Beruflich Dokumente
Kultur Dokumente
of Food Science and Nutrition, University of Minnesota, 1334 Eckles Avenue, St. Paul, MN 55108, USA
of Food Science and Nutrition, University of Minnesota, St. Paul, MN 55108, USA
ABSTRACT: Mechanisms of destabilization and kinetic parameters of shelf-life in dilute beverage emulsions
were investigated at six different temperatures. Close fit of the Arrhenius equation to emulsion breakage time
indicated the occurrence of similar mechanisms throughout the temperature range and validated accelerated shelflife tests at higher temperatures. Creaming increased by a factor of 10 between the lowest .4 C/ and highest
.55 C/ temperatures. Ostwald ripening was highly significant and more important than coalescence in influencing
emulsion stability. Copyright 2001 John Wiley & Sons, Ltd.
KEY WORDS: beverage emulsions; shelf-life; destabilization; kinetics
Introduction
Beverage emulsions are oil-in-water (O/W) emulsions
comprising two categories: flavour emulsions and cloud
emulsions. The former provides the beverage with flavour, cloudiness and even colour in certain formulae,
whereas the latter provides only cloudiness with no
flavour.1 A typical flavour emulsion composition includes flavour oils and weighing agents in the oil phase, and
water, hydrocolloids, citric acid, sweetener and preservatives in the water phase. Flavour oils are essential
oils, typically orange, lemon or lime. In cloud emulsions,
the flavourless oil can be orange terpenes or vegetable
oils. Hydrocolloids, typically gum arabic (gum acacia),
serve as emulsifiers and stabilizers. Modified starches or
other gums (guar, xanthan, tragacanth, locust bean or
carrageenan) can act as substitutes for gum arabic.2
Beverage emulsions are a unique class of emulsions
differing from other food emulsions in that they are
consumed in a highly diluted form rather than in their
original concentrated form. They are first prepared as an
emulsion concentrate which is later diluted several hundred times in sugar/acid solution in order to produce the
finished beverage, either carbonated or non-carbonated.1
For beverage emulsions, the most critical criterion of
stability is its stability in the finished soft drink. Emulsion stability in the concentrate is easier to achieve
because the viscosity is much higher due to the high
*Correspondence to: G. A. Reineccius, Department of Food Science
and Nutrition, University of Minnesota, 147 Food Science and Nutrition Building, 1334 Eckles Avenue, St. Paul, MN 55108, USA.
E-mail: greinecc@che1.che.umn.edu
concentration of hydrocolloid. The dilute beverage emulsion can almost be described as the concentrate being
dispersed in a second water phase, that is, from a
gum-solution water phase to a sugar-solution water
phase.3
Mechanisms of instability of beverage emulsions
include creaming, coalescence, flocculation and Ostwald
ripening. In the industry, the common term for creaming in bottled soft drinks is ringing because the flavour
emulsion separates from the soda, floats to the top and
shows a white creamy ring or oily ring at the neck of
the bottle. Coalescence implies localized disruption of
neighbouring droplets in aggregates, so that oil droplets
merge together to form large ones. This obviously leads
to a decreased number of droplets, enhances creaming
and eventually causes emulsion breakdown. Flocculation occurs when oil droplets of the dispersed phase
form aggregates or clusters without coalescence. These
aggregates behave as single large drops, and the rate
of creaming is accelerated. In emulsion concentrates, a
perceptible increase in viscosity can be observed when
flocculation occurs. In a soft drink system, droplet concentration is so low that flocculation is often reversible.
The aggregates can be readily redispersed when the interactions between droplets are weak.2 Ostwald ripening is
defined as the growth of larger droplets at the expense of
smaller ones, due to mass transport of soluble dispersed
phase through the dispersing medium. Ostwald ripening
is negligible unless the dispersed phase is at least sparingly soluble in the continuous phase. Since essential
oils are somewhat soluble in water, beverage emulsions
are prone to Ostwald ripening.4
Particle size determination, centrifugation and elevated temperature storage were evaluated as potential
predictors of stability in dilute beverage emulsions. Stability was monitored by absorbance (loss of turbidity) at
400 nm. Storing emulsions at high temperatures gave the
most accurate prediction of emulsion stability. Storage
at 45 C increased the rate of loss of turbidity by factors
of 2.54 over room temperature storage. The accelerating effect was similar for emulsions with and without a
weighing agent in the dispersed phase, except that the
rate of loss of turbidity was 35 times greater for the
former.5
The objectives of this study were to assess the significance of the different mechanisms of instability in dilute
beverage emulsions as a function of temperature, and to
evaluate shelf-life and related kinetic parameters.
Emulsion Preparation
droplet size <1 m and narrow particle size distribution) was achieved by running the premixes through a
high-pressure valve homogenizer (Microfluidizer Model
M-110Y, Microfluidics International Corporation, Newton, MA) at 89.6 MPa (13 000 psi) in a single pass. The
resulting concentrates were diluted to 0.25% (w/w) and
5% (w/w) in 10% sugar solution for emulsion stability
and particle size monitoring, respectively, and the pH
adjusted to 2.5 (pH meter GamRad, Novi, MI) with 2 M
citric acid. For the evaluation of kinetic parameters, samples of both dilute emulsions were stored at six different
temperatures: 4, 9, 23, 30, 37 and 55 C.
Measurements
Emulsion Stability
static light scattering using a Malvern Series 2600 Particle Size Analyzer (Malvern Instruments Ltd., Malvern,
Worcestershine, UK). A single daily particle size determination was done per sample up to the end of shelf-life,
as described in the above section. The 5% (w/w) concentration was necessary to create enough obscuration
in the instrument throughout the prospective shelf-life
of samples at each temperature. Before readings, samples were vigorously hand-shaken and inverted in order
to distribute oil droplets eventually stratified by creaming, and to break eventual weak flocs (see later section
on mechanisms of destabilization). Aliquots were then
placed in a metal jar that circulated the sample through
the measuring glass cuvette of the instrument. A laser
beam was directed through the sample, scattered by the
droplets in a characteristic pattern dependent of their
size, and detected by an array of photodiodes located
behind the cuvette. A computer program calculated the
particle size distribution as the best fit between the measured scattered pattern and that predicted by light scattering theory.
interrelate temperature and emulsion stability. The wellknown Arrhenius relation is:
k D kA e
EA
RT
bT
where D shelf-life at absolute temperature T, the constant 0 D shelf-life at the y intercept, and b D the
slope of the shelf-life plot. In practice, for a relatively
small temperature range, a linear plot results for the relation log () vs. T: b becomes a constant and 0 the
shelf-life at 0 C.9 The Water Analyzer SeriesReaction
Kinetics Program8 was used to perform all computations.
Viscosity
Evaluation of Mechanisms of Destabilization
Based on the first-order reaction constants for emulsion breakage obtained at six different temperatures, as
described above, the Arrhenius approach was utilized to
Copyright 2001 John Wiley & Sons, Ltd.
2gr 2 .2 1 /
91
r2
4
9
23
30
37
55
0.9353
0.9204
0.9288
0.9667
0.9690
0.8926
Standard
deviation
k
7.716E
8.688E
1.003E
1.856E
2.339E
6.448E
3
3
2
2
3
2
1.818E
2.555E
2.488E
2.812E
3.742E
3.106E
3
3
3
3
3
2
Breakage
time (h)
298.4
265.0
229.6
124.1
98.4
35.7
3.70 103
1
T
[r 2 D 0.9132]
0 D 3.486 107
D 3.486 107 e
0.0415T
[r 2 D 0.9374]
Mechanisms of Destabilization
11
amount of emulsifier in the system. Decreasing Ostwald ripening by increasing the gum acacia layer on
the particles is problematic, since the emulsion is ultimately diluted so greatly. In fact, dilution leads to a
shrinkage of this layer.14 Thus, narrowing the droplet
distribution appears to be the most effective method
of minimizing Ostwald ripening in dilute beverage
emulsions.
Regression analysis also indicated some significance
for coalescence. Gum acacia has been reported to be
quite effective in preventing destabilization by coalescence.3 The formation of a thick adsorbed layer around
the oil droplets keeps them apart far enough by steric
interaction, which also minimizes attractive Van der
Waals forces. In this study, the increase in creaming
rates because of the lack of a weighing agent in the oil
phase may have caused higher rates of coalescence as a
result of more numerous thermodynamically favourable
collisions among droplets. This observation was supported by the experimental data because particle growth
was greater and faster at higher temperatures. In addition, progressive accumulation of droplets at the top of
the sample due to creaming may have also caused coalescence as a consequence of prolonged contact, especially
in those samples stored at higher temperatures (higher
rates of creaming).
Finally, regression coefficients for both Ostwald ripening and coalescence were comparable throughout the
temperature range, a clear indication of the occurrence of
similar mechanisms of destabilization. This is in fact the
strongest argument to justify running accelerated tests
of stability at higher temperatures and provides a solid
physicochemical explanation to data previously reported
in the literature.5
the interfacial tension (in direct relationship with Ostwald ripening rate) or increasing layer thickness (to
retard diffusion of the dispersed phase through the
layer of emulsifier around the droplet).4,10 The last
two methods are evidently linked to the kind and
4 C
9 C
0.0018
0.0084
0.0127
0.0142
0.0174
0.0232
0.0268
23 C
0.0019
0.0112
0.0151
0.0190
0.0207
0.0330
0.0469
0.0023
0.0174
0.0243
0.0309
0.0350
0.0602
30 C
0.0024
0.0205
0.0333
0.0404
0.0468
37 C
55 C
0.0026
0.0443
0.0500
0.0657
0.0031
0.0807
0.0921
Table 3. Regression coefficients for Ostwald ripening and coalescence characterizing equations in dilute beverage emulsions within
the temperature range 455 C
Temperature . C/
r 2 (Ostwald ripening)
r 2 (Coalescence)
4
9
23
30
37
55
0.981
0.911
0.964
0.986
0.924
0.877
0.671
0.731
0.646
0.681
0.588
0.675
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