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Ultrasonics Sonochemistry
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Article history: The use of emulsifying methods is frequently required before spray drying food ingredients, where using
Received 29 August 2016 high concentration of solids increases the drying process yield. In this work, we used ultrasound to obtain
Received in revised form 28 November 2016 kinetically stable palm oil-in-water emulsions with 30 g solids/100 g of emulsion. Sodium caseinate,
Accepted 29 November 2016
maltodextrin and dried glucose syrup were used as stabilizing agents. Sonication time of 3, 7 and
Available online 1 December 2016
11 min were evaluated at power of 72, 105 and 148 W (which represents 50%, 75% and 100% of power
amplitude in relation to the nominal power of the equipment). Energy density required for each assay
Keywords:
was calculated. Emulsions were characterized for droplets mean diameter and size distribution, optical
Sonication
Palm oil
microscopy, confocal microscopy, f-potential, creaming index (CI) and rheological behavior. Emulsions
High energy emulsification presented bimodal size distribution, with D[3,2] ranging from 0.7 to 1.4 lm and CI between 5% and
Flocculation 12%, being these parameters inversely proportional to sonication time and power, but with a visual kinet-
ically stabilization after the treatment at 148 W at 7 min sonication. D[3,2] showed to depend of energy
density as a power function. Sonication presented as an effective method to be integrated to spray drying
when emulsification is needed before the drying process.
2016 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.ultsonch.2016.11.038
1350-4177/ 2016 Elsevier B.V. All rights reserved.
L. Consoli et al. / Ultrasonics Sonochemistry 38 (2017) 772782 773
stabilized by a great variety of low molecular weight emulsifiers, water containing 0.01% sodium azide, in order to avoid microbial
proteins, hydrocolloids and combinations among these materials. growth. The solutions were stirred overnight at room temperature
Although emulsification by ultrasound technique has been much (25 C). After this period, they were mixed with equal propor-
explored in the last years [1618], the integration of this technol- tions of maltodextrin and DGS, until it achieved a final protein/car-
ogy with spray drying still need investigation, since it perfectly bohydrate ratio of 1/5. The pH was then adjusted to 7.5 with NaOH
matches the requirement of producing low diameter oil-in-water 1 M.
emulsions. Current works concerning the use of ultrasound to pro-
duce oil-in-water emulsions employ moderate to high solids con- 2.2.2. Coarse emulsion
centration, such as 23% [19,20], 3135% [2123] and 42% [22]. Ethanol (0.4 g/100 g emulsion) was added to palm oil at 50 C
However, the oil/total solids ratio used in these works is too high and the mixture was magnetically stirred for 15 s. This oily phase
(> 0.80) and thus not suitable for spray drying. was added to the aqueous mixture prepared as described in Sec-
The choice for natural biopolymers, such as proteins, for emul- tion 2.2.1 and the system was stirred at 4000 rpm for 2 min, using
sions stabilization has been preferred in relation to synthetic emul- a rotorstator device (Silverson L5 M-A Laboratory Mixer, Che-
sifiers, as a clean label claim [24]. Dairy proteins have been sham, Buckinghamshire, UK). Assays were performed with 300g
extensively used as food ingredients due to their excellent emulsify- (285 mL) of emulsion.
ing properties [25]. The caseins, more specifically, have relevant
importance as emulsifiers, because they are capable of rapidly con- 2.2.3. Ultrasound treatment
ferring low interfacial tension during droplet formation, due to the Coarse emulsion was completely transferred to a jacketed bea-
strong amphiphilic characteristics of the major individual caseins ker connected to a thermostatic bath, in order to keep the temper-
[26]. Sodium caseinate is obtained by the acidification of the whole ature below 35 C in all assays. An ultrasonic processor Q700
casein to pH 4.6, followed by addition of NaOH up to pH 6.7, and fur- (700 W full power, 20 kHz frequency QSonica Newton, CT,
ther pasteurization and spray drying [27]. Because of its outstanding USA) was used. The probe ( = 12.5 mm) was immersed 24 mm
emulsifying properties, sodium caseinate has been used as ingredi- into the liquid. Sonication time and ultrasound power amplitude
ent in many products, and much investigation has been conducted in were varied in order to obtain optimum conditions for the produc-
order to better clarify its role in emulsion stabilization and to opti- tion of palm oil-in-water emulsions. Emulsions were sonicated for
mize its performance for each system in which it is applied. 3, 7 and 11 min at power amplitudes of 50%, 75% and 100%, which
Apart from emulsifiers, the use of hydrocolloids as thickening resulted in power values of 72, 105 and 148 W, as given by the
agents is also common in emulsions formulations, because their ultrasound equipment. In this document, all other mentions to pro-
ability to increase viscosity favors stability. Additionally, when cess conditions will be done by means of power and not power
designing emulsions for spray drying, hydrocolloids also con- amplitude. Ranges within parameters were evaluated were defined
tribute for reaching a suitable concentration of solids. Starch considering results from preliminary trials, in which we verified
derivatives, such as maltodextrins, and glucose syrups, have been that 3 min was the minimum period of sonication enough to pro-
commonly used with this finality and, beyond functionality, they mote droplet disruption, and intervals lower than 4 min did not
represent an economic choice in comparison to other ingredients, cause significant changes in the system. Since this formulation will
such as some gums and modified starches [5]. be used in further studies for spray drying, with the addition of a
This work had as main goal evaluating the effect of the ultra- bioactive material, we considered that the use of excessive sonica-
sound process parameters of power amplitude and sonication time tion periods could bring negative effects to the bioactive mole-
on high solid emulsions formation, in order to set the best condi- cules, and then set 11 min as the maximum sonication period. All
tion to produce food emulsions for further spray drying. assays were performed in duplicate.
D0:9 D0:1 duced into the device to the processed volume of the fluid [30]. For
Span 3
D0:5 ultrasound processors operating in batch, ED is calculated by Eq.
(7) [31], which can also be used for rotor-stator devices, replacing
where ni is the number of droplets with diameter Di , and D0:1 , D0:5
tson by the stirring time used. The power, in this case, can be
and D0:9 represent the diameter of accumulated distribution of
obtained by Eq. (8).
10%, 50% and 90% of total droplets, respectively.
ED P t son =V 7
2.3.2. Optical microscopy
Emulsions microstructure was visualized using an optical where P is the Power delivered to the system (W); tson is the soni-
microscope Carl Zeiss Axio Scope A1 (Gottingen, Alemanha), with cation time and V is the volume of the fluid.
a 100x objective. Images were captured by the software Axio P U i 8
Vision Rel. 4.8.
where P is the power delivered to the system (W), U is the electric
2.3.3. Confocal laser scanning microscopy (CLSM) tension (V Volts) and i is the electric current (A Ampre).
CLSM was used in order to ensure the formation of oil-in-water The ultrasound processor used in this work displayed, during
emulsions, and also for observing the modification caused by pro- the process, the power delivered to the fluid and, at the end of
cess conditions with improved image quality. The oily phase of the process, the total amount of energy employed. The energy val-
emulsions was labeled with the Nile Red dye, in the concentration ues displayed by the equipment were very close to those obtained
of 0.002 g/100 g oil. Samples were examined using a Zeiss LSM using Eq. (7). The energy input of the rotor-stator device was calcu-
780-NLO confocal on an Axio Observer Z.1 microscope (Carl Zeiss lated using Eq. (8), using the electric current measurement given
AG, Germany) using 63x and 100x objectives. Images were col- by the equipment (Silverson L5 M-A Laboratory Mixer, Chesham,
lected using 514 nm laser line for excitation and 527728 emission Buckinghamshire, UK). The results for energy density were then
filters for Nile Red, with pinholes set to 1 airy unit for each channel, correlated to the volume-surface mean diameter (D[3,2]) of emul-
1024 1024 image format, and 1x and 2x optical zoom. sions droplets, measured immediately after preparation. Power
and logarithmic functions, Eqs. (9) and (10), were fitted to experi-
2.3.4. f-potential mental data for comparison.
The determination of f-potential of oil droplets was made using
a Zetasizer Nano Series (Malvern Instruments, Worcestershire, UK). D3;2 aEDb 9
The measurement is based on the application of an electrical field
to the electrodes of the cell in which sample is placed. f-potential is D3;2 a ln EDb 10
related to the mobility of the charged droplets between the two
electrodes. 100 lL of each emulsion were diluted in 9.9 mL of where D[3,2] is the volume-surface mean diameter, ED is the energy
Milli-Q water. Measurements were performed in triplicate. density and a and b are constants.
2.3.6. Rheological behavior Sonication significantly reduced the droplet diameter of emul-
Emulsions flow curves were obtained using a cone-plate geom- sions, independently of the intensity of the treatment, as shown
etry ( = 60 mm) in a stress-controlled rheometer AR1500ex (TA by the parameters D[3,2] and D[4,3] in Table 1. The reduction in dro-
Instruments, Elstree, UK). The analysis was done in the range plet diameter, promoted by sonication, can also be clearly seen on
between 0 and 1000 s1, in 3 min, in a three-step sequence: up- the micrographs from Figs. 1 and 3. With respect to the droplets
down-up. The second up curve data was fitted to the Newtonian size distribution, the polydispersity indices (Span) of both coarse
model (Eq. (5)) and to the Power Law (Eq. (6)). Rheological mea- and sonicated emulsions were very similar, although the increase
surements were conducted only immediately after sample prepa- in sonication time affected it, as will be further discussed in this
ration, due to the creaming that was observed 24 h later. section.
r gc_ 5 Regarding the sonicated emulsions, the majority of them pre-
sented bimodal size distribution, independently on the power
r k c_ n 6 employed. However, droplet size was strongly affected by such fac-
tor: in Fig. 2, it can be seen that, for the same sonication time, the
in which r is the shear stress (Pa), g is the viscosity (Pa.s), c_ is the curves were shifted to the left when the power was increased. This
shear rate (s1), k is the consistency index (Pa.sn) and n is the fact is also demonstrated by data presented in Table 1: at a fixed
behavior index (dimensionless). sonication time, the higher the power amplitude, the lower D[3,2]
and D[4,3] mean diameters. Sonication time affected these parame-
2.4. Energy density calculation ters in the same way. That is, given a fixed power, droplet diame-
ters reduced when the ultrasound treatment was longer, except for
The concept of energy density (ED) is applicable for the produc- a slight increase in D[4,3] of emulsions sonicated for 11 min, in com-
tion of emulsions by mechanical devices. It relates the power intro- parison to those sonicated for 7 min at 148 W. These observations
L. Consoli et al. / Ultrasonics Sonochemistry 38 (2017) 772782 775
Table 1
Mean droplet diameter of palm oil-in-water emulsions obtained by rotor-stator device and ultrasound.
Power (W) Sonication time (min) Immediately after preparation 24 h after preparation
D3;2 D4;3 Span D3;2 D4;3 Span
(lm) (lm) (lm) (lm)
0 4.28 0.29fA 9.55 0.90dA 1.87 0.11aA 7.98 1.15dB 17.87 2.70bB 1.79 0.16abA
eA bcA aA cA aA
72 3 1.46 0.066 2.25 0.06 1.76 0.02 1.47 0.15 2.27 0.32 1.77 0.10aA
7 1.38 0.05deA 2.38 0.11cA 2.37 0.09bdA 1.34 0.15abcA 2.18 0.31aA 2.23 0.16abcA
11 1.18 0.02cdA 2.05 0.08abcA 2.54 0.18bcA 1.11 0.11abcA 1.90 0.25aA 2.47 0.27bcA
105 3 1.36 0.08deA 2.18 0.39bcA 1.87 0.27aA 1.41 0.18bcA 2.17 0.55aA 1.86 0.41abA
7 1.05 0.14bcA 1.99 0.31abcA 2.76 0.32bcB 0.99 0.01abcA 1.69 0.06aA 2.21 0.18abcA
11 0.87 0.01abA 1.69 0.08abcA 2.70 0.28bcA 0.86 0.02abA 1.65 0.14aA 2.61 0.38cA
148 3 1.24 0.04cdeA 2.07 0.10abcA 2.03 0.23adA 1.28 0.00abcA 2.07 0.01aA 2.06 0.02abcA
7 0.73 0.01aA 1.22 0.13aA 1.64 0.14aA 0.73 0.03aA 1.26 0.23aA 1.71 0.19aA
11 0.68 0.05aA 1.45 0.10abA 2.95 0.40cA 0.72 0.01aA 1.40 0.10aA 2.73 0.57cA
Values are averages of two experiments, with each individual sample analyzed in triplicate. Different lowercase letters in each column and different capital letters in each
row, for the same parameter, represent statistically significant difference (p 6 0.05).
confirm that emulsions characteristics are controlled both by son- usually significantly lower than that required for sonication pro-
ication time and by power when a fixed frequency is used. cesses and, therefore, the mean diameter of emulsions droplets
Increasing sonication time from 7 to 11 min, at fixed power, obtained by ultrasound are expected to be very smaller. The results
resulted in similar D[3,2] diameters, which suggests that there is a found in this work are in accordance with this observation and
limit on the time of ultrasound treatment that still promotes with those of previous works [21,22,31,34].
droplet rupture when using the same power. Above this limit, The achievement of a saturation diameter with the increase in
any amount of energy delivered to the system will be dissipated sonication time, which was found in our work, follows the trend
as heat. Although the volume-weighed diameter D[4,3] showed described by other authors that also used ultrasound to produce
dimension variation due to process conditions, it did not follow oil-in-water emulsions [31,34,35].
the trends of increasing or decreasing as straight as D[3,2] did, The main differences in the trends between D[4,3] and D[3,2]
and its value was statistically similar on most of the assays. diameters may be related to the polydispersity of samples. The
The effect of sonication time was much stronger on the Span of presence of droplets with larger diameters has higher impact on
emulsion droplet sizes than that of power. Long periods of sonica- the calculation of D[4,3] (Eq. (2)) than on D[3,2](Eq. (1)) [36]. There-
tion expose droplets to high amounts of energy, promoting not fore, the volume-weighed mean diameter is frequently referred to
only droplet rupture, but also droplet collision and, thus, re- as more sensitive to the detection of fat droplet aggregation when
coalescence and flocculation, explaining the larger variability in compared to the volume-surface mean diameter [20,21,37]. This
droplet size. Furthermore, the droplet rupture does not affect uni- same reason also explains the increase in D[4,3] when sonication
formly all the droplets, since the droplets in locations closer to the time was incremented from 7 to 11 min at 148 W of power: the
probe are exposed to a much more intense cavitation than those last treatment resulted in the broadest size distribution of all,
more distant from it [31]. So, part of the droplets will keep the orig- and the parameter calculation was then affected. The larger distri-
inal size or have lower reduction, and part of them will be signifi- bution may have occurred due to droplet coalescence favored by
cantly smaller. This also corroborates to the presence of the two the excessive amount of energy employed in this treatment. This
peaks in size distribution. phenomenon is also referred as over-processing [31].
After 24 h of emulsions preparation, analyses were repeated for The micrographs obtained by confocal laser scanning micro-
comparison. In coarse emulsions, diameters were significantly scopy (Fig. 3) confirmed that our process produced oil-in-water
increased after this period, which may indicate droplet coalescence emulsions, where the oil droplets are red-labeled by the Nile Red
with time. Although creaming was observed in the sonicated emul- dye. Variations in size distributions, already discussed in this sec-
sions (further discussed in Section 3.2), the remaining droplets in tion, can also be clearly observed.
the continuous phase presented little or no variation in the mean
diameters and size distribution, as it can be seen in Table 1 and
in Fig. 2. Even with no statistical significance, there was a trend 3.2. f-potential and kinetic stability
towards reduction of emulsions Span after 24 h, which may be evi-
dence of larger droplets migrating to the cream phase. Immediately after preparation, the f-potential of emulsions var-
Rotor-stator equipments have the ability to mix liquids from ied from 54.596 to 48.247 mV (Table 2), with no significant dif-
separated phases or to reduce droplet size of a coarse emulsion. ference among assays.
When fed into the device, the liquid flows through a narrow gap The negative charge occurred mainly because of sodium casei-
between a rotating disc (rotor) and a static disk (stator). Droplets nate, a dairy protein which acted as stabilizing agent in the system.
are formed or reduced when colliding against the stator wall by Sodium caseinate is negatively charged at pH 7.5 (50 mV data
the shear stress in the gap [32], but sizes smaller than 1 lm are not shown), at which emulsions were prepared. The carbohydrates
not generally reached. In the sonication process, the mechanism used also have negative charge at this pH value, although con-
for droplet rupture is the acoustic cavitation phenomenon, which tributing little compared to the protein. Systems with net charge
consists of growth and collapse of micro bubbles of gas dissolved between 30 and 60 mV, as were emulsions here obtained, are gen-
in the medium. The collapse of these bubbles produces powerful erally considered moderately stable due to electrostatic repulsion
shock waves that radiate near the probe and propagate into the [38].
medium, leading to droplets breakdown. This energy can also be The kinetic stability was observed visually by taking the height
converted into thermal energy, resulting in increased temperatures measurements of the cream and the continuous layers of emul-
[32,33]. The amount of energy employed in rotor-stator devices is sions placed in glass tubes, in a period of 24 h after preparation.
776 L. Consoli et al. / Ultrasonics Sonochemistry 38 (2017) 772782
Fig. 1. Optical micrographs of emulsions prepared at different process conditions. Scale bar: 5 lm.
Results are expressed as the creaming index (CI) and are presented the same variation on the process conditions resulted in similar
in Fig. 4. droplet size. This result is also important because shows that
Creaming index of sonicated emulsions is more strongly equivalent stability properties may be achieved even when signif-
affected by power than by sonication time. Power of 72 W showed icantly lower energy is employed. Considering these findings, we
low effectiveness against phase separation at all sonication times. assume that the condition of 148 W of power and 7 min of sonica-
The same observation is valid for 3 min sonication, at any power tion time had the best performance and will be set for the continu-
used. For emulsions sonicated for more than 3 min, the higher ity of the work.
the power employed, the lower the creaming index. The most It is interesting to notice that, although the CI obtained for the
stable emulsions were those with smallest droplet sizes (148 W, coarse emulsion was close to those obtained for some fine emul-
with 7 or 11 min of sonication). sions, a more intense separation was observed in it. Fig. 5 illus-
At 148 W of power, the use of a sonication time higher than trates the pictures of the coarse emulsion and that sonicated for
7 min did not imply significant reduction of creaming index. This 7 min at 148 W, observed after 24 h of preparation. As can be seen,
is in accordance with the observations found in Section 3.1, where the sonicated emulsion remained wholly turbid, and the line
L. Consoli et al. / Ultrasonics Sonochemistry 38 (2017) 772782 777
Fig. 2. Droplet size distribution diagrams of emulsions obtained using different process conditions.
between the cream layer and the continuous phase is difficult to Creaming is the instability mechanism that occurs by gravita-
visualize. For the coarse emulsion, the separation is much more tional separation, due to the lower density of the disperse phase.
clear, and the continuous phase shows a very low turbidity. The It is one of the most common mechanisms of emulsion destabiliza-
upper phase is more intensively yellow colored, as is the palm tion found in the food industry. Flocculation is the process by
oil, which demonstrates that separation was more intense. which droplets associate to each other, without losing their indi-
Emulsions stabilized by proteins are principally affected by four vidual characteristics [41]. In some cases, the formation of droplet
main destabilization mechanisms: creaming, coalescence, floccula- aggregates by flocculation may accelerate the creaming process,
tion and Ostwald ripening, but the later occurs less frequently in because those aggregates can move to the top of the emulsion
oil-in-water food emulsions, since oils commonly used are mainly more rapidly than individual droplets [27].
composed of long chain tryacylglycerols that show low solubility The relative concentration of protein-to-oil is one of the main
in water, and thus do not diffuse through the water phase [39,40]. parameters when considering flocculation in protein-stabilized
778 L. Consoli et al. / Ultrasonics Sonochemistry 38 (2017) 772782
Fig. 3. Micrographs obtained by confocal laser scanning microscopy for emulsions obtained by the rotor-stator treatment and sonication at 72 W, 105 W and 148 W for
7 min. Scale bar: 5 lm.
Table 2
f-potential measured for oil-in-water emulsions immediately and 24 h after
preparation.
Table 3
Apparent viscosity determined for palm oil-in-water emulsions by fitting the Newtonian model to flow curves data (R2 > 0.9995 for all assays). Results are expressed in mPa.s.
0 W power corresponds to the rotor-stator treatment. Values are averages of two experiments, with each individual sample analyzed in duplicate. Different lowercase letters
in each column and different capital letters in each row represent statistically significant difference (p 6 0.05).
*
Coarse emulsion viscosity was statistically similar (p P 0.05) to all other treatments.
Table 4
Parameters found from fitting power and logarithmic functions (Eqs. (9) and (10),
respectively) to experimental data for energy density and volume-surface mean
diameter D[3,2], of coarse and sonicated emulsions. Parameters are dimensionless.
Function Parameter R2
a b
Power 4.56 0.29 0.9931
Logarithmic 4.34 0.66 0.9897
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