Food Hydrocolloids 43 (2015) 275e282

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Food Hydrocolloids
journal homepage: www.elsevier.com/locate/foodhyd

Stabilizing oil-in-water emulsion with amorphous cellulose

Xuejuan Jia a, Ranran Xu a, Wei Shen b, Mengxia Xie b, Muhammad Abid a, c, Saqib Jabbar a,
Peng Wang a, Xiaoxiong Zeng a, Tao Wu a, *
a

College of Food Science and Technology, Nanjing Agricultural University, Weigang 1, Nanjing 210095, People's Republic of China
College of Science, Nanjing Agricultural University, Weigang 1, Nanjing 210095, People's Republic of China
c
Department of Food Technology, Pir Mehr Ali Shah Arid Agriculture University, Rawalpindi, Pakistan
b

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 17 November 2013
Accepted 29 May 2014
Available online 9 June 2014

Non-derivative cellulose is usually not considered an amphiphilic biopolymer with emulsion stabilization ability. In this study, we have demonstrated, using a dissolution and regeneration process, that the
obtained non-derivative amorphous cellulose can effectively stabilize oil-in-water emulsions. Freshly
prepared emulsions with cellulose contents of 0.07e0.56% are not stable against creaming. After
increasing the cellulose content to 0.83%, the emulsions remain completely stable for months. All previously gravitationally unstable liquid-like emulsions were transformed into stable gel-like emulsions
and persisted in this form during storage. Optical and uorescence microscopy demonstrated the
adsorption of cellulose on the surface of oil droplets. Rheology study indicates that the resulting
emulsions are attractive emulsions with typical shear-thinning gel characteristics. The underlying
emulsion stabilization mechanism is a combination of Pickering and network mechanisms. The ndings
of this research explore a more practical way of utilizing non-derivative cellulose in the food industry as a
novel food ingredient.
2014 Elsevier Ltd. All rights reserved.

Keywords:
Phosphoric acid
Amorphous cellulose
Emulsion stabilization
Shear-thinning
Gel
Attractive emulsion

1. Introduction
Food emulsions are usually stabilized by small molecular surface
active emulsiers, amphiphilic biopolymers, including proteins and
polysaccharides, and nano/micro-particles (Dickinson, 2009). A
number of naturally occurring polysaccharides, such as gum arabic,
pectin, chitosan, and galactomannans, are capable of stabilizing
emulsions, although there is debate regarding the underlying
mechanisms and whether they involve surface activity or thickening effects (McClements, 2005). Traditionally, natural starches
and cellulose are not considered as amphiphilic biopolymers with
good emulsion stabilization ability, unless chemical modications
are made to introduce surface active groups (McClements, 2005;
Xhanari, Syverud, & Stenius, 2011). Starches are essentially hydrophilic molecules with poor surface activity, whereas cellulose is
hydrophilic as well, but it is insoluble in water because of strong
intermolecular hydrogen bonds (McClements, 2005).
Recently, the role of hydrogen bonding in the solubility and
insolubility properties of cellulose has been challenged (Glasser
et al., 2012; Medronho, Romano, Miguel, Stigsson, & Lindman,

* Corresponding author. Tel./fax: 86 25 84395671.

E-mail addresses: twu@njau.edu.cn, wutao007@hotmail.com (T. Wu).
http://dx.doi.org/10.1016/j.foodhyd.2014.05.024
0268-005X/ 2014 Elsevier Ltd. All rights reserved.

2012). It is believed that the properties of cellulose are also

signicantly inuenced by hydrophobic interactions, and the surface of crystalline cellulose has both hydrophobic and hydrophilic
planes (Cho, Gross, & Chu, 2011; Glasser et al., 2012; Medronho
et al., 2012; Parthasarathi et al., 2011; Yamane et al., 2006). As a
result of this amphiphilic character, it is not surprising to see that
crystalline cellulose is capable of forming stable emulsions if they
are dispersed well. Earlier studies have found colloidal microcrystalline cellulose (MCC) (11% MCC 1% sodium carboxymethylcellulose) can stabilize oil-in-water emulsions and water-in oil-in
water (w/o/w) multiple emulsions by forming a network around
the emulsied oils (Oza & Frank, 1986, 1989). The function of MCC is
to orient at the oil-in-water interface thus providing a mechanical
barrier to droplet coalescence, whereas the sodium carboxymethylcellulose functions as a dispersing and protective colloid for the
MCC (Oza & Frank, 1986). Recent studies have demonstrated that
cellulose nanocrystals, without any dispersing agent, can also
effectively stabilize oil-in-water emulsions (Kalashnikova, Bizot,
Cathala, & Capron, 2011, 2012). Moreover, high internal phase
emulsions (HIPEs) with oil volume fractions more than 0.9 can be
stabilized by less than 0.1% cellulose nanocrystals (Capron &
Cathala, 2013). These nanocrystals are needle- or rod-shaped
crystalline cellulose with widths of a few nanometers and lengths
varying from tens of nanometers to several micrometers. They are

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X. Jia et al. / Food Hydrocolloids 43 (2015) 275e282

prepared by acid hydrolysis of the native cellulose ber (Habibi,

Lucia, & Rojas, 2010). It is believed that the amphiphilic character
of cellulose nanocrystals resides in the crystal organization at the
elementary brick level, and their emulsion stabilization mechanism
is Pickering stabilization (Kalashnikova, Bizot, Cathala, & Capron,
2012). In Pickering stabilization, nano/micro-particles are absorbed at the oil-water interface and protect emulsion droplets against
occulation and coalescence by a steric barrier (Dickinson, 2013).
Both oil-in-water and water-in-oil emulsions can be formed
depending on the particle wettability (Dickinson, 2010).
The supramolecular structure of cellulose has both crystalline
and amorphous domains (Habibi et al., 2010). The preparation of
crystalline cellulose products, such as MCC or cellulose nanocrystals, usually employs hydrochloric or sulfuric acid to hydrolyze
the amorphous domain and release the crystalline domain (Habibi
et al., 2010). The hydrolysis of amorphous domain results in a signicant loss of the cellulose biomass, and thus, yields of crystalline
cellulose are usually low. For example, the yield of cellulose
nanocrystals is as low as 30%, even after optimization of the
preparation method (Bondeson, Mathew, & Oksman, 2006).
Although mechanical methods can be used to prepare crystalline
cellulose, such as microbrillated or nanobrillated cellulose, such
methods suffer from extremely high energy consumption (Klemm
et al., 2011). Compared with the enormous research on crystalline
cellulose for food applications, amorphous cellulose, which can be
prepared in high yield by solvent dissolution and anti-solvent
regeneration, has received little research attention in the food industry. This under appreciation is caused by a lack of a good cellulose solvent and little exploration of its functional properties for
food applications. Current solvents are either expensive, such as
ionic liquids, or organic-solvent based, such as N-methylmorpholine-N-oxide (NMMO) and N, N-dimethylacetamide (DMAc)/LiCl,
and thus, their practical applications in the food industry are
limited. Recently, a new solvent system consisting of NaOH/urea,
NaOH/thiourea or LiOH/urea has been developed, but it is only
effective in dissolving cellulose with a weight-average molecular
weight below 1.2  105 (Luo & Zhang, 2013). Nevertheless, the
functional properties of the resulting cellulose as bers, membranes, microspheres and hydrogels have also been studied but
mainly in the areas of packaging, separation science, textile and
biomedicine (Luo & Zhang, 2013). Another study found that
amorphous cellulose prepared by regeneration from ionic liquids
can stabilize both oil-in-water and water-in-oil emulsions (Rein,
Khaln, & Cohen, 2012). Other than the aforementioned cited references, little research can be found in the current literature
regarding the food applications of functional amorphous cellulose.
In our previous works, we have successfully prepared amorphous cellulose by using a benign solvent e phosphoric acid and
demonstrated that prepared amorphous cellulose has excellent
rheological properties (Jia et al., 2013; Jia et al., 2014). The dissolution of cellulose in phosphoric acid is believed to be an esterication process: celluloseeOH H3PO4 / cellulosee
OePO3H2 H2O. The regeneration of cellulose in water results in
amorphous cellulose by the reverse reaction: cellulose
eOePO3H2 H2O / celluloseeOH H3PO4 (Zhang, Cui, Lynd, &
Kuang, 2006). Compared with other solvents, phosphoric acid is
inexpensive and has good solubility for cellulose from different
sources with molecular weights up to 5.5  105 (Zhang & Lynd,
2005). In this study, we demonstrated the prepared amorphous
cellulose has excellent emulsion stabilization ability as well.
Although previous studies have demonstrated the emulsion stabilization of amorphous cellulose (Jia et al., 2013; Rein et al., 2012),
the characteristics of the resulting emulsions, such as their microstructure and rheology properties has not been studied to date.
Because of the sensory perception of food emulsion, such as

mouthfeel and texture, essentially rely on these properties, they

become the top priorities of this investigation.
2. Experimental details
2.1. Materials
MCC powder, 85% phosphoric acid (H3PO4) and other common
chemicals were purchased from Sinopharm Chemical Reagent Co,
Ltd. (Shanghai, China). Dodecane (99%) obtained from Sigma
Aldrich (Shanghai, China) was puried through water extraction
extensively. Calcouor White was purchased from SigmaeAldrich
(Shanghai, China). Deionized water was used throughout the
experiment.
2.2. Preparation of amorphous cellulose
The phosphoric acid was equilibrated to 4  C in a refrigerator
(Haier, China). Then, 2.00 g of MCC was wetted with 6 ml of
deionized water and mixed with 50 ml of 85% phosphoric acid to
reach a homogenous state, followed by the addition of another
50 ml of 85% phosphoric acid. The obtained cellulose suspensions
were incubated in a shaking bath with temperature set at 0  C and a
speed of 150 rpm for 24 h to obtain a clear solution. Then, 500 ml of
deionized water was used to dilute the cellulose solution to obtain a
milky dispersion, followed by centrifugation at 16,700 g (Beckman,
J-30I, USA) for 20 min. The supernatant was discarded, and the
pellet was washed with deionized water repeatedly until a constant
pH was obtained. The concentration of cellulose in the nal
dispersion was determined gravimetrically to be 1.38% w/v.
2.3. Emulsions preparation
An amorphous cellulose dispersion (1.38% w/v) was diluted with
deionized water to obtain cellulose dispersions at a series of concentrations, i.e., 1.10, 0.83, 0.55, 0.28, and 0.07% w/v. Four milliliters
of puried dodecane was then added into a 50 ml plastic tube
containing 16 ml of cellulose dispersions and then dispersed by a
disperser (IKA T18 homogenizer, Germany) at 10,000 rpm for 3 min
in a cold water bath to avoid overheating of the sample.
2.4. Visual inspection of emulsion stability
Ten milliliters of prepared emulsion was immediately transferred to a 10 ml glass tube. The stability of emulsions was visually
checked after storage at 1, 7 and 90 days at room temperature. After
preparation, emulsions with low concentration of cellulose added
were phase separated. The clear bottom phase is designated as
serum and the top phase, which is a concentrated layer of droplets,
is designated as emulsion cream. The volumes of the emulsion
cream are calculated from their thickness, which were measured
with a digital caliper. And these volumes are used to calculate the
dodecane fraction and nal concentration of cellulose in emulsion
cream.
2.5. Optical and uorescence microscopy
The optical and uorescence photographs of o/w emulsions
were captured using an Eclipse microscope equipped with a digital
camera (Nikon 80i, Japan). Calcouor White was used as uorescent dye of cellulose at a concentration of 0.1% w/v. A drop of Calcouor White solution was added on the slide followed by the
addition of a drop of emulsion. The diameters (d32) of the emulsions
were measured using Image J software by taking the average of at
least 500 droplets. For emulsion with volume of v and internal

X. Jia et al. / Food Hydrocolloids 43 (2015) 275e282

277

Fig. 1. Dispersion states of amorphous cellulose as a function of cellulose concentration. From left to right, the concentrations of cellulose are 0.07, 0.28, 0.56, 0.83 and
1.10% (w/v), respectively.

phase volume fraction of , the total interfacial area of droplets is

calculated as 6v/d32.
To image the distribution of amorphous cellulose on the surface
of emulsion droplets, Styrene was mixed with radical initiator
azobisisobutyronitrile (AIBN) at a ratio of 100/1 (w/w). 2 ml of this
mixture was added to 8.0 ml 0.4% amorphous cellulose suspension,
dispersed by a disperser (IKA T18 homogenizer, Germany) at
10,000 rpm for 3 min to prepare an emulsion. Then the emulsion
was polymerized at 50  C for 12 h to synthesize solid polystyrene
particles. These particles were deposited on the slide, air-dried and
observed by optical and polarized microscopes.
2.6. Rheological measurements
The rheological properties of the freshly prepared emulsions (1 day
storage) and emulsions stored for 7 days were analyzed using a
rotational Physical MCR 301 rheometer (Anton Paar, Graz, Austria) and
a 50 mm diameter parallel plate (PP50) with a gap xed at 0.5 mm gap.
All the rheological measurements were carried out at 25  C. Shear
viscosity was tested with the shear rate ranging from 0.01 to 1000 s1.
A pre-shear process of 100 s at 100 s1 and a time-waiting process of
50 s were applied before each test. A linear viscoelastic region (LVR)
test was conducted with strain from 0.01 to 1000% at a xed frequency
of 1 Hz. Frequency sweep tests was conducted with a strain of 0.1% and
frequencies ranging from 0.1 to 100 Hz.

Fig. 2. Effects of amorphous cellulose concentration on the stability of oil-in-water

emulsions (a e 1 day of storage; b e 7 days of storage). From left to right, the concentrations of cellulose are 0.07, 0.28, 0.56, 0.83 and 1.10%, respectively.

3. Results and discussion

3.1. Effects of cellulose concentration on the stability of oil-in-water
emulsion
In our previous work, we have determined that cellulose regenerated from phosphoric acid is primarily amorphous with little
residual crystallinity of cellulose II, and its yield is high, reaching
87% consistently, which is an advantage over the production of
crystalline cellulose (Jia et al., 2013). As shown in Fig. 1, amorphous
cellulose can transform between a uid and solid-gel state as a
function of the cellulose concentration. When the concentration is
increased to 1.10%, amorphous cellulose becomes a self-supporting
gel as demonstrated by turning the test tube upside-down.

Fig. 3. Effects of initial concentration of amorphous cellulose added to the emulsion on

serum fraction, dodecane fraction in emulsion cream and nal concentration of cellulose
in emulsion cream (% w/v). Values are represented as means standard deviation (n 3).

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X. Jia et al. / Food Hydrocolloids 43 (2015) 275e282

However, rheology tests demonstrate a gel-like characteristic at

lower concentrations (Jia et al., 2014). At concentrations of 0.07 and
0.28%, the sedimentation of cellulose is observed, which indicates
that amorphous cellulose is denser than water. These results also
indicate that the surface charge density of amorphous cellulose is
not high enough to stabilize itself in aqueous medium by electrostatic repulsion. With respect to cellulose nanocrystals prepared by
acid hydrolysis, their surfaces are usually more charged and thus
present better stability in water (Araki, Wada, Kuga, & Okano,
1998). However, this property of less charge density may be advantageous in term of emulsion stabilization. It is known that
strongly charged cellulose nanocrystals prepared by H2SO4 hydrolysis cannot stabilize emulsions unless the surface charges are
screened by salt (Kalashnikova et al., 2012).

When the concentrations of cellulose are less than 0.83%, the

freshly prepared emulsions (1 day storage) are not stable against
creaming as dodecane is less dense than water (Fig. 2a). The
extent of creaming decreases with the amount of cellulose
added. According to Stoke's law, the creaming stability of emulsion can be improved by reducing droplet size, increasing viscosity of the continuous phase, or minimizing density differences
between droplets and the continuous phase (McClements, 2005).
With increasing cellulose concentration, the viscosity is undoubtedly increased. In addition, as demonstrated by the microscopy studies described later, the adsorption of cellulose at
the emulsion droplet surface should increase the effective density of the droplets, thus minimizing the density difference between the droplets and continuous phase. Both factors may

Fig. 4. Typical optical micrographs of emulsions stabilized by amorphous cellulose at varied cellulose concentrations (a-0.07%, b-0.28%, c-0.55%, d-0.83% w/v; 1 day of storage) and
their corresponding droplet size during storage (e). The scare bar is 50 mm.

X. Jia et al. / Food Hydrocolloids 43 (2015) 275e282

contribute to the improved stability against creaming. It is

possible to create buoyancy neutral droplets (data not shown) to
improve the emulsion stability by changing the cellulose concentrations and internal phase fraction to match the density of
droplets with that of continuous phase, as indicated in the
Pickering emulsions stabilized by quinoa starch granules (Rayner,
Timgren, Sjoo, & Dejmek, 2012). At higher concentrations of
0.83% and 1.10%, a complete retardation of creaming up to 3
months is achieved, which can be explained by the formation of
a three-dimensional network in the continuous phase that prevents the oil droplet from freely moving. It should be noted that
the color of the 1.10% emulsion is not as whitish as others, and a
layer of pure oil oats on the top of the emulsion at such a
concentration. This is most likely because the emulsion viscosity
at this concentration is too high to be emulsied well in our
shear condition. Nevertheless, no oiling-off is observed for all
other emulsions. These results reveal that amorphous cellulose is
very effective in preventing coalescence, which is the major
cause of oiling-off. The freshly prepared emulsions are still
owable, but with 7 days storage, this uidity is lost completely
even at the lowest concentration, as demonstrated by turning the
test tubes upside-down (Fig. 2b). It appears that the amorphous
cellulose is realigned and associated together to form a threedimensional network during storage. This is similar to the
behavior of nanocrystalline cellulose (Derakhshandeh, Petekidis,
Sabet, Hamad, & Hatzikiriakos, 2013). During aging, the rearrangement of the microscopic nanocrystalline cellulose particle
occurs and leads to the increase of the storage modulus
(Derakhshandeh et al., 2013).

279

The nal compositions of the emulsions are calculated and

plotted in Fig. 3. With increasing cellulose concentration in total
liquid from 0.07 to 0.83%, the serum fraction is decreased from 0.68
to zero, and the corresponding dodecane fraction in the emulsion
cream is decreased from 0.62 to 0.20. It shows glass-system
emulsions with an internal phase more than 60% can be stabilized by amorphous cellulose at concentration as low as 0.17%,
which is corresponding to 9 mg cellulose per m2 of the interfacial
area stabilized. Although it is not as impressive as that of cellulose
nanocrystal stabilization of HIPEs (Capron & Cathala, 2013), these
results demonstrate excellent emulsion stabilization ability in
comparison with MCC and modied starch, with which a concentration of 1.5e2.5% is required to achieve a total emulsion stabilization (Kargar, Fayazmanesh, Alavi, Spyropoulos, & Norton, 2012).
3.2. Microstructures and droplet sizes of the emulsions
As shown in Fig. 4, the prepared emulsions all have similar
microstructures and droplet sizes between 20 and 40 mm regardless
the initial concentrations of cellulose added. Usually the droplet
sizes are decreased with increasing amount of particle added to
stabilize the emulsions (Rayner et al., 2012). This may be caused by
the less powerful dispersing tool we used and the high viscosity in
our emulsion. A combination of the mechanical limit and high
viscosity disables the further reduction of particle size to demonstrate the effects of initial cellulose concentration. During storage,
the droplet sizes were found to have little change from day 1 to day
7. Some droplet sizes were even decreased, probably caused by the
measurement variability between replicates. Similar trend has

Fig. 5. Typical uorescence micrographs of emulsions stabilized with amorphous cellulose at varied cellulose concentrations (a e 0.07%; b e 0.28%; c e 0.55%; d e 0.83%, 1 days of
storage). The scare bar is 10 mm.

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X. Jia et al. / Food Hydrocolloids 43 (2015) 275e282

been observed during the storage of starch granules stabilized

emulsions (Rayner et al., 2012). Nevertheless, our emulsions have
very good long term stability even after three months storage (data
of 90 days not shown).
With respect of cellulose nanocrystals, the Pickering mechanism
is believed to be the main mechanism of emulsion stabilization
(Kalashnikova et al., 2011). Our uorescence study also demonstrates the role of the Pickering mechanism in emulsion stabilization of amorphous cellulose (Fig. 5). Isolated drops with uorescent
surfaces are observed as well as a uorescent signal from the
external phase. This suggests that cellulose is adsorbed on the
drops surfaces as well as being present in the continuous phase.
Previously, the amphiphilic character of cellulose was believed to
reside in the surface of cellulose crystals (Kalashnikova et al., 2012).
Our study indicates that the amorphous cellulose chain can be
amphiphilic as well. It is possible that the amorphous cellulose
chain presents the hydrophilic hydroxyl groups to water and the
more hydrophobic planes of glucopyranose rings toward the oil
(Rein et al., 2012), which thus leads to the adsorption behavior on
the oil droplet surface. However, network stabilization undoubtedly also plays a key role in emulsion stabilization, as shown by the
complete retarding of creaming at higher concentrations of amorphous cellulose and loss of uidity after storage (Fig. 2).
Due to the problem of out-of-focus signal associated with conventional uorescence microscope, we have employed another
method to conrm the distribution of amorphous cellulose on the
surface of emulsion droplets. A styrene-in-water emulsion stabilized by amorphous cellulose was prepared and polymerized using
an oil-soluble radical initiator AIBN. The synthesized solid polystyrene particles were observed by conventional optical and
polarized optical microscopes. Air-dried amorphous cellulose
forms solid aggregates with irregular shape (Fig. 6a), and they

demonstrate birefringence under polarized lights (Fig. 6b). This

birefringence has only been observed in the dried samples because
fresh-prepared amorphous cellulose lost birefringence completely
in wet status (Jia et al., 2013). The presence of these amorphous
cellulose aggregates on the surface of polystyrene particles can be
clearly observed in Figs. 6c and d, suggesting the absorption of
amorphous cellulose on the original emulsion. Although scanning
electron microscope may provide a better image, these polystyrene
particles are quite large so that the conventional optical micrographs already have very good resolution.
Therefore, our study has demonstrated that the emulsion stabilization mechanism of amorphous cellulose is a combination of
Pickering and network mechanisms. This stabilization mechanism
is similar to what has been reported for microbrillated cellulose
extracted from mangosteen rind (Winuprasith & Suphantharika,
2013). Given that the Pickering mechanism is believed to be more
effective than the network mechanism in emulsion stabilization
(Ghosh, Tran, & Rousseau, 2011), their combination is most likely
responsible for the excellent emulsion stabilization effects.
3.3. Rheological properties of emulsions
The emulsion viscosity as a function of shear rate with varied
cellulose concentrations is shown in Fig. 7. For clarity, the viscosity
data are multiplied by a factor of 0.2, 0.5, 2.0 or 5.0 for cellulose
concentrations of 0.07, 0.28, 0.55 or 0.83, respectively. The insets
are the original data. Only the 0.07% sample displays typical shear
thinning behavior. For high concentrations, a three-region (shear
thinning e plateau or shear thickening e shear thinning) viscosity
prole is observed, which has been observed for amorphous cellulose dispersions alone. This prole is explained by the shearinduced occulation of cellulose particle (Karppinen et al., 2012).

Fig. 6. Typical bright-eld optical (a, c and d) and polarized optical micrographs (b) of air-dried amorphous cellulose (a and b), and styrene Pickering emulsion (c and d) stabilized
by amorphous cellulose and polymerized using AIBN as initiator. The scare bar is 100 mm.

X. Jia et al. / Food Hydrocolloids 43 (2015) 275e282

281

Fig. 8. Strain sweep test of oil-in-water emulsions stabilized with amorphous cellulose
at varied concentrations (1 day of storage).

Fig. 7. Viscosity as a function of shear rate for o/w emulsions stabilized with amorphous cellulose at varied concentrations (a e 1 day of storage; b e 7 days of storage).
For clarity, viscosity data are multiplied by a factor of 0.2, 0.5, 2.0 or 5.0 for cellulose
concentrations of 0.07, 0.28, 0.55 or 0.83, respectively. The insets are the original data.

Our result indicates that the rheology behavior of an amorphous

cellulose stabilized emulsion is largely controlled by the rheology
behavior of the continuous phase. When we compared the
apparent viscosity values of one-week stored and freshly prepared
emulsions (Fig 7 e insets), we found a signicant increase of these
values after storage, although the values are not very easy to
distinguish in the log scale plot. For the freshly prepared emulsions,
the 0.07% sample displays a lower apparent viscosity than the
others (Fig. 7a e inset). After storage, the emulsion's viscosity
increased to match higher concentration emulsions (Fig. 7b e
inset). These results, combined with the visual inspection results,
conrm that rearrangement of amorphous cellulose is occurring
during storage, leading to this increase of apparent viscosity.
The emulsion yield was studied by measuring the g dependence
of G0 and G00 . G0 decreases slowly for g > 1% before falling sharply as
g > 10% (Fig. 8). G00 exhibits a single, well-dened peak at g 10%. A
recent study demonstrated that the G00 of repulsive emulsions exhibits a single peak only when the droplet volume fraction is above
the random close packing (fRCP) of spheres at 0.64, whereas
attractive emulsions exhibit one peak below fRCP and two peaks
above fRCP (Datta, Gerrard, Rhodes, Mason, & Weitz, 2011). These
two peaks are explained by the break-up of the weakest bonds in
the stress-bearing connected network composed of compact
droplet aggregates and droplet congurational rearrangements,
respectively (Datta et al., 2011). As the droplet volume fractions of

our emulsions are all below fRCP (Fig. 3), these results indicate that
the oil-in-water emulsions stabilized by amorphous cellulose are
characterized by droplets with attractive interactions. The nature of
this attractive interaction could be hydrogen bonding or hydrophobic interactions, and further studies are required.
As shown in Fig. 9, the elastic behavior of an oil-in-water
emulsion is characterized by frequency sweep. All emulsions
display a higher storage modulus (G0 ) values than loss modulus
(G00 ), and both moduli are almost frequency independent, presenting a gel-like behavior. For freshly prepared emulsions, both G0
and G00 are increased with the increase of cellulose concentration.
The G0 and G00 of 0.07% sample are signicantly lower than those at
higher concentrations. After 7 days of storage, the G0 and G00 of
0.07% sample increase to match with that of the 0.28% sample,
whereas the moduli of all other concentrations remain rather
constant, which conrms the structure rearrangement of the 0.07%
emulsion during storage as we discussed earlier.
4. Conclusions
Our study has demonstrated that amorphous cellulose prepared
by an inexpensive solvent, phosphoric acid, can effectively stabilize
oil-in-water emulsions at a concentration less than 1% through
combined Pickering and network stabilization mechanisms. The
resulting emulsions are shear-thinning with typical gel characteristics and can be described as emulsions with attractive interactions. Compared with cellulose derivatives, the use of
crystalline cellulose or amorphous cellulose in emulsion stabilization may be advantageous in terms of regulation and consumer
acceptance, although it may be argued that the cellulose

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X. Jia et al. / Food Hydrocolloids 43 (2015) 275e282

Fig. 9. Storage modulus (lled symbols) and loss modulus (empty symbols) as a
function of frequency for oil-in-water emulsions stabilized with amorphous cellulose
at different concentrations (a e 1 day of storage; b e 7 days of storage).

nanocrystals and amorphous cellulose are still native cellulose, as

acid hydrolysis or solvent regeneration has been used in their
preparation. Nevertheless, these celluloses are essentially insoluble
dietary bers, which not only can function as thickening agents or
emulsion stabilizers but also can bring about health benets. In
particular, amorphous cellulose can be obtained with a high yield
by a simple dissolution and regeneration process and can perform
the same or better functions as that of crystalline cellulose.
Therefore, amorphous cellulose has considerable potential to be
used as a new hydrocolloid in the food industry in addition to
cellulose derivatives.
Acknowledgments
This work is supported by a startup fund (804080) from Nanjing
Agricultural University and projects funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD), the General Program of National Natural Science
Foundation of China (31271829), and the Natural Science Foundation of Jiangsu Province (BK2012770).
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