Food Research International 37 (2004) 851859

www.elsevier.com/locate/foodres

Stability and rheology of corn oil-in-water emulsions

containing maltodextrin
Utai Klinkesorn a, Pairat Sophanodora a, Pavinee Chinachoti b, D.J. McClements
a

b,*

Department of Food Technology, Faculty of Agro-Industry, Prince of Songkla University, Hat Yai, Songkhla 90112, Thailand
b
Department of Food Science, Chenoweth Laboratory, University of Massachusetts, Amherst, MA 01003, USA
Received 14 April 2004; accepted 4 May 2004

Abstract
The inuence of maltodextrin concentration (035 wt%) and dextrose equivalent (DE 1036) on the stability and rheology of
5 wt% corn oil-in-water emulsions stabilized by Tween 80 was studied. Creaming stability, mean droplet diameter, f-potential, and
apparent shear viscosity of emulsions were measured. Rapid creaming was observed when the maltodextrin concentration exceeded
a particular value, referred to as the critical occulation concentration (CFC), which was attributed to depletion occulation caused
by the non-adsorbed maltodextrin. The CFC (wt%) decreased as the DE value of the maltodextrin decreased, i.e., as the molecular
weight increased. Above the CFC, emulsions showed a small increase (<15%) in mean droplet diameter (d43 ) after one week storage,
which was attributed to enhanced coalescence of the occulated droplets. The apparent viscosity of emulsions increased steeply
when the maltodextrin concentration exceeded the CFC, and the emulsions exhibited distinct shear thining behavior. The results
were interpreted in terms of the impact of maltodextrin on the strength of the colloidal interactions between the emulsion droplets.
Addition of maltodextrins to emulsions can be used to create emulsions with dierent physicochemical and stability properties.

2004 Elsevier Ltd. All rights reserved.
Keywords: Maltodextrin; Nonionic surfactant; Oil-in-water emulsion; Critical occulation concentration; Rheology

1. Introduction
Maltodextrins and corn syrup solids are hydrolysis
products of starch consisting of a-(1,4) linked D -glucose
oligomers and/or polymers (Shahidi & Han, 1993). They
may be hydrolyzed by acid, enzyme, or acid/enzyme
combinations (Reineccius, 1991; Shahidi & Han, 1993).
They dier in average molecular size and are classiled
on the basis of their dextrose equivalent (DE). Dextrose
equivalent is a measure of the reducing power of starchderived polysaccharide/oligosaccharides compared with
D -glucose on a dry-weight basis (Wang & Wang, 2000).
Normally, maltodextrins are dened as having a DE
value <20, whereas corn syrup solids are dened as
having a DE value P20 (Reineccius, 1991; Shahidi &
Han, 1993). Nevertheless, in this paper the term mal*
Corresponding author. Tel.: +1-413-545-1019; fax: +1-413-5451262.
E-mail address: mcclements@foodsci.umass.edu (D.J. McClements).

0963-9969/$ - see front matter
2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.foodres.2004.05.001

todextrin will be used to include both maltodextrins

and corn syrup solids because they have similar properties and applications in food emulsions.
Maltodextrins with dierent DE values have dierent
physicochemical properties, including solubility, freezing temperature, viscosity, etc. (Dokic, Jakovljevic, &
Dokic-Baucal, 1998; Dokic-Baucal, Dokic, & Jakovljevic, 2004). However, maltodextrins with the same DE
value may also have dierent properties depending on
the hydrolysis procedure, source of starch (maize, potato, rice), and amylose to amylopectin ratio (DokicBaucal et al., 2004). Maltodextrins are widely used in
food emulsions as stabilizers (Chronakis & Kasapis,
1995; Chronakis, 1997; Dokic-Baucal et al., 2004; Hardas, Danviriyakul, Foley, Nawar, & Chinachoti, 2000;
Hogan, McNamee, ORiordan, & OSullivan, 2001).
A stabilizer can be dened as single or mixed chemical
component that confers long-term stability on emulsions. Stabilisers may operate by acting as emulsiers or
as texture modiers (McClements, 1999). Emulsiers are
surface-active ingredients that adsorb to the surface of

U. Klinkesorn et al. / Food Research International 37 (2004) 851859

emulsion droplets and prevent them from aggregating.

Texture modiers are ingredients that increase the viscosity of the continous phase of emulsions so as to slow
down the gravitational separation of the droplets.
Maltodextrins are not particularly surface-active, and so
their main stabilizing action in oil-in-water emulsions is
believed to be through viscosity modication or gelation
of the aqueous continuous phase surrounding the oil
droplets (Dickinson, 2003). Emulsions containing
maltodextrins as stabilizers therefore require an additional emulsifying agent for the production of a stable
emulsion (Hogan et al., 2001). In an emulsion system
containing surfactant and polysaccharide, the nature
and strength of emulsion stability will depend on thesurfactantpolysaccharide interactions at the surface of
the emulsion droplets as well as in the aqueous medium
between the droplets (Dickinson, 2003). For example, it
has been shown that small molecule surfactants bind to
maltodextrins by inserting their non-polar tails into a
helical coil formed by the maltodextrin chain
(Wangsakan, Chinachoti, & McClements, 2001, 2003).
These interactions could potentially alter the functionality of both the surfactant and the maltodextrin in an
emulsion. In addition, molecular characteristics of
maltodextrin, such as concentration and chain length,
will aect the overall rheology and stability of oil-inwater emulsions. In this work, our objective was to
systematically study the eects of maltodextrin type and
concentration on the stability and rheology of oil-inwater emulsions stabilized by a non-ionic surfactant. In
particular, we have interpreted out results in terms of
quantitative theories describing the inuence of nonadsorbed biopolymers on colloidal interactions and
emulsion rheology.

2. Materials and methods

Maltodextrins with dierent DE, designated as M100,
M150, M200 and M250, obtained by an acid/enzyme
hydrolysis of native corn starch were donated by Grain
Processing Corporation (Muscatine, IA). Another maltodextrin, designated as DRI SWEET 36, was obtained
from Roquette America. Inc. (Keokuk, IA). Mazola
corn oil (CPC International Inc., NJ) purchased from a
local supermarket was used. Polyoxyethylene (20) sorbitan monoleate (Tween 80), sodium azide (NaN3 ),
hydrochloric acid (HCl) and sodium hydroxide (NaOH)
were purchased from the Sigma Chemical Co.
(St. Louis, MO).
An emulsier solution was prepared by dissolving
1.0 wt% Tween 80 into double-distilled water containing
0.1 wt% sodium azide as an antimicrobial agent. Different maltodextrins were dissolved in double-distilled
water at various concentration (045 wt%). The pH of
the solutions was adjusted to 7.0 using HCl or NaOH.

Concentrated corn oil-in-water emulsions (20 wt%

oil, 0.8 wt% emulsier) were made by blending 20 wt%
corn oil with 80 wt% aqueous emulsier solution using a
high-speed blender (M133/1281-0, Biospec Products,
Inc., ESGC, Switzerland), followed by one pass at 5000
psi through a two-stage high-pressure valve homogenizer (LAB 1000, APV-Gaulin, Wilmington, MA). Diluted emulsions with varying composition (5 wt% corn
oil, 0.2 wt% Tween 80, 0.02 wt% NaN3 and 035 wt%
maltodextrins) were prepared by diluting concentrated
emulsions with aqueous maltodextrin solutions. The pH
of the emulsions was adjusted back to 7.0 using HCl or
NaOH.
Rheological measurments were carried out at 30 C
using a dynamic shear rheometer (Constant Stress
Rheometer, CS10, Bohlin Instruments, Cranbury, NJ)
operating in the shear stress range 0.025.0 Pa. The
emulsion was contained in a double-gap concentric
cylinder cell (the diameter of the inner cylinder was
25 mm, and the diameter of the outer cylinder was
27.5 mm) with a thin layer of mineral oil on top of the
sample to prevent water evaporation.
Creaming of emulsion samples (10 ml or 67 mm) was
monitored at room temperature by visual observation of
the height of the serum layer formed at the bottom of
glass tubes (HS ), expressed as a percentage of the total
height of the emulsions in the tubes (HE ): Creaming
Index 100
(HS /HE ).
The particle size distribution of the emulsions was
measured using a static light scattering instrument
(Malvern Mastersizer Model 3.01, Malvern Instruments, Worcs., UK). To prevent multiple scattering effects the emulsions were diluted with double-distilled
water prior to analysis so the droplet concentration was
less than 0.02 wt%. All the emulsion droplet size distributions were approximately log-normal and monomodal (Fig. 1).

9
8
7

Frequency (vol %)

852

6
5
4
3
2
1
0
0.01

0.1

10

Diameter (m)
Fig. 1. Droplet size distribution of diluted 5 wt% corn oil emulsion
stabilized by Tween 80 for 30 wt% of maltodextrin DE20 after storage
at room temperature for one week.

U. Klinkesorn et al. / Food Research International 37 (2004) 851859

The f-potential of oil droplets in the emulsions was

determined using a particle electrophoresis instrument
(ZEM5003, Zetamaster, Malvern Instruments, Worcs.,
UK). The emulsions were diluted to a droplet concentration of approximately 0.008 wt% using double-distilled water prior to analysis to avoid multiple scattering
eects.
All experiments were carried out in at least duplicate using freshly prepared samples and results are reported as the mean and standard derivation of these
measurements.

3. Results and discussion

3.1. Inuence of maltodextrin concentration and DE on
creaming stability
The creaming stability of 5 wt% corn oil-in-water
emulsions was determined by measuring the height of
the serum layer formed at the bottom of the emulsions
after 24 h storage at room temperature (Fig. 2). A distinct serum layer was observed in some of the emulsions,
whose height depended on maltodextrin concentration
and DE value. Rapid creaming occurred when a critical
maltodextrin concentration was exceeded, which was
attributed to depletion occulation of the droplets by
the non-adsorbed maltodextrin molecules in the aqueous phase of the emulsions (Dickinson, 2003; DokicBaucal et al., 2004; McClements, 2000). Non-adsorbed
polymers generate an attractive osmotic force between
droplets that increases as the polymer concentration
increases, until eventually it becomes large enough to
overcome the repulsive forces acting between the droplets. The minimum amount of maltodextrin required to
promote rapid creaming was dened as the critical
occulation concentration (CFC).

853

In this study, the CFC of the dierent types of maltodextrin was determined precisely by carrying out turbidity measurements on the serum layer of the creamed
emulsions. Fifty microliter of liquid was withdrawn
from the middle of the serum layer of a creamed emulsion and then diluted with double-distilled water to ve
milliliter. The transmittance of the serum layer was then
measured at 600 nm using an UVvisible spectrophotometer (Spectronic 21D, Milton Roy, Rochester, NY).
The CFC was dened as the lowest concentration of
maltodextrin that gave a transmittance less than that of
a non-creamed 1 wt% oil-in-water emulsion (prepared
by diluting the original emulsion). In other words, the
CFC was dened as the maltodextrin concentration
where at least 80% of the droplets in the original
emulsion had occulated and creamed to the top. The
CFC decreased as the DE of maltodextrins decreased,
being 35, 21, 21, 17 and 13 wt% maltodextrin for DE 36,
25, 20, 15 and 10, respectively. The average molecular
masses of the maltodextrin ingredients used in this study
have been calculated previously from their DE values as:
1,800, 1,200, 900, 720 and 500 Da for DE 36, 25, 20, 15
and 10, respectively (Danviriyakul, 2001; Dokic-Baucal
et al., 2004; GPC, 2003). Hence, the CFC decreased as
the molecular weight of the maltodextrin molecules increased (Fig. 3). This phenomenon can be attributed to
the inuence of molecular weight and conformation on
the magnitude of the depletion attraction between the
droplets (see Section 3.4).
Information about the kinetics of creaming in emulsions containing dierent maltodextrin concentrations
(DE 10) is shown in Fig. 4. There was no evidence of
creaming in emulsions containing less than 13 wt%
maltodextrin. At 15 wt% maltodextrin, the creaming
rate was rapid, with complete phase separation being
observed in less than 2 h. When the maltodextrin concentration was increased further, to 25 or 35 wt%, the

40
100

DE 10
DE 25
DE 36

80

CFC (wt%)

Creaming Index (%)

DE 15

60

40

30

20

20

0
0

10

20

30

40

Maltodextrin (wt%)

Fig. 2. Eect of maltodextrin concentration and dextrose equivalent on

creaming stability of 5 wt% corn oil emulsions stabilized by Tween 80
after 24 h storage at room temperature.

10
500

1,000

1,500

2,000

MW (g/mol)
Fig. 3. Critical occulation concentration (CFC) of dierent maltodextrins in 5 wt% corn oil emulsions stabilized by Tween 80 after 24 h
storage at room temperature.

854

U. Klinkesorn et al. / Food Research International 37 (2004) 851859

creamed layer (McClements, 1999). These results are in

agreement with those of other workers who have also
observed a decrease in creaming rate when the concentration of non-adsorbing polymer is increased above the
CFC (Dickinson et al., 1995).

100

Creaming Index (%)

80

60

3.2. Inuence of maltodextrin concentration and DE on

droplet characteristics

40

15%
25%
35%

20

0
0

50

100

150

200

Time (hrs)
Fig. 4. Eect of maltodextrin concentration on the creaming rate of
5 wt% corn oil emulsions stabilized by Tween 80 storage at room
temperature.

14

DE10

12

DE20
DE36

d43 (%)

10
8
6
4
2
0
0

10

15

20

25

30

35

Maltodextrin (wt%)

Fig. 5. Droplet mean diameter of 5 wt% corn oil emulsion stabilized by

Tween 80 with dierent maltodextrin concentration and dextrose
equivalent after 7 days storage at room temperature.

creaming rate decreased appreciably, which can be attributed to the increase in continuous phase viscosity
and network formation by the aggregated droplets in the

In this section, we examine the inuence of maltodextrin characteristics on droplet size and electrical
charge. We observed no signicant change in the mean
droplet diameter in the emulsions at any maltodextrin
concentration (035 wt%) or dextrose equivalent (DE
1036) after 24 h storage: d32 0:41  0:02. On the
other hand, a small but signicant increase (p < 5%) in
mean droplet diameter (up to 12%) was observed in
emulsions containing maltodextrin concentrations
above the CFC after 7 days storage (Fig. 5). The shape
of the particle size distribution remained fairly constant
throughout the observation period (Fig. 1), but the
maximum in the distribution shifted to slightly higher
diameters (data not shown). These results suggest that
there may have been some coalescence of the droplets in
the occulated emulsions. Droplet coalescence may have
been promoted because the droplets were in contact for
extended periods in the occulated emulsions and
therefore hole formation was more likely (Kabalnov,
1998) and/or because the droplets were forced closer
together at high maltodextrin concentrations because of
the strong depletion attraction between them (Ye, Hemar, & Singh, 2004).
The f-potential of corn oil-in-water emulsions stabilized by Tween 80 in the presence of dierent maltodextrin concentrations and DE values at pH 7 are shown
in Table 1. These emulsions were diluted about 1000fold prior to making the measurements using double
distilled water. It is interesting to note that even though
the droplets were stabilized by a non-ionic surfactant they had an appreciable negative charge ( 40
mV). The same phenomenon has been reported by a

Table 1
f-Potential (mV) of diluted corn oil-in-water emulsions stabilized by Tween 80 with dierent maltodextrin concentration and DE after storage for
24 h at room temperature
Maltodextrin
concentration (wt%)

Dextrose equivalent of maltodextrin

10

15

20

25

36

0
5
10
15
20
25
30
35

)42.6  1.7
)40.8  2.2
)39.1  1.7
)38.6  1.8
)38.0  2.3
)38.4  3.0
)38.2  3.3
)36.6  2.8

)41.7  1.2
)39.6  1.9
)38.8  0.7
)37.4  0.5
)37.4  0.5
)36.4  0.6
)36.2  0.9
)36.8  1.5

)42.4  1.2
)39.4  0.9
)37.7  0.7
)37.4  0.4
)37.6  0.6
)36.1  2.2
)36.7  2.3
)36.3  1.1

)42.3  0.7
)40.3  1.2
)39.9  2.2
)39.8  2.5
)38.2  1.0
)38.2  1.2
)38.3  1.3
)37.0  1.3

)41.4  0.3
)42.3  1.5
)43.9  1.4
)44.1  2.7
)44.3  0.9
)42.8  3.7
)44.5  0.5
)44.4  0.2

U. Klinkesorn et al. / Food Research International 37 (2004) 851859

number of other researchers, who reported that the fpotential depended on the pH and ionic strength of the
aqueous phase (Ahmad, Ho, Fong, & Toji, 1996; Ho &
Ahmad, 1999; Hsu & Nacu, 2003). The electrical charge
measured on droplets stabilized by non-ionic surfactants
has been attributed to adsorption of H3 O ions (low
pH) or OH ions (high pH) from water (Ho & Ahmad,
1999). It is also possible that some of the electrical
charge on the corn oil droplets used in our study arose
from anionic impurities present within the oil, e.g., free
fatty acids or phospholipids.
Our results showed that there was a slight decrease in
the magnitude of the droplet f-potential ( 42 to
 36 mV) with increasing maltodextrin concentration
(Table 1) for all DE values except DE 36. Previous
studies have shown that small molecule surfactants will
bind to maltodextrin, which has been attributed to the
incorporation of non-polar surfactant tail groups into a
helical coil formed by the maltodextrin chain (Semenova
et al., 2003; Wangsakan et al., 2001, 2003). It is therefore
possible that the maltodextrin molecules bound anionic
surface active lipids that were originally associated with
the corn oil droplets, thereby reducing the negative
charge on the oil droplets. A previous study has shown
that surfactantmaltodextrin binding only occurs when
the chain length of the maltodextrin molecules exceeds a
particular value, corresponding to about 12 glucose
units (Wangsakan et al., 2003). This may explain why we
observed no change in f-potential for the maltodextrin
with the lowest degree of polymerization (DE 36), i.e.,
there were no maltodextrin molecules with chain lengths
suciently long to interact with the anionic surface active lipids.

100

3.3. Inuence of maltodextrin concentration and DE on

rheology
The apparent viscosity of 5 wt% corn oil-in-water
emulsions and aqueous solutions containing dierent
maltodextrin types and concentrations was measured as
a function of shear stress. The relative viscosity of the
emulsions was then calculated so that we could focus on
the inuence of the droplets (rather than the continuous
phase) on emulsion rheology: grelative gE =g1 , where gE
is the apparent viscosity of the emulsion at a particular
shear stress and g1 is the viscosity of the aqueous continuous phase at the same shear stress. The variation of
relative viscosity with shear stress for dierent concentrations of maltodextrin (DE 20) are shown in Fig. 6. At
relatively low maltodextrin concentrations ( 6 20 wt%)
the relative viscosity was slightly higher than unity
across the whole shear stress range, as would be expected for a non-occulated oil-in-water emulsion. For
example, the Einstein equation for dilute emulsions
predicts that gE =g1 1 2:5/, which is approximately
equal to 1.125 for our system since /  0:05 (McClements, 1999). At higher maltodextrin concentrations
(>20 wt%), the relative viscosity was much greater than
unity at low shear stresses (Fig. 6), which can be attributed to extensive droplet occulation (McClements,
1999; Quemada & Berli, 2002). In addition, there was an
appreciable decrease in the relative viscosity with increasing shear stress, which can be attributed to progressive disruption of the ocs as the shear stress was
increased (Quemada & Berli, 2002).
The dependence of the relative viscosity on maltodextrin concentration and type at a xed shear stress
(0.1 Pa) is shown in Fig. 7. The relative viscosity increased
appreciably when a critical maltodextrin concentration was exceeded, which was attributed to depletion
occulation. The relative viscosity of an emulsion increases when the droplets become occulated because the

30%
35%

10

1
0.01

100

Relative Viscosity

Relative Viscosity

20%
25%

0.1

855

DE 10
DE 15
DE 25
DE 36

10

10

Shear Stress (Pa)

Fig. 6. Dependence of relative viscosity on shear stress and concentration of maltodextrin DE20 for 5 wt% corn oil emulsions stabilized
by Tween 80. The data points represent the viscosity of an emulsion
containing maltodextrin (see annotation box) at a particular shear
stress divided by the viscosity of the emulsion in the absence of maltodextrin at the same shear stress.

1
0

10

15

20

25

30

35

40

Maltodextrin (wt%)

Fig. 7. Dependence of relative viscosity on maltodextrin concentration

and dextrose equivalent for 5 wt% corn oil emulsions stabilized by
Tween 80.

U. Klinkesorn et al. / Food Research International 37 (2004) 851859

eective volume fraction of the particles in the system is

increased due to the presence of the continuous phase
trapped between the droplets in the ocs (McClements,
1999). As the DE of the maltodextrin increased, the
maltodextrin concentration where the relative viscosity
of the emulsions started to substantially increase became
higher. In other words, occulation occurred at lower
maltodextrin concentrations as the molecular weight of
the maltodextrin molecules increased. These results
therefore support the creaming stability measurements
described earlier, and can be attributed to the inuence of
maltodextrin on the depletion interactions between the
droplets (see below).
3.4. Calculation of depletion attraction between the
droplets
The objective of this section was to provide some
rationalization for the inuence of maltodextrin type
and concentration on the properties of oil-in-water
emulsions in terms of the physical phenomenon involved. The presence of non-adsorbed biopolymers in
the aqueous phase of an oil-in-water emulsion is known
to increase the attraction between the droplets through a
depletion mechanism. The magnitude of this attractive
interaction can be calculated using the following equations (McClements, 1999):

3


2 3
rc  3
h
wdepletion h  pr POSM 2 1
1
3
2r
r
!




rc 2
h
3 1
1
;
1
2r
r
POSM

ckTNA
M


2cRv
1
;
qm

where wdepletion h is the inter-droplet pair potential due

to depletion interactions at a surface-to-surface droplet
separation of h, r is the droplet radius, POSM is the osmotic pressure arising from the exclusion of non-adsorbed polymer molecules from a narrow region ( rc )
surrounding the emulsion droplets, and rc is the eective
radius of the polymer molecules in solution. In addition,
c, M and qm are the mass concentration (in kg m3 ),
molecular weight (in kg mol1 ) and molecular density (in
kg m3 ) of the polymer molecules, NA is Avogadros
number, k is Boltzmanns constant, and T is the absolute
temperature. The parameter, Rv , is referred to as the
volume ratio, which is equal to the eective volume of a
polymer molecule in solution divided by the actual
volume of the constituent atoms making up the molecule
(McClements, 2000). If a polymer molecule adopts a
compact spherical conformation, like a globular protein,
then Rv  1. However, if the polymer molecules entrain
large quantities of solvent as they rotate in solution,

then Rv  1. In this paper we have assumed that the

maltodextrin molecules act like rigid rods in solution so
that (McClements, 2000)
pn3 l3 qm NA
;
3
6M
where n is the number of monomer segments per molecule ( M=M0 , M is the molecular weight of the whole
molecule, M0 is the molecular weight of a monomer
segment, l is the length of a monomer segment and qm is
the density of the polymer chain. For oligosaccharide or
polysaccharide molecules, M0  168 g mol1 , l  0:47
nm and qm  2000 kg m3 (McClements, 2000). The
molecular characteristics of the maltodextrin used in our
calculations of the interaction potentials are shown in
Table 2.
The above equations were used to calculate the inuence of maltodextrin characteristics on the depletion
attraction between emulsion droplets (r 0:21 lm),
assuming that the maltodextrin molecules act as rigid
rods. The variation of the depletion attraction with
droplet separation for maltodextrins with dierent DE
values, but the same overall aqueous phase concentration (10 wt%) is shown in Fig. 8. Both the magnitude and the range of the attractive depletion
interaction increased with decreasing maltodextrin DE.
This gure indicates that the depletion attraction between oil droplets is relatively strong, and increases

Rv

Table 2
Molecular characteristics of the maltodextrin molecules used in the
theoretical calculations
Name

MW (g/mol)

Rv

rg (nm)

DE10
DE15
DE20
DE25
DE36

1800
1200
900
720
500

10.7
7.1
5.4
4.3
3.0

36
16
9.0
5.7
2.8

2.5
1.7
1.3
1.0
0.7

n, average number of monomers per molecule; RV , volume ration;

rg is radius of gyration. It was assumed that the maltodextrin molecules were rod-like in conformation.
0.1

10

0
-50
DE 36

-100

w (h ) /kT

856

-150
-200

DE 20
DE 15

-250
-300

DE 10

-350

h (nm)
Fig. 8. Depletion attraction for maltodextrins with dierent DE values
at 10 wt% overall aqueous phase concentration.

U. Klinkesorn et al. / Food Research International 37 (2004) 851859

with increasing maltodextrin molecular weight. An

estimate of the overall strength of the depletion attraction in a particular system can be obtained by
calculating the magnitude of wdepletion when the droplets are in contact:


2
wdepletion h 0 2prc2 POSM r rc :
4
3
The dependence of wdepletion h 0 on maltodextrin
concentration and DE value was calculated (Fig. 9). The
strength of the depletion attraction increases progressively with maltodextrin concentration, with the increase
being larger for lower DE values. These calculations can
be used to explain the dependence of the CFC on maltodextrin DE seen in Section 3.1. In the absence of
maltodextrin the emulsion droplets are prevented from
occulating because the repulsive dropletdroplet interactions (e.g., steric, electrostatic and hydration repulsion) dominate the attractive interactions (e.g., van
der Waals) (McClements, 1999). Addition of maltodextrin to the emulsions increases the depletion attraction
between the droplets, until eventually the overall attractive interactions outweigh the repulsive interactions
and the droplets occulate. As the molecular weight of
the maltodextrin molecules increases, a smaller amount
of maltodextrin needs to be added to the emulsion in
order to generate the additional attraction required to
promote droplet occulation.
3.5. Prediction of inuence of maltodextrin on emulsion
rheology
It would also be useful to obtain a more quantitative
understanding of the inuence of maltodextrin on the
rheology of the emulsions. A mathematical model has
recently been developed to describe the inuence of
shear stress on the apparent viscosity of weakly occulated emulsions (Quemada & Berli, 2002)

10

20

30

40

w (h =0) /kT

DE 36

-500
DE 20
DE 15

-1000
DE 10

-1500

h (nm)
Fig. 9. Dependence of wdepletion h 0 on maltodextrin concentration
and DE value of 5 wt% corn oil emulsion stabilized by Tween 80.


gs g1

1 s=si
R s=si

857

2
;

where g1 is the apparent viscosity of the emulsion at an

innitely high shear stress, s is the applied shear stress, si
is the critical applied shear stress, and R is the rheological index. For an emulsion in which the droplet concentration is suciently low to prevent the formation of
a three-dimensional network of aggregated droplets, the
rheological index is given by (Quemada & Berli, 2002)


1  /=/c /i;0
R
:
6
1  /=/c /i;1
Here, / is the volume fraction of droplets within the
overall emulsion /c is the packing parameter for a suspension of spherical particles (0.6), and /i;0 and /i;1
are the volume fractions of droplets within the ocs at
low and high shear stress. Typically, /i will have a value
somewhere between 0.2 (highly open packing) to 1
(highly dense packing) depending on the nature of the
interactions in the system, and the applied shear stress.
The value of si depends on the size of the individual
droplets and the strength of the attraction between the
droplets (Quemada & Berli, 2002)


kT
Umin
si 3 1
;
7
r
kT
where Umin is the strength of the attractive interaction
between the droplets, i.e., the magnitude of the interaction potential at the droplet separation where the
interaction potential is a minimum: jwhmin j. The
value of the apparent viscosity of the emulsion at
innitely high shear stresses can be calculated from
the following expression:

2
g1
/
1
;
8
/c /i;1
g0
where /c is the packing parameter for a suspension of
spherical particles (0.6), g0 is the viscosity of the continuous phase, and g is the intrinsic viscosity (2.5).
Predictions of the dependence of the relative viscosity
(g=g0 ) on applied shear stress (s) for 5 wt% oil-in-water
emulsions with dierent attractive strengths between the
droplets are shown in Fig. 10. The variables used in these
calculations were assumed to be similar to those for the
experimental measurements made in this study: / 0:05,
r 0:21 lm, /i;0 0:1 (very open ocs), and /i;1 1
(i.e., no occulation). The relative viscosity decreases
from a high plateau value at low shear stresses to a low
plateau value at high shear stresses. The shear stress
where the relative viscosity begins to fall increases as the
strength of the attraction between the droplets increases.
Experimental measurements made on emulsions
containing 35 wt% maltodextrin are compared with
theoretical predictions calculated assuming dierent

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U. Klinkesorn et al. / Food Research International 37 (2004) 851859

4. Conclusions

Relative Viscosity

100

0.1
1
10
Data

10

1
0.01

0.1

10

Shear Stress (Pa)

Fig. 10. Dependence of the relative viscosity (g=g0 ) on applied shear
stress (s) for 5 wt% oil-in-water emulsions with dierent attractive
strengths between the droplets (shown in annotation box as Umin =kT ).
The predictions are compared with measurements made on corn oil-inwater emulsions containing 35 wt% maltodextrin.

interaction strengths in Fig. 10. The theory and experimental data are in rough qualitative agreement, there
being a large decrease in relative viscosity once a particular shear stress is exceeded. Nevertheless, this decrease occurs at lower shear stresses in the experimental
measurements than in the theoretical predictions, and
no low and high shear stress plateau regions were observed in the experimental measurements. These dierences between theory and experiment indicate that there
is some discrepancy between theory and experiment.
The theory makes a number of simplifying assumptions
about the system that may not be valid in practice, e.g.,
about the size, shape and internal structure of the ocs
(Quemada & Berli, 2002). In addition, the experimental
measurements may be prone to errors due to wall-slip or
creaming phenomenon (see below). Even so, the comparison between theory and experiment does suggest
that the bonds holding the droplets together in the ocs
were relatively weak and easily disrupted by shearing.
This suggests that there must be a relatively strong repulsive interaction that balances the relatively strong
depletion attraction generated between the droplets by
the presence of maltodextrin (see Section 3.4).
It should also be noted that the theoretical predictions were made using the assumption that the occulated droplets had a very open structure at low shear
stresses (/i;0 0:1). This value of the packing of the
droplets within the ocs seems relatively low for occulated emulsions. It is possible that the relative viscosity was high at low shear stresses because of some
creaming of the droplets within the rheometer. Nevertheless, the rheology measurements only took about 5
10 min to carry out, and we observed little creaming
during this time in the creaming stability measurements,
except for the emulsions where the CFC was just exceeded (Fig. 4).

Addition of maltodextrin to corn-oil-in-water emulsions stabilized by a non-ionic surfactant (Tween 80) had
a pronounced inuence on emulsion stability and rheological behavior. The presence of maltodextrins in emulsions leads to an enhanced rate of creaming above a
critical concentration due to depletion occulation and
the rate of creaming depends on the concentration and
DE value of the maltodextrins. Above the CFC, emulsions were highly viscous and showed strong shear thining. Control of maltodextrin characteristics can therefore
be used to create emulsions with dierent physicochemical properties for various applications in food processing.
Acknowledgements
This material is based upon work supported by the
Cooperative State Research, Extension, Education Service, United States Department of Agriculture, Massachusetts Agricultural Experiment Station (Project
No. 831), and an United States Department of Agriculture, CREES, NRI Grant (Award Number 2002-01655).
The authors also thank The Thailand Research Fund,
Royal Golden Jubilee Ph.D. Program for nancial
support.
References
Ahmad, K., Ho, C. C., Fong, W. K., & Toji, D. (1996). Properties of
palm oil-in-water emulsions stabilized by nonionic emulsiers.
Journal of Colloid and Interface Science, 181, 595604.
Chronakis, I. S. (1997). Structuralfunctional and water-holding
studies of biopolymers in low fat content spreads. LebensmittelWissenschaft und-Technologie, 30, 3644.
Chronakis, I. S., & Kasapis, S. (1995). Preparation and analysis of
water continuous very low fat spreads. Lebensmittel-Wissenschaft
und-Technologie, 28, 488494.
Danviriyakul, S. (2001). The properties of spray-dried milk fat
emulsions as aected by types of wall materials and processing
and storage conditions. Doctoral Dissertation, University of
Massachusetts (Amherst), USA.
Dickinson, E. (2003). Hydrocolloids at interfaces and the inuence on
the properties of dispersed systems. Food Hydrocolloids, 17, 2539.
Dokic, P., Jakovljevic, J., & Dokic-Baucal, L. (1998). Molecular
characteristics of maltodextrins and rheological behaviour of
diluted and concentrated solutions. Colloids and Surfaces A, 141,
435440.
Dokic-Baucal, L., Dokic, P., & Jakovljevic, J. (2004). Inuence of
dierent maltodextrins on properties of O/W emulsions. Food
Hydrocolloids, 18, 233239.
GPC. (2003). Maltrin: Maltodextrins and corn syrup solids for food
formulations. Iowa, USA: Grain processing Corporation.
Hardas, N., Danviriyakul, S., Foley, J. L., Nawar, W. W., &
Chinachoti, P. (2000). Accelerated stability studies of microencapsulated anhydrous milk fat. Lebensmittel-Wissenschaft und-Technologie, 33, 506513.
Ho, C. C., & Ahmad, K. (1999). Electrokinetic behavior of palm oil
emulsions in dilute electrolyte solutions. Journal of Colloid and
Interface Science, 216, 2533.

U. Klinkesorn et al. / Food Research International 37 (2004) 851859

Hogan, S. A., McNamee, B. F., ORiordan, E. D., & OSullivan, M.
(2001). Emulsication and microencapsulation properties of sodium caseinate/carbohydrate blends. International Dairy Journal,
11, 137144.
Hsu, J. P., & Nacu, A. (2003). Behavior of soybean oil-in-water
emulsion stabilized by nonionic surfactant. Journal of Colloid and
Interface Science, 259, 374381.
Kabalnov, A. (1998). Thermodynamic and theoretical aspects of
emulsions and their stability. Current Opinion in Colloid & Interface
Science, 3, 270275.
McClements, D. J. (1999). Food emulsions: Principles, practice and
techniques. Boca Raton, FL: CRC Press.
McClements, D. J. (2000). Comments on viscosity enhancement and
depletion occulation by polysaccharides. Food Hydrocolloids, 14,
173177.
Quemada, D., & Berli, C. (2002). Energy of interaction in colloids and
its implications in rheological modeling. Advances in Colloid and
Interface Science, 98, 5185.
Reineccius, G. A. (1991). Carbohydrates for avor encapsulation.
Food Technology, 144149.

859

Semenova, M. G., Belyakova, L. E., Antipova, A. S., Polikarpov, Y.

N., Klouda, L., Markovic, A., & Ilin, M. M. (2003). Eect of
maltodextrins on the surface activity of small-molecule surfactants.
Colloids and Surfaces B: Biointerfaces, 31, 4754.
Shahidi, F., & Han, X.-Q. (1993). Encapsulation of food ingredients.
Critical Reviews in Food Science and Nutrition, 33, 501547.
Wang, -J., & Wang, L. (2000). Structures and properties of commercial
maltodextrinsfromcorn,potato,andricestarches.Starch/Starke,52,296304.
Wangsakan, A., Chinachoti, P., & McClements, D. J. (2001).
Maltodextrin-anionic surfactant interactions: Isothermal itration
calorimetry and surface tension study. Journal of Agricultural and
Food Chemistry, 49, 50395045.
Wangsakan, A., Chinachoti, P., & McClements, D. J. (2003). Eect of
dierent dextrose equivalent of maltodextrin on the interactions
with anionic surfactant in an isothermal titration calorimetry study.
Journal of Agricultural and Food Chemistry, 51, 78107814.
Ye, A., Hemar, Y., Singh, H. (2004). Enhancement of coalescence by
xanthan addition to oil-in-water emulsions formed with extensively
hydrolysed whey proteins. Food Hydrocolloids, in press,
doi:10.1016/j.foohyd.2003.11.010.