W. Liu).
both cellulose and water, and the gelatinized cationic starch is not
an efficient emulsion stabilizer, a large amount of cationic starch
(equivalent to 3–5 times the amount of ASA) has to be employed to
reduce the hydrolysis of ASA and obtain satisfactory sizing perfor-
mance (Hubbe, 2007). Consequently, ASA emulsions must be of low
concentrations due to the high viscosity of gelatinized starch dis-
persions, resulting in low production efficiency for ASA emulsions
as well as high energy consumption for pumping material.
In addition to conventional surfactants and polymers, solid
particles can also act as emulsion stabilizers by attaching to
the oil–water interface when they are partly wetted by oil and
water (Aveyard, Binks, & Clint, 2003). Particle-stabilized emulsions,
known as Pickering emulsions, generally show high coalescence
stability due to formation of particle barriers around emulsion
droplets (Binks, 2002). In recent years, considerable effort has been
made to stabilize ASA emulsions with fine particles, such as mont-
morillonite (Yu, Lin, & Li, 2013), titanium dioxide (Li, Liu, Zhang,
Yin et al., 2013; Zhao, Liu, Liu, Ding, & Li, 2013), Fe3 O4 (Lin, Yu, &

http://dx.doi.org/10.1016/j.carbpol.2017.02.007
0144-8617/© 2017 Elsevier Ltd. All rights reserved.
14 B. Gong et al. / Carbohydrate Polymers 165 (2017) 13–21
Li, 2015) and laponite (Qian et al., 2013; Zhang et al., 2014; Gong
et al., 2017), after their wettabilities were tailored by surfactants,
polymers or short amines. Particle-stabilized ASA emulsions gener-
ally possess enhanced ASA concentration, high coalescence stability
and reduced hydrolysis of ASA due to the formation of particle
barriers around ASA droplets (Tan et al., 2014). Consequently, ASA
emulsions stabilized by fine particles, especially laponite particles,
not only have high ASA concentration but also show rather high siz-
ing performances (Li, Liu, Zhang, Qian, & Wang, 2013; Wang, Liu,
Zhou, Li, & Qian, 2013). However, the previously reported parti-
cle stabilizers for ASA emulsions are all inorganic mineral particles
that are not renewable or biodegradable. It has not yet been inves-
tigated whether the advantages of using nanoparticles to stabilize
ASA emulsions still exist when the nanoparticles have the same
chemical components as the polymers.
Starch nanocrystals (SNCs) are crystalline nanoparticles of
starch prepared by disruption of amorphous regions from
semicrystalline starch granules by acid hydrolysis (Le Corre, Bras,
& Dufresne, 2010). SNCs made from waxy maize starch granules
have been reported to be competent stabilizers for paraffin emul-
sions (Li, Sun, & Yang, 2012; Li, Li, Sun, & Yang, 2014) and can act
as a stabilizer for the emulsion polymerization of butyl methacry-
late (Haaj, Thielemans, Magnin, & Boufi, 2014). Meanwhile, SNCs
derived from different native starch granules or preparation meth-
ods show different morphologies and particle sizes (García, Ribba,
Dufresne, Aranguren, & Goyanes, 2011; Gong et al., 2016; Kim, Lee,
Kim, Lim, & Lim, 2012; Le Corre, Bras, & Dufresne, 2011; Putaux,
Molina-Boisseau, Momaur, & Dufresne, 2003), providing options
for particle-stabilized emulsions. Herein, we selected SNCs with
short tubular structures as a particle stabilizer for ASA emulsions
and compared the stability, droplet size and sizing performance of
SNC-stabilized ASA emulsions with that of starch-stabilized ASA
emulsions. The SNCs were found to stabilize ASA-in-water emul-
sion with higher stability, smaller droplet size and better sizing
performance than starch. However, the SNCs were still not able
to provide adequate stability for ASA emulsions at a typical SNC-
to-ASA mass ratio of 2%. Our previous study shows that SNCs from
normal maize starch granules exhibit a greater water contact angle,
i.e., higher oil-wettability, than native starch granules because of
the removal of the amorphous regions (Gong et al., 2016), which is
unfavorable for preparing stable ASA-in-water emulsions. For this
reason, the water-wettability of SNCs must be improved.
Since ASA is a paper sizing agent, which is required to be well-
distributed on cellulose fiber surfaces as an ASA-in-water emulsion,
the wettability of particle stabilizer to ASA must be carefully tai-
lored to prepare ASA emulsions with small droplet size and uniform
droplet size distribution (Tan et al., 2014; Zhang et al., 2014). The
method most extensively used for increasing the water wettability
of SNCs is to introduce hydrophilic groups onto SNCs’ surfaces by
chemical modifications (Wei, Sun et al., 2016). However, chemical
modification is not well-suited for tailoring the wettability of SNCs
to ASA because of the substantial changes in the SNCs’ wettability
even at low levels of surface substitution (Espino-Pérez et al., 2016;
Wei, Zhang et al., 2016).
Carbon dots (CDs) are fluorescent quasi-spherical carbon
nanoparticles with diameters of 2–10 nm that have carbon cores
and surface functional groups containing oxygen, nitrogen, or sulfur
(Fernando et al., 2015; Georgakilas, Perman, Tucek, & Zboril, 2015;
Zhu et al., 2015). Previously, many green synthetic approaches
using biocompatible but inexpensive staring materials for fabri-
cation of CDs have been reported to prepare CDs with low cost,
high water-solubility, excellent biocompatibility and many poten-
tial applications such as chemical sensing, biosensing, bioimaging,
nanomedicine, photocatalysis and electrocatalysis (Lim, Shen &
Gao, 2015; Wang & Hu, 2014). In addition, CDs have been found to
show surface activity and be able to co-stabilize paraffin-in-water
emulsions with laponite nanoparticles (Tan et al., 2015). Therefore,
CDs prepared by hydrothermal carbonization of gelatin were used
as a fluorescent particle co-stabilizer of ASA emulsions in order
to balance the wettability of SNCs to ASA and water. Gelatin was
selected as the starting material for preparing CDs due to its abun-
dant amino and carboxyl groups, which provide it with the ability
to interact with the SNCs. The interaction of CDs with SNCs sig-
nificantly reduced the hydrophobicity and negative zeta potential
of SNCs and lowered the interfacial tension between ASA and SNC
aqueous dispersion. Consequently, the SNCs became an excellent
particle stabilizer for ASA-in-water emulsions in the presence of
CDs, producing ASA emulsions with high stability, small droplet
size and excellent sizing performances. Meanwhile, CDs were also
found to enhance the stability, reduce the droplet size and improve
the sizing performance of starch-stabilized ASA emulsions. Further-
more, the morphology of the emulsions and the distribution of SNCs
and CDs could be traced under UV excitation.
2. Experimental
2.1. Materials
Normal maize starch was kindly provided as white powder
with purity greater than 99.5 wt% (based on oven-dried starch) by
Yanzhou Xilai Fine Chemistry Co., Ltd. (Shandong, China). Gelatin
was purchased from Aladdin Chemistry Co., Ltd. (Shanghai, China)
and was used without further purification. Alkenyl succinic anhy-
dride (ASA) was a commercial product of Dixie Chemical Co., Inc
(Pasadena, Texas, US). It is an amber liquid with a density of
0.947 g/cm3 at 25 ◦ C. According to the supplier’s specification, the
ASA is composed of 94.9 wt% of octadecenylsuccinic anhydride
(C22 H38 O3 ), 3.38 wt% of hexadecenylsuccinic anhydride (C20 H34 O3 )
and residual olefins. Aspen bleached chemi-thermomechanical
pulp (BCTMP) was supplied as pulp board by Shandong Chen-
ming Paper Group Co., Ltd. After being torn to pieces, immersed
in tap water overnight and disintegrated using a standard dis-
integrator, the BCTMP was beaten to 40◦ SR using a laboratory
valley beater before use. Cationic polyacrylamide (CPAM) with
a trade name of Percol 292 was obtained from Ciba Specialty
Chemicals Ltd. Laponite is a product of Rockwood Additives Ltd.
(U.K.), supplied as a white powder named as Laponite RD. Sulfuric
acid, ammonia (NH3 ·H2 O, 25–30 wt%), sodium hydroxide, and alu-
minum sulfate (Al2 (SO4 )3 ·18H2 O, >99.0%) are analytical reagents.
Deionized water, which was prepared by ion exchange, was used
throughout the experiment except for dispersing BCTMP and mak-
ing handsheets.
2.2. Preparation and characterization of SNCs
Starch nanocrystals (SNCs) with short tubular structures were
prepared according to the procedure in our previous report (Gong
et al., 2016). In a typical process, 36.72 g of normal native maize
starch granules were dispersed in 250 mL of 3.16 M H2 SO4 solution.
The mixed suspension was warmed to 40 ◦ C and was magnetically
stirred for 7 days at 100 rpm. The resulting suspension was cen-
trifuged at 4500 rpm and washed with deionized water until its
pH value reached 5. The centrifuged cake was further treated with
1 wt% ammonia for 20 min and washed by successive centrifuga-
tion at 4500 rpm with distilled water until pH 9. After relaxation
for 5 days at 4 ◦ C, SNCs with short tubular structures were obtained.
The morphology of the as-prepared SNCs was analyzed by a JEOL
JEM 2100F high-resolution transmission electron microscopy (HR-
TEM), in which the samples were prepared by dripping a drop of
dilute SNC dispersion on a TEM ultra-thin carbon supporting film.
 B. Gong et al. / Carbohydrate Polymers 165 (2017) 13–21
The zeta potential of the SNCs in aqueous dispersion was tested at
25 ◦ C with a Zetasizer 3000 (Malvern Instruments, UK).
2.3. Preparation and characterization of CDs
CDs were synthesized by dissolving gelatin in warm water fol-
lowed by hydrothermal treatment at 200 ◦ C for 3 h, according to
the procedure reported by Liang et al. (Liang, Ma, Shi, Li, & Yang,
2013). In a typical process, 1.6 g gelatin was added to 80 mL of
water and warmed to 40 ◦ C under agitation. After the gelatin was
dissolved, the mixture was transferred into a 100 mL Teflon-lined
autoclave and heated at 200 ◦ C for 3 h. The autoclave was then natu-
rally cooled to room temperature. The sample was then centrifuged
at 16,000 rpm for 30 min. The supernatant, a light brown aque-
ous liquid, contained the obtained CDs. The as-prepared CDs were
imaged by a JEOLJEM2100F high-resolution transmission electron
microscope (HR-TEM). The optical properties of the CDs were stud-
ied using a fluorescence spectrophotometer and a digital camera.
The chemical characteristics of the CDs were analyzed by Fourier
transform infrared (FT-IR) spectroscopy with a Nicolet Avatar 370
infrared spectrometer in the range of 400–4000 cm−1 using pressed
KBr disks.
2.4. Effects of CDs on properties of SNCs and SNC aqueous
dispersion
The as-prepared SNCs were diluted with deionized water to
form a 2 wt% aqueous dispersion under agitation. Meanwhile, a
gelatinized starch dispersion was prepared by dispersing 6 g of
maize starch granules into 100 mL of deionized water and heating
the resulting dispersion at 90 ◦ C for 20 min. After being cooled to
room temperature, the gelatinized starch dispersion was diluted to
2 wt% with deionized water. A CD aqueous dispersion was directly
added to the SNC/gelatinized starch aqueous dispersion at a pre-
determined mass ratio of CD-to-SNC/starch under agitation. Part
of the mixed SNC and CD aqueous dispersion was freeze-dried and
compressed into a circular disk with a thickness of approximately
1 mm using an HY-12 tablet machine under a pressure of 16 MPa.
The disk was carefully placed at the bottom of a transparent ves-
sel followed by pouring ASA oil into the vessel. After the disk was
kept in the oil for more than 3 min, a drop of deionized water was
placed on the compressed disk. After 10 s, the appearance of the
water drop was recorded using an optical contact angle measuring
device (JC2000C1, Shanghai Powereach Co., Ltd), and the value of
the contact angle was determined by the photogoniometric method
(Zhao et al., 2013). The leftover sample was diluted with deionized
water to form an aqueous dispersion with an SNC mass fraction of
0.67%. The zeta potential of SNCs in the aqueous dispersion, the pH
and conductivity of the aqueous dispersion at 25 ◦ C were measured
with a Zetasizer 3000 (Malvern Instruments, UK), PHS-25 pH meter
(digital, Shanghai Precision & Scientific Instrument Co., Ltd., China)
and a DDS-11 digital conductivity meter (Shanghai Pengshun Sci-
entific Instrument Co., Ltd., China), respectively. The surface tension
of CD-SNC aqueous dispersions and the interfacial tension between
ASA and the CD-SNC aqueous dispersions were tested by a Krüss
K100MK2 tensiometer (KRÜSS GmbH, Germany) at 25 ◦ C
2.5. Preparation and characterization of ASA emulsions
ASA emulsions were prepared by adding 15 mL of aqueous CD-
SNC dispersion into 5 mL of ASA and homogenizing the mixture
using an FM200 high shear emulsifier (FLUKO Equipment Shang-
hai Co., Ltd.) with a 1.0 cm head at 6000 rpm for 3 min at 25 ◦ C.
Immediately after homogenization, the conductivity of the emul-
sions was determined with a DDS-11A digital conductivity meter to
determine their emulsion type. The emulsion stability was charac-
15
terized by the emulsion phase volume fraction, which was the ratio
of emulsion phase volume to the total volume of the emulsified sys-
tem after being stored at room temperature (25 ◦ C) for 24 h (Tan
et al., 2014; Zhang et al., 2014). The morphology of the emulsion
was recorded on a Rise-3002 optical biomicroscope (Jinan Runzhi
Science and Technology Co., Ltd.) after the emulsion was prepared
for one hour. The average diameter of the emulsion droplets was
calculated using microscopic image analysis software provided by
the manufacturer. The distribution of CDs on emulsion droplet sur-
faces ware observed using a laser confocal microscope (Leica TCS
SP8, Germany).
2.6. Handsheet manufacturing and sizing degree measurement
The performance of the as-prepared ASA emulsions as an inter-
nal sizing agent was tested by making sized handsheets with a
basis weight of approximately 60 g/m2 on a PTI Rapid-Köthen
Blattbildner-sheet Former and measuring the sizing degree of the
handsheets according to China National Standard GB/T460-2008
(Ding, Liu, & Zhao, 2011; Li, Liu, Zhang, Qian et al., 2013). To pre-
pare the sized handsheets, 2 wt% of aluminum sulfate (based on
oven-dried BCTMP, the same bellow) was added to 1 wt% BCTMP
suspension with a pH of approximately 7.5 at a stirring speed of
750 rpm, followed by addition of the as-prepared ASA emulsion,
and this was followed by 0.03 wt% of CPAM in sequence. After each
addition, the pulp suspension was stirred for 60 s. The mixture
then underwent high shearing with the stirring speed increased
to 1200 rpm. The stirring speed was then returned to 750 rpm, and
0.3 wt% of laponite was added and mixed for 60 s. After that, hand-
sheets were made with the above-mentioned instrument and dried
using a speed dryer at 105 ◦ C. To measure the sizing degree, a hand-
sheet was cut into square paper samples of 30 mm × 30 mm and
conditioned at 23 ± 1 ◦ C and 50 ± 2% relative humidity for over 24 h.
A paper sample was then folded into a square vessel with a bot-
tom dimension of 20 mm × 20 mm. The paper vessel was floated
on the surface of 2 wt% ammonium thiocyanate solution, and a
drop (approximately 0.06 mL) of 1 wt% ferric chloride solution was
dripped onto the bottom of the vessel. The penetration time was
determined as the time required for red ferric thiocyanate spots to
appear. The sizing degree of the hand-sheet was the average per-
meation time of 10 paper vessels. Half of the inner bottoms showed
permeation to the wire-side of the handsheet.
3. Results and discussion
3.1. Characterization of as-prepared SNC and CDs
The structure, morphology and chemical composition of as-
prepared SNCs made from normal maize starch have been
characterized in our previous report (Gong et al., 2016). The SNCs
show a typical A-type starch crystalline pattern of normal maize
starch granules, but they have an improved crystallinity, more
O C O groups and a greater water contact angle (Gong et al., 2016).
They occur as aggregates with apparent particle sizes of 30–300 nm,
possess tubular structures, as shown in TEM images in Fig. 1a and b,
and carry negative charges as determined by the tested zeta poten-
tial of −28.4 mV at pH 7.8. The negative charge of SNCs originates
from carboxyl and sulfate ester groups (Romdhane, Aurousseau,
Guillet, & Mauret, 2015).
As shown in Fig. 1c, the as-prepared CDs possess a nearly spher-
ical shape with sizes ranging from 3 to 10 nm. The FTIR spectrum
of the CDs shown in Fig. 1d exhibits bands at 3204, 1637 and
1083 cm−1 , demonstrating that the CDs possess carboxylic acid
and other oxygen-containing functional groups (Zhu, Zhai, & Dong,
2012). The bands at 3070 and 1562 cm−1 suggest the existence of
16 B. Gong et al. / Carbohydrate Polymers 165 (2017) 13–21

Fig. 1. TEM images of (a, b) SNCs and (c) CDs; (d) FTIR spectrum of CDs; appearance of CD aqueous dispersion under (e) nature and (f) UV light; (g) photoluminescence (PL)
emission spectra of CDs excited by light with different wavelengths, where the mass fraction of CDs is 1.72%.

amino-containing functional groups, which can also be confirmed
by the occurrences of the element N in the XPS survey spectrum
and functional group C N in the high resolution C1s XPS spectrum
of the CDs (Figs. S1a and b, Supplementary data). Therefore, the CDs
inherit their amphoteric feature from gelatin (Tan et al., 2015). The
zeta potential of the CDs at pH 7.2 was tested to be −9.23 mV, i.e.,
the CDs carry net negative charges at neutral pH.
The aqueous dispersion of CDs exhibits a green color under
UV excitation (Fig. 1f). When excited at 330 nm, an emission peak
appears at 434 nm (Fig. 1g). With the increase in excitation wave-
length, the emission peak red shifts. The intensity of the emission
spectrum is increased by the increase in excitation wavelength
from 330 nm to 370 nm, and it is decreased by the increase in excita-
tion wavelength from 370 nm to 410 nm. The maximum excitation
wavelength of the synthetized CDs is 370 nm, at which the emission
wavelength is 449 nm.
3.2. Effect of CDs on properties of SNCs, SNC aqueous dispersion
and interfacial tension between ASA and water in the presence of
SNCs
The as-prepared SNCs carry negative charges, while the as-
synthesized CDs carry both positive and negative charges after their
amino and carboxyl groups are ionized in aqueous medium. There-
fore, the CDs are expected to interact with the SNCs in aqueous
media by electrostatic neutralization, changing the properties of
SNCs and SNC aqueous dispersions. The wettability of a particle
stabilizer, which can be quantitatively determined by observing
its contact angle at the oil–water interface, significantly influences
the type and stability of a surfactant-free emulsion. Particles with
contact angles less than 90◦ preferentially stabilize O/W emulsions
for systems with equal volume fractions of oil and water (Aveyard
et al., 2003; Binks, 2002). The contact angle of CD-SNC stabilizer sys-
tem at ASA-water interface is hard to measure directly due to their
 B. Gong et al. / Carbohydrate Polymers 165 (2017) 13–21
Fig. 2. Contact angle of a water drop on a compressed CD-SNC disk immersed in ASA
oil as a function of CD-to-SNC mass ratio. The insets are corresponding photographs
of water drops.
Fig. 3. Effect of CD-to-SNC mass ratio on conductivity and pH of SNC aqueous dis-
persion and zeta potential of SNCs in aqueous medium. The mass fraction of the
SNCs in aqueous dispersion is fixed at 0.67%.
small particle sizes. Herein, the contact angle was determined by
measuring the contact angle of a water drop on a compressed CD-
SNC disk immersed in ASA oil (Fig. S2, Supplementary data). Fig. 2
shows the contact angle as a function of the CD-to-SNC mass ratio.
The measured contact angle of SNCs at the ASA-water interface
is much greater than 90◦ , theoretically implying a relatively high
wettability of SNCs to ASA (Gong et al., 2016). However, the large
contact angle can also be attributed to a contact-angle amplification
due to the roughened surface of the compressed SNC disk (McHale,
Shirtcliffe, & Newton, 2004), the resistance of ASA for contact and
spreading of the water drop on the SNC disk due to the small dif-
ference in density between ASA and water (0.947 g/cm3 , compared
to 0.997 g/cm3 of water at 25 ◦ C), high viscosity of ASA (201 mPa s,
compared to 0.9 mPa s of water at 25 ◦ C) and the strong interaction
between ASA and water (Zhao et al., 2013). It can also be found from
Fig. 2 that the contact angle is significantly reduced by increasing
the CD-to-SNC mass ratio due to the high hydrophilicity of CDs.
Therefore, the introduction of CDs is expected to be beneficial for
preparing ASA-in-water emulsions stabilized by SNCs.
Fig. 3 shows the effects of the CD-to-SNC mass ratio on the pH
value and conductivity of SNC aqueous dispersions and on the zeta
potential of SNCs in aqueous media. The mass fraction of the SNCs in
the aqueous dispersion is fixed at 0.67%. The pH of the SNC aqueous
dispersion is 7.8, which is only slightly decreased by the introduc-
tion of CDs, even when the CD-to-SNC mass ratio is as high as 140%.
Therefore, when the effect of CDs on the properties of the SNC
aqueous dispersion is considered, the contribution of pH can be
neglected.
As shown in Fig. 3, the conductivity of the SNC aqueous disper-
sion without CDs is 28.2 ␮s/cm. It is significantly increased by the
17
Fig. 4. (a) PL emission spectra of CD aqueous dispersions at the presence of SNCs
with different SNC-to-CD mass ratio, where the CDs’ concentration is 1.72 wt%, and
the excitation wavelength is 370 nm; (b) water surface tension and ASA-water inter-
facial tension in the presence of SNCs with a concentration of 0.67 wt% in aqueous
medium, plotted against CD-to-SNC mass ratio.
introduction of CDs and the increase in CD-to-SNC mass ratio, sug-
gesting ionization of the CDs’ functional groups (Tan et al., 2015).
The introduction of CDs significantly reduces the negative zeta
potential of the SNC when the CD-to-SNC mass ratio is less than 60%,
providing direct evidence for the interaction between CDs and SNCs
by charge neutralization. After the CD-to-SNC mass ratio exceeds
60%, the negative zeta potential is only slightly decreased, indicat-
ing that the interaction of CDs with SNCs in aqueous medium has
reached an equilibrium, while the added CDs do not significantly
change the zeta potential of SNCs due to the amphoteric nature of
the CDs.
Fig. 4a shows the effect of the SNC-to-CD mass ratio on the flu-
orescence of CD aqueous dispersions. The concentration of CDs is
1.72 wt%. The introduction of SNCs can significantly quench the flu-
orescence of CDs due to the electrostatic interaction between the
amino groups of CDs and the acidic groups of SNCs (Bai et al., 2011).
However, even when the mass fraction of SNCs is as high as 120%,
the CD aqueous dispersion still shows some fluorescence.
Fig. 4b shows the effect of the CD-to-SNC mass ratio on water
surface tension and ASA-water interfacial tension in the presence
of SNCs and CDs. As shown, the surface tension of the SNC aque-
ous dispersion is 69.8 mN/m, slightly lower than the water surface
tension (71.9 mN/m), confirming the weak surface activity of the
as-prepared SNCs. The introduction of the as-prepared CDs fur-
ther significantly reduces the surface tension when the CD-to-SNC
mass ratio is less than 40%, demonstrating the surface activity of
CDs. The surface activity of the CDs is attributed to carbonization
and the inheritance of hydrophilic functional groups from gelatin
(Tan et al., 2015). As the CD-to-SNC mass ratio exceeds 40%, the
water surface tension is only reduced insignificantly. This is almost
18 B. Gong et al. / Carbohydrate Polymers 165 (2017) 13–21
Fig. 5. Emulsion phase volume fractions of ASA emulsions stabilized by SNC and by
gelatinized starch after being prepared for 24 h as a function of CD-to-SNC/starch
mass ratio. The mass ratio of SNC/starch-to-ASA is 2%. The insets show the appear-
ance of corresponding emulsions with CD-to-SNC/starch mass ratios of 0, 20%, 40%,
60%, 80%, 100%, 120% and 140% from left to right, respectively.
Fig. 6. Average droplet size of ASA emulsions stabilized by SNC/starch as a func-
tion of CD-to-SNC/starch mass ratio after being prepared for one hour. The mass
ratio of SNC/starch-to-ASA is 2%. The insets are the optical microscope images of
corresponding emulsions, where the scale bar is 50 ␮m.
consistent with the effect of CD-to-SNC on zeta potential of SNCs,
indicating that the adsorbed CDs exert greater impact on the water
surface tension than free CDs. The ASA-water interfacial tension in
the presence of SNCs is also significantly reduced with an increase
in the CD-to-SNC mass ratio due to the surface activity of the CDs
when the CD-to-SNC mass ratio is less than 40%. However, the
reduction in the interfacial tension is even accelerated at CD-to-SNC
mass ratios of 40–100% and continues persistently until the CD-to-
SNC mass ratio reaches 120%. This observation indicates that free
CDs can efficiently reduce the interfacial tension by adsorbing at
the ASA-water interface because the interaction between the CDs”
amino groups and ASA’s anhydride groups promotes the orienta-
tion of ASA molecules with their hydrophilic groups toward water
at the interface (Li, Liu, Zhang, Yin et al., 2013).
3.3. Preparation and characterization of ASA emulsion stabilized
by CDs and SNCs
To evaluate the performance of the as-prepared SNCs as an
emulsion stabilizer, an SNC-stabilized ASA emulsion with an SNC-
to-ASA mass ratio of 2% was prepared by homogenizing the mixture
of ASA and SNC aqueous dispersion at a fixed ASA volume faction of
25%. As a control, an ASA emulsion stabilized by the same amount of
gelatinized starch was also prepared. Although the SNC-stabilized
ASA emulsion possesses a higher emulsion phase volume fraction
than the starch-stabilized ASA emulsion, the SNCs still cannot pro-
vide adequate stability for the ASA emulsion when it is used as the
lone stabilizer at the typical addition level for a particle stabilizer
such as laponite (Li, Liu, Zhang, Qian et al., 2013). Both the aqueous
phase and the ASA phase are released from the SNC-stabilized ASA
emulsion after the emulsion was prepared for 1 h, indicating that
ASA emulsions stabilized solely by SNCs are unstable to coalescence
and creaming. The aqueous phase separated from the emulsion is
an aqueous dispersion of SNCs, suggesting that the SNCs cannot
completely attach onto ASA-water interface. By introduction of the
as-prepared CDs, ASA-in-water emulsions can be prepared with-
out release of water and ASA within 6 h, which provides a potential
application for the ASA emulsions as paper sizing agents. To com-
pare the stability of ASA emulsions stabilized by SNCs and by starch,
their emulsion phase volume fractions were calculated after the
emulsions were prepared for 24 h. Fig. 5 shows the effect of the CD-
to-SNC/starch mass ratio on the emulsion phase volume fraction
of ASA emulsion stabilized by SNCs and by gelatinized starch. The
insets are pictures of the appearance of the corresponding emul-
sions with CD-to-SNC/starch mass ratios ranging from 0 to 140%.
As shown in the figures, the emulsion phase volume fraction of ASA
emulsion stabilized by gelatinized starch is only slightly improved,
and ASA oil and a starch aqueous dispersion are still released from
the emulsion even as the CDs-to-starch mass ratio is as high as
140% due to the weak interaction between non-ionic starch and
amphoteric CDs and too small of a particle size of CDs. The former
cannot significantly improve the adsorption of starch at the ASA-
water interface while the latter cannot form adequate mechanical
barriers around ASA droplets to protect against the coalescence
of the emulsion. However, for the SNC-stabilized ASA emulsions,
the emulsion phase volume fraction can be significantly increased
by increasing the CD-to-SNC mass ratio, especially when the CD-
to-SNC mass ratio is less than 40%. No ASA is released, and the
separated aqueous phase is clear water even when the CD-to-SNC
mass ratio is as low as 20%, indicating good adsorption of SNCs at
the ASA-water interface and formation of particle barriers against
droplet coalescence. The improved adsorption of SNCs at the ASA-
water interface is attributed to the interaction between CDs and
SNCs, which increases the aggregation tendency of SNCs due to
the reduction of the negative charges of SNCs, especially when the
CD-to-SNC mass ratio is less than 40% (Fig. 3) (Romdhane et al.,
2015). The improvement of the SNCs’ water wettability by intro-
duction of CDs (Fig. 2) favors formation of water-holding barriers
around ASA droplets, thus improving the creaming stability of the
SNC-stabilized ASA emulsion.
When the CD-to-SNC mass ratio falls within the range of 40–80%,
the emulsion phase volume faction of ASA emulsion stabilized by
SNCs does not change significantly. This phenomenon is proba-
bly due to the sharp decrease in the ASA-water interfacial tension
induced by free CDs (Fig. 4), which favors break-up of large emul-
sion droplets, leading to increased exposure of ASA-water interface.
However, a small amount of free CDs cannot provide adequate
particle barriers for the increased ASA-water interface, restraining
the proportional increase in ASA emulsion phase volume fraction.
When the CD-to-SNC mass ratio is higher than 80%, the increase
in the ASA-water interfacial tension becomes slower. In this case,
less increased ASA-water interface is required to be stabilized. The
emulsion phase volume fraction can be further increased and can
reach as high as 97% at the CD-to-SNC mass ratio of 140% by increas-
ing the water-holding ability of CD-SNC stabilizer system (Fig. 2).
Fig. 6 shows the morphology (inset) and average droplet size of
the ASA emulsions co-stabilized by CDs and SNCs. The results were
compared with those co-stabilized by CDs and starch. The optical
microscope images were taken after the emulsions were prepared
 B. Gong et al. / Carbohydrate Polymers 165 (2017) 13–21 19

Fig. 7. Confocal microscope images of CDs with (a) SNCs and (b) starch co-stabilized ASA emulsions with a CD-to-SNC/starch mass ratio of 100%. The mass ratio of SNC/starch-
to-ASA is 2%.

for one hour. As shown, the SNC-stabilized ASA emulsion pos-

sesses much smaller average droplet size than the starch-stabilized
ASA emulsion, further corroborating the superiority of SNCs as an
ASA emulsion stabilizer compared to starch. Similar to starch, the
droplet size of SNC-stabilized ASA emulsions is diminished by the
introduction of CDs when the CD-to-SNC mass ratio is less than
120% due to the reduction of ASA-water interfacial tension (Fig. 4),
which favors the break-up of large emulsion droplets (Tan et al.,
2014; Zhang et al., 2014). When the CD-to-SNC mass ratio is greater
than 120%, the average droplet size does not change significantly,
which is in accordance with the reduction of ASA-water interfacial
tension.

3.4. Photoluminescence imaging of an ASA emulsion co-stabilized

by CDs and SNCs

The performance of CDs as a fluorescent probe in co-stabilizing

ASA emulsions was investigated using laser scanning confocal
microscopy. Fig. 7 shows the confocal microscope images of
CDs and SNC/starch co-stabilized ASA emulsions with a CD-to-
SNC/starch mass ratio of 100%. Green fluorescence emitted from the
CDs under UV excitation (488 nm) clearly traces the morphology of
either SNC or starch co-stabilized emulsions, and all of the fluo-
rescent points in the images are located on the emulsion droplet
surfaces. Therefore, the CDs are both an excellent co-stabilizer
of ASA emulsions and a competent fluorescent probe even for
starch-stabilized emulsions. It is also observable in the confocal
microscope images that the ASA emulsion co-stabilized by SNCs
and CDs has a smaller droplet size, further corroborating the advan-
tage of SNCs as an ASA emulsion stabilizer over starch.

Fig. 8. (a) Sizing performance of ASA emulsion with a CD-to-SNC/starch mass ratio
3.5. Sizing performance of ASA emulsion co-stabilized by CDs of 100%; (b) sizing effect of SNC/starch and CD co-stabilized ASA emulsions with
with SNCs various CD-to-SNC/starch mass ratios, where the mass fraction of ASA is 0.25% based
on oven-dried pulp. The mass ratio of SNC/starch-to-ASA is 2%.

The application of the as-prepared ASA emulsions co-stabilized

by SNCs and CDs as a paper sizing agent was investigated and com-
pared with that of the emulsions co-stabilized by starch and CDs.
Fig. 8 shows the sizing performance of the ASA emulsions with a CD-
to-SNC/starch mass ratio of 100% and the sizing effects of the ASA
emulsions with various CD-to-SNC/starch mass ratios. As shown
in Fig. 8a, the sizing degrees of handsheets sized by the SNC co-
stabilized and starch co-stabilized ASA emulsions increases linearly
with an increase in the mass fraction of ASA in the handsheets. As
the mass fraction of ASA reaches 0.3%, the sizing degree of hand-
sheets sized by the SNC co-stabilized and starch co-stabilized ASA
emulsions can be as high as 144 s and 79 s, respectively. There-
fore, even though the starch and CD co-stabilized emulsion shows
a rather good sizing performance due to the introduction of CDs, the
SNCs and CD co-stabilized emulsion performs much better than the
starch and CD co-stabilized emulsion because of its higher stability
and smaller droplet size.
It can be confirmed from Fig. 8b that the introduction of CDs
significantly improves the sizing effect of either SNC or starch co-
stabilized ASA emulsions. When the CD-to-SNC/starch mass ratio
is less than 80% for SNC co-stabilized emulsions, or less than 60%
for starch co-stabilized emulsions, the sizing effects of the two
CDs co-stabilized ASA emulsions are improved with an increasing
CD-to-SNC/starch mass ratio due to the enhancement in emulsion
stability and reduction in emulsion droplet size (Figs. 5 and 6).
When the CD-to-SNC/starch mass ratio becomes greater than 80%
for the SNC co-stabilized emulsion, or greater than 60% for the
starch co-stabilized emulsion, the sizing effects of the SNC co-
stabilized and starch co-stabilized ASA emulsions start to decrease
20 B. Gong et al. / Carbohydrate Polymers 165 (2017) 13–21
with an increasing CD-to-SNC/starch mass ratio, probably due to
the interference of CDs unbounded with SNCs or starch. Therefore,
the SNCs co-stabilized and starch co-stabilized emulsions show
their highest sizing effects at the CD-to-SNC/starch mass ratios
of 80% and 60%, respectively. It is also notable that the SNCs and
CD co-stabilized ASA emulsion displays a much better sizing effect
than the starch and CD co-stabilized one at all of the tested CD-to-
SNC/starch mass ratios, because the former is more stable against
both coalescence and creaming, and it possesses a smaller droplet
size than the latter.
4. Conclusions
SNCs, which are made from normal maize starch by H2 SO4
hydrolysis, are negatively charged and stabilize ASA emulsions with
a higher emulsion phase volume fraction than starch, but they can-
not provide adequate stability for emulsions when used as lone
stabilizers at a mass fraction of 2% based on ASA and an ASA-to-
water volume ratio of 1:3. By interaction with amphoteric CDs
made hydrothermally from gelatin, the water-wettability and neg-
ative zeta potential of SNCs and the interfacial tension between
SNC aqueous dispersion and ASA are reduced, which improves
the stability and diminishes the droplet size of SNC-stabilized ASA
emulsions. The introduction of CDs can also improve the stabil-
ity and reduce the droplet size of starch-stabilized ASA emulsions.
Consequently, the sizing performances of the SNC-stabilized and
starch-stabilized ASA emulsions are significantly improved. The
SNCs and CD co-stabilized ASA emulsion shows the highest siz-
ing performance at a CD-to-SNC mass ratio of 80%. The SNCs and
CD co-stabilized ASA emulsion shows much higher sizing perfor-
mance due to its higher stability and smaller emulsion droplet size
than the starch and CD co-stabilized ASA emulsion. In addition,
the morphology and stabilizer distribution of SNCs/starch and CDs
co-stabilized ASA emulsions can be traced under UV excitation.
Acknowledgments
The project was funded by the National Natural Science Foun-
dation of China (Grant Nos. 31270625 and 21406122). The authors
thank Mr. Ruoyu Liu from Reed College for his thorough English
revision and academic discussion on the manuscript.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.carbpol.2017.02.
007.
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