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Chemical Engineering & Processing: Process Intensification 155 (2020) 108045

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Chemical Engineering & Processing: Process Intensification


journal homepage: www.elsevier.com/locate/cep

Ultrasound-assisted hydration of wheat grains at different temperatures and T


power applied: Effect on acoustic field, water absorption and germination
Bianca Guimarãesa, Tiago Carregari Polachinia,*, Pedro E.D. Augustob,c, Javier Telis-Romeroa
a
Food Engineering and Technology Department, São Paulo State University (Unesp), Institute of Biosciences, Humanities and Exact Sciences (Ibilce), São José do Rio Preto,
SP, Brazil
b
Department of Agri-food Industry, Food and Nutrition (LAN), Luiz de Queiroz College of Agriculture (ESALQ), University of São Paulo (USP), Piracicaba, SP, Brazil
c
Food and Nutrition Research Center (NAPAN), University of São Paulo (USP), São Paulo, SP, Brazil

A R T I C LE I N FO A B S T R A C T

Keywords: Wheat has been increasingly employed as malt in the food industry. As the malting process demands long
Soaking processing time, ultrasound can be a clean intensifying alternative. This work studied the ultrasound-assisted
Grains hydration of wheat grains at different nominal input power (0−1500 W) and temperatures (15−25 °C). The
Emerging technologies actual acoustic field within the reactor was characterized. The effects of the studied variables on hydration
Malting
kinetics were assessed separately by the Weibull and Peleg Models. Thermodynamic parameters were evaluated.
Mathematical modeling
Sprouting
Grains germination was also addressed under the studied conditions. Increasing temperature as well as higher
acoustic density caused an improvement in the hydration kinetics, reaching 72 % when both variables were
combined. Hydration was an endothermic and non-spontaneous process. In the range of actual acoustic density
(0.061–0.102 W mL−1) and hydration temperature, the maximum germination was kept at ∼5 days with 86 %
germinated grains.

1. Introduction medium for several hours. After reaching the desired moisture content,
the grains follow to partial or complete germination under low tem-
Wheat is one the most cultivated grains in the world, with an annual peratures A suitable moisture content is considered to be in the range of
production over than 700 millions of tons in the recent years [1]. Its 75–80 g of water per 100 g of dry matter, as reported in literature for
large production and relative low costs have been the main reasons for cereals malting [15,16]. In the germination (or sprouting) step, en-
the partial to complete replacement of barley malt for wheat malt in zymes as amylases and proteases are developed into the grains during
many food applications [2]. hours or days. They hydrolyze the starchy endosperm and the protein
The interest for wheat malt has increased not only for wheat reserves into soluble compounds, which serve as nutrients for the ra-
brewing purposes [3] but also for its functionality as food ingredient. dicle to grow [13]. When the desired level of germination is acquired,
Wheat malt has been incorporate to formulations to improve poly- the germinated cereal (green malt) is dried to undergo a selective en-
phenols content, antioxidant properties, sensorial and/or structural zyme inactivation.
characteristics of cookies dough [4], probiotic beverages [5,6], wheat Once the malting process demands long periods of hydration and
bread [7,8], water biscuits [9], weaning foods [10] ciabatta bread [11] germination, assisting technologies has been studied in order to accel-
and many other food products. Its wide applicability is mainly attrib- erate processing. Although several non-conventional and emerging
uted to the presence of hydrolytic enzymes and bioactive compounds technologies are reported to enhance malting [17], ultrasound tech-
together with the degradation of anti-nutritional compounds that are nology (US) is highlighted due to its capacity for increasing the water
developed during malting process of wheat – in special in the germi- absorption with possible benefits to germination step [18].
nation step [12,13]. High-intensity ultrasound technology, specifically, comprises sound
However, the malting process consists of complex steps that should waves in the frequency range of 20–1000 kHz and acoustic intensities
be adequately controlled [14]. The grains should pass by an initial above 1 W cm−2. During the propagation, these waves produce suc-
water uptake to breakdown the cereal dormancy. Hydration, or soaking cessive cycles of compression and decompression that promote the
(or even steeping), is performed by immersing the grains into aqueous development of cavitation bubbles in the liquid medium and interesting


Corresponding author.
E-mail address: tiagopolachini@terra.com.br (T.C. Polachini).

https://doi.org/10.1016/j.cep.2020.108045
Received 6 April 2020; Received in revised form 31 May 2020; Accepted 8 July 2020
Available online 16 July 2020
0255-2701/ © 2020 Elsevier B.V. All rights reserved.
B. Guimarães, et al. Chemical Engineering & Processing: Process Intensification 155 (2020) 108045

effects in the liquid-solid interface. On the other hand, mechanical ef- 2.3. Acoustic field characterization
fects like squeezing and releasing are expected in solid materials [19].
In the specific case of grains hydration, indirect or direct mechanisms Only part of the input power is converted by the ultrasound
are more pronounced accordingly to the hydration stage [20]. The equipment into acoustic power into the product. Consequently, the real
magnitude of the ultrasound effects is dependent on the applied power. acoustic power delivered in the system needs to be determined (al-
Moreover, it is always desirable to use the smallest possible level of though many literature works neglected this evaluation). In this work,
power, which reinforces the need by evaluating a given process in a the acoustic field was characterized through the calorimetric method.
range of applied energy. Ultrasound can also be combined with tem- This method considers the temperature rise promoted during ultra-
perature to obtain milder or more intense effects [21]. sound application is a consequence of the cavitation process [30]. For
In fact, there are some recent studies regarding the use of ultrasound this, the Eq. (1) was used [31]:
for enhancing the grains hydrations [14,22–25]. Even though few stu-
dT
dies concerned the ultrasound-assisted hydration of wheat grains PUS = mcp
dt (1)
[26,27], they evaluated hydration at lower acoustic power (< 480 W of
nominal power) and higher temperatures (> 30 °C) than the ones re- where PUS is the acoustic power (W), m is the processed mass (kg) of
ported in the present work which may affect the malt quality – mainly water, cp is the specific heat of water (4.18 kJ kg−1·ºC−1), dT/dt is the
regarding α- and β-amylases, proteases and glucanases with adequate temperature rise recorded during the first 90 s of ultrasound application
enzymatic activity [28]. Although one work [26] was more focused on (ºC·s−1). The acoustic intensity (W cm-2), acoustic density (W mL−1)
simulating the hydration process by artificial neural networks, both of and yield of power conversion were determined by dividing the PUS
them recommended the ultrasonication as an enhancing technology for values by the emitter surface area of the tip (3.8 cm2), volume of treated
mass transfer and showed the significant effect of power applied and medium (1000 mL) and nominal input power, respectively.
temperature on the hydration processes. Notwithstanding, the authors The measurements were performed using the same volume of dis-
encouraged the investigation about the effects of other ultrasound tilled water as used for the grain hydration (1000 mL). Initial tem-
conditions on the wheat hydration. In addition, no effects on germi- perature was set at 15 °C, since initial temperatures below 60 °C did not
nation of wheat grains were addressed in both works [26,27]. More- affect the measurements [32]. Type K thermocouples were connected to
over, there is missing detailed information about the acoustic field the data acquisition system NI9213 (National Instruments, USA) and
characterization reported in the literature for US-assisted hydration. the temperature rise was registered during 90 s in 4 radial positions (r
Such type of study is needed for scaling-up purposes. = 0; 0,022; 0,044; e 0,066 m) at 6 different angular positions (θ = 0,
Therefore, the present work aimed evaluating the effects of ultra- 60, 120, 180, 240 and 300°) – totaling 16 points placed 1.5 cm below
sound application and temperature on the hydration kinetics of wheat the sonotrode. Acoustic power was calculated for the different nominal
grains. For this, the acoustic field was previously characterized re- input power applied: 500, 1000 and 1500 W. Temperature records were
garding the different exposure areas of probe-type ultrasound to cal- acquired with the aid of the LabView 2010 software (National Instru-
culate the actual acoustic density. Peleg and Weibull models were fitted ments, USA) and, then, the slope dT/dt could be calculated for the
to the experimental hydration data in order to provide important in- different points.
formation about the kinetics. Hydration processes were also analyzed
according to the thermodynamic parameters. Finally, the effect of ul- 2.4. Experimental design
trasound power and temperature on germination parameters was ad-
dressed. Approximately 100 g of wheat grains were placed in the stainless
steel basket, which was immersed into the reactor with distilled water.
Wheat grains with initial moisture content X0 were hydrated until
2. Materials and methods reaching 0.75 g of water per 100 g of dry matter. This target moisture
was chosen as it is the necessary condition for breaking the cereal
2.1. Raw material dormancy [15].
Moisture content was monitored by weighing the drained samples at
Clean and whole wheat (Triticum spp.) grains were kindly provided time intervals throughout the experiments (1, 2, 3, 4, 6, 8, 10, 14 and
by the malting unit Malteria Blumenau (Blumenau, Santa Catarina, 24 h). The weighing frequency was altered if the desired moisture
Brazil). Initial moisture content was determined by drying the grains in content was reached before or after the predefined time intervals.
a convective oven at 105 °C in triplicate, according to the method from Hydrations were performed based on a complete factorial design by
AOAC [29]. Grains were, then, stored at room temperature in plastic varying the water temperature (15; 20 and 25 °C – considering the
bags until their use. temperature range used for wheat malt production) and the input ul-
trasonic power level (0, 500, 1000 and 1500 W). In the ultrasound-
assisted experiments, ultrasound was applied using pulsed system (1 s
2.2. Experimental set-up on; 4 s off). This was the best condition tested in which ultrasound
could be applied at the higher input power without overheating the
The experiments assisted by ultrasound were performed using a si- medium.
milar system as used by Carvalho et al. [14]. It consists of an ultrasonic
processor VCX-1500 (Sonics & Materials Inc., USA), operating at 20 kHz 2.5. Mathematical modeling
of frequency and input nominal power able to vary from 300 W to 1500
W. It is coupled with a cylindrical titanium sonotrode of 2.2 cm dia- Hydration kinetics was described using the Peleg Model (Eq. (2),
meter, being the tip positioned 1.5 cm from the perforated stainless [33]) and the Weibull Model (Eq. (5), [34]):
steel basket (5 cm height; 12.5 cm diameter) where the wheat samples
t
were placed. The temperature of the reactor (stainless steel; 15 cm X (t ) = X0 +
k1 + k2 t (2)
diameter; 22 cm height) was controlled by driving cooled water from
the thermostatic bath (MA-184 model, Marconi, Brazil) through the Where X(t) is the moisture content (g of water per g of dry matter) at
jacketed side of the vessel. Hydrations without ultrasound were carried time t, X0 is the initial moisture content (g of water per g of dry matter),
out in the same experimental set-up, but without ultrasound applica- t is the hydration time (h), and k1 (g of dry matter h g−1·of water) and
tion. k2 (g of dry matter g−1 of water) are model parameters.

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B. Guimarães, et al. Chemical Engineering & Processing: Process Intensification 155 (2020) 108045

Complementary parameters can be obtained from the Peleg model activation entropy is related to disorder degree [41].
constants. The rate R0 (g of water g−1 of dry matter h−1) of water
absorption at the beginning of the process can be obtained as the in- 2.7. Germination power
versed of k1:
After hydration up to ∼0.75 g of water per 100 g of dry matter, the
dX (t ) 1
= R0 = wheat grains were germinated to simulate malting.
dt t→0 k1 (3)
For that, 50 units of hydrated wheat grains were placed in rectan-
On the other hand, the equilibrium moisture content (Xeq) can be gular trails (13 cm long, 9 cm width and 4 cm height) and covered by
estimated from k2, considering long periods of hydration (t → ∞) by Eq. perforated plastic film to allow gas exchange. The trails were condi-
(4): tioned in an incubator (MA 415, Marconi, Brazil) at 16 °C during 8 days.
The moisture content of the wheat grains was controlled by weighing
1
Xeq = X0 + the trails every 12 h and humidifying the grains when needed.
k2 (4)
At specific time intervals (0, 24, 48, 72 and 96 h), the grains were
The Weibull Model, is an exponential empirical model very useful evaluated and photographed. The germination percentage (%GER) was
due to its simplicity and good accuracy in describing complex processes determined during the whole period of germination. This percentage
with high variability [14,35,36]. corresponds to the number of germinated grains per total number of
α grains as given by Eq. (11):
X (t ) − X0 t
= 1 − exp ⎡−⎛⎜ ⎞⎟ ⎤ n
Xeq − X0 ⎢ β ⎥ %GER = × 100
⎣ ⎝ ⎠ ⎦ (5) N (11)
where α is the shape parameter (dimensionless), which was also asso- where n is the number of germinated grains and N is the total number of
ciated to the initial rate of water uptake [37], and β is the time scale grains.
parameter (h), which represents the kinetics (and the required time to The average time needed for germination (ATG) could be also cal-
reach 63 % of the equilibrium moisture content). Moreover, the shape culated over the 8 days of incubation, as given by Eq. (12):
parameter α can be interpreted as a behavior index that is related to the
moisture migration mechanism during hydration: Values higher than 1 ∑ n i ti
ATG =
indicates the process is governed by internal moisture diffusion as well ∑ ni (12)
as external mass transfer, while external mass transfer is considered
where ni is the number of germinated grains per day, ti is the incubation
negligible when α < 1 [38,39].
time; and i varied from 1 up to 8 days [42].
Non-linear regressions were performed using the OriginPro 9.0
software (OriginLab Corporation, Northampton, USA). The accuracy of
3. Results and discussions
the models was evaluated through the adjusted correlation coefficient
2
(Radj ) and root-mean-square error (RMSE).
3.1. Acoustic field characterization

2.6. Thermodynamic properties


Fig. 1 shows temperature increments after 90 s of ultrasound ap-
plication at the different power levels studied.
The estimation of the thermodynamic properties can provide in-
Ultrasound application caused an increment in the medium tem-
sights about the variables influence and the nature of the process. At
perature as a consequence of the collapse of cavitation bubbles. This
first, the effect of temperature on the specific parameter was evaluated
phenomenon provides useful information for determining the real
by fitting an Arrhenius-type equation (Eq. (6)) in each studied para-
acoustic power produced from established electrical input power, as
meters (PT):
well as its distribution inside the reactor. As the electrical energy cur-
E rent reaches the piezoelectric crystal, it starts to oscillate, contract and
PT = A exp ⎛ a ⎞
⎝ RT ⎠ (6) expand, and the mechanical waves are produced. These waves are
propagated to the bath cube, then towards the medium, causing the
where A is the pre-exponential factor, Ea is the activation energy (J
molecular displacement until the breakdown of the intermolecular
mol−1), R is the universal gas constant (8.314 J mol−1 K−1) and T is
forces [43]. In this moment, cavitation bubbles are formed and their
the temperature (K).
collapse generates pressure and heat gradients.
After obtaining the activation energy (Ea) for the different condi-
The temperature increase showed a linear trend over the ultrasound
tions, the thermodynamic properties could be determined. Thus, acti-
exposure time with determination coefficient higher than 0.99 for all
vation enthalpy (ΔH#; J mol−1), the activation Gibbs free energy (ΔG#;
the measurements. It reinforces the validity of using the calorimetric
J mol−1) and the activation entropy (ΔS#; J mol−1 K−1) were calcu-
method to estimate the delivered ultrasound power, and the heat
lated for the kinetic parameters of both models, i.e., the scale parameter
transfer to the surrounds could be neglected in the process (of only 90 s
(β), of the Weibull Model, as well as for the hydration rate (k1), for the
of duration).
Peleg Model, using the following equations [40]:
The slope (dT/dt) was used to calculate the acoustic power as well
ΔH # = Ea − RT (7) as the acoustic intensity, acoustic density and the yield of power con-
version at each condition. These parameters are described in Table 1.
P h As expected, acoustic power and derived acoustic parameters in-
ΔG # = −RT ln ⎛ T ⎞ ⎜ ⎟

⎝ kB T ⎠ (8) creased with increasing nominal power applied – although it was not
linear. Both the trend and values magnitude are in accordance to pre-
ΔH # − ΔG #
ΔS # = vious study regarding the acoustic field produced in aqueous medium
T (10)
used for improving barley grains hydration [14]. The low values of
−34
In these equations, h is the Plank's constant (6.6262 × 10 J·s−1) yield of power conversion (∼12−20%) must be highlighted, which
−23 −1
and kB is the Boltzmann's constant (1.3806 × 10 J K ). The acti- reinforce the need for determining the actual power delivered to the
vation enthalpy represents the required energy for binding water mo- system (instead of considering the nominal values). The yield of power
lecules to the wheat grains in order to form the activated complex; the conversion was also higher for the highest power level studied, evi-
Gibbs free energy is related to the process spontaneity; and the dencing a higher efficiency of the equipment in converting higher

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B. Guimarães, et al. Chemical Engineering & Processing: Process Intensification 155 (2020) 108045

distribution in the reactor, the most affected areas were located just
below the sonotrode. The rises in temperature tended to decrease as the
points are analyzed axially away from the center, due to acoustic at-
tenuation. Similar observations were done by Fan et al. [45] and Po-
lachini et al. [44], who observed higher acoustic power in the same
direction of the ultrasound transducer in both ultrasonic bath and
probe-type devices, respectively.
Even though the acoustic field presents some differences over the
reactor, it does not compromise our evaluation, since the wheat grains
were placed all over it, being also constantly moved during the process
(by evaluating the water absorption), which guaranteed process
homogeneity.
From now on, all the described ultrasound power parameters are
related with the actual measured values (in the exception when the
“nominal” term is applied).

3.2. Hydration kinetics

3.2.1. Required hydration time


Fig. 2 shows the necessary time needed by each treatment to reach
the desired moisture content (0.75 g of water per g of dry matter, which
is the dashed gray lines in the following Figs. 3 and 4). The higher was
the hydration temperature and the nominal power applied, the shorter
was the time required to humidify the grains. This time varied from
∼44 h for hydrations performed without ultrasound assistance at 15 °C
to 12 h when temperature was increased to 25 °C under sonication at
acoustic density of 0.102 W mL−1.
The time required for hydration was improved by ∼30−40 % when
temperature was raised from 15 to 20 °C. Increasing the temperature
from 15 to 25 °C caused an improvement in the processing time of ∼55
% for all acoustic density studied. On the other hand, experiments
carried out with ultrasound tended to last ∼28−42% shorter than
experiments performed without ultrasound. This value is in accordance
to literature, which reported an improvement by the use of ultrasound
of 40 % for Andean lupin beans [46], 35 % for corn kernels [47], 40 %
for sorghum [23], 40 % for navy beans [48] and 36 % for wheat grains
[26]. Moreover, when temperature and ultrasound application was
combined, an improvement of up to 72 % was noticed for the required
processing time.
For the range of variables studied, temperature had a higher im-
provement in the hydrations time. However, these effects should be
specifically evaluated regarding the hydration kinetics and quality
parameters as germination [28].
Grain’s water absorption was differently enhanced by varying pro-
cess conditions as seen by temperature and acoustic density in Figs. 3
and 4, respectively. Despite the differences over the processing time, all
of the hydration curves showed a similar downward concave shape –
typical for this kind of cereal – without a lag phase of very low water
absorption rate. Moreover, the wheat hydration presented only one
continuous behavior, differently to the hydration in two-parts described
for corn [47] and oat [49], reinforcing the use of Peleg and Weibull
Models.
At the beginning of the process, the rate of water absorption was
very high and it tended to decrease as the grain is hydrated. Literature
attributes the rapid water absorption through the free pores and ca-
Fig. 1. Temperature rise distribution inside the reactor after 90 s of ultrasound pillaries, and ultrasound can accelerate the water flow in the capillaries
application at (a) 500 W, (b) 1000 W and (c) 1500 W of nominal input power. through the so called “sponge effect” and inertial flow [47]. Once these
spaces are occupied by the water molecules, the difference between the
amounts of electrical energy into acoustic power [44]. wheat moisture content and its equilibrium moisture content decreased.
In addition to the higher acoustic field, the application of higher This reduced driving force leads the water absorption rate to decrease
nominal power is reported to increase the microagitation of the [50–52].
medium [19], leading to a more homogeneous exposure to ultrasound
application by the grains. Even so, the acoustic field is not perfectly 3.2.2. Kinetics modeling
homogeneous. Higher temperature increments are represented in Fig. 1 Table 2 shows the parameters of Peleg Model (Eq. (2)) while Table 3
by the zones with yellow to red coloration, covering wider areas as the presented the ones for Weibull Model (Eq. (5)). Both of them presented
2
nominal applied power increased. Concerning the temperature rise high accuracy (Radj > 0.9842 and RMSE < 0.0220), although Weibull

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B. Guimarães, et al. Chemical Engineering & Processing: Process Intensification 155 (2020) 108045

Table 1
Acoustic parameters for the different nominal input power applied.
Parameters Nominal input power

500 W 1000 W 1500 W

−1
dT/dt (ºC·s ) 0.015 ± 0.002c 0.020 ± 0.001b 0.025 ± 0.001a
Acoustic power (W) 61.45 ± 8.87c 83.60 ± 2.66b 102.41 ± 4.39a
Acoustic intensity (W cm−2) 16.16 ± 2.33c 21.99 ± 0.69b 26.94 ± 1.16a
Acoustic density (W mL−1) 0.061 ± 0.009c 0.084 ± 0.003b 0.102 ± 0.004a
Yield of power conversion (%) 12.29 ± 1.77c 16.72 ± 0.53b 20.48 ± 0.88a

Means and standard deviation followed by the same letter in the same line represent no significant difference by the Tukey test at 95 % of confidence.

physical properties of the grains. The physical properties of grains are


also related to the water absorption capacity by the grains (Xeq). No big
differences (0.7664–0.7769 g of water per g of dry matter) were ob-
served for the estimated equilibrium moisture content (Xeq) in the ex-
periments without ultrasound at the different temperatures studied. It is
in agreement with the values of k2 and Xeq from Peleg’s model, which
presented approximately constant values for the wheat capacity for
water absorption over the temperature range. No changes in the Xeq was
reported in literature for other food products, including grains such
barley, wheat and wheat flour [50,55], although the variations in the
equilibrium moisture content depends on the thermosensitivity and
temperature range studied [22,26].
The hydration curves of wheat grains were also affected by the
acoustic power applied into the medium. By both Figs. 2 and 4, it could
be seen that hydration experiments assisted by ultrasound reached the
aimed moisture content earlier as the power level increased. This ob-
servation is in close agreement to that observed for the time required to
Fig. 2. Processing time required by each experiment to reach the moisture reach 63 % of the Xeq (β): β values decreased as the nominal power was
content needed for wheat germination. Different lowercase and capital letters increased, although this decrease was more significant at lower tem-
represent significant difference (p < 0.05) by the Tukey test among the tem- peratures. During ultrasound application, the sound waves cause a
perature under the same acoustic density applied and among the acoustic series of compressions and decompressions in the solid material. This
density applied at the same temperature, respectively. sponge effect provoke the pores to contract and to expand successively,
promoting the water pumping towards the grain [46]. In the liquid side,
Model presented slightly higher adjusted determination coefficients and the cavitation bubbles generate high pressure and temperature gra-
slight lower root-mean-square error. After performing the statistical dients, besides microjets. It leads to the creation of microchannels in the
analysis, it could be seen the fitting parameters differed among the food matrix and an enhanced mass transfer. Thus, the access by the
experiments (p < 0.05). Therefore, these differences could be discussed water molecules to the grains’ microstructure is improved when com-
as follow. pared to conventionally agitated medium [19,20]. Because of these
The β values decreased when the medium temperature was in- effects, with increasing acoustic density, ultrasound caused an increase
creased, being in close agreement with the results shown in Fig. 2. This in the water absorption capacity (estimated by the equilibrium moisture
decrease in the β values is related to the increased water diffusivity at content - Xeq) in all studied temperatures. Besides the possible creation
higher temperatures as a consequence of the lower viscosity and the of micropores, ultrasound is also able to prevent their clogging by the
expansion of the grain pores [53]. The decrease in β with increasing removal of existing and/or extracted solids located into the micro-
temperature was even more noticeable for ultrasound-assisted experi- channels [22,56], which can contribute for the higher water absorption.
ments than for conventional hydration (without ultrasound). This ob- After observing lower enthalpy values for barley hydration with the
servation was accompanied by a slight increase in the equilibrium presence of ultrasound, Shafaei et al. [50] reinforced the energetic
moisture content (Xeq) of wheat grains under sonication, mainly at contribution by ultrasound to create active sites to bind water mole-
higher acoustic densities. cules.
The shape parameter α can be related to the mechanisms of water The indirect mechanisms (erosion in the solid-liquid interface, mi-
migration from the medium towards the center of the grain, but its crochannels formation and microagitation) are supposed to occur more
inverse also gives insights about the initial rate of hydration [38,39,54]. intensively at high water activity. In fact, the displacement between the
Analogous to the statement of Corzo et al. [38] and Marabi et al. [39] hydration curves of ultrasound-assisted experiments are more evi-
for drying and rehydration processes, α values lower than 1 indicated denced at higher moisture content. The experimental curves with in-
the water migration is governed by the internal resistance to mass creasing acoustic power tended to differ more noticeably among them
transfer. Since the α values in the present work varied from 0.5953 up at the end of the process. Miano et al. [57] stated that ultrasound effects
to 0.7950, it can be assumed that external resistance to water transfer is are more pronounced when the grains have higher water content as a
much lower than internals for hydration processes. In fact, Patero and consequence of the reduced difference in the acoustic impedance as
Augusto [23] highlight that food hydration is a reaction limited by well as the cavitation inside the grain. Grains with higher moisture
internal resistance to the mass transfer, even though ultrasound reduces content have their values for acoustic impedance close to the ones en-
the convective resistance by the intense turbulence in the aqueous countered for aqueous medium. This condition reduces the wave’s re-
medium. flectance and increases ultrasound effects. In fact, the rate of water
Internal resistances are not only attributed to the water diffusion but absorption in the beginning of the process did not present much var-
also to phenomenon as capillarity, which is more associated to the iation among the power levels applied: Close values of α, from Weibull

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B. Guimarães, et al. Chemical Engineering & Processing: Process Intensification 155 (2020) 108045

Fig. 3. Influence of temperature on the hydration experiments performed under (a) no sonication; sonication at acoustic density of (b) 0.061 W·mL−1, (c) 0.084
W·mL−1 and (d) 0.102 W·mL−1. The dots are the experimental values; the bars the standard deviation; the lines the best fitted model (Weibull Model). The horizontal
dashed line represents the moisture of 0.75 g of water per 100 g of dry matter.

Model, and R0, from Peleg Model, were noticed among the experiments – thus causing the enthalpy for binding water to increase until it covers
at a same temperature and reinforce this theory. Similar behavior was the strongest bind sites [59]. So, when hydration takes place at 0.061
observed for Andean lupin, different beans and grains as the own wheat and 0.084 W mL−1, the additional energy demanded by the new sites
[27,46,58]. are higher than the contribution of ultrasound to reduce their activation
energy. As the acoustic density reached 0.102 W mL−1, ultrasound
3.2.3. Thermodynamic properties effects could compensate the water binding onto the additional stronger
Estimating the thermodynamic parameters associated to the hy- dry sites with the reduction in the activation energy. This observation is
dration rate (β, from Weibull Model, and k1, from Peleg Model) can give in close agreement with enthalpy data presented as follow and can
insights about the influence of the variable on the hydration kinetics. describe the obtained data.
At first, Table 4 showed good fitting results of the Arrhenius-type The estimated activation energy values were required for the cal-
equation to β and k1. This equation provides information about the culation of activation enthalpy (ΔH#), activation Gibbs free energy
amount of energy (Ea) that is needed to form the activated complexes (ΔG#) and activation entropy (ΔS#), all expressed in Table 5. Activation
water-dry sites. The experiments without ultrasound had lower Ea enthalpy represents the binding energy or intermolecular forces be-
(46.59 kJ mol−1) than most of the ultrasound-assisted hydrations (at tween water and the food matrix [60]. This parameter followed the
0.061 and 0.084 W mL−1 of acoustic density). In a first moment, this is same trend as discussed for Ea, maintaining positive values for all of the
the opposite behavior of that described in literature for common beans, conditions. In other words, this endothermic reaction requires an ex-
barley and wheat grains [27,40,50] when studying ultrasound-assisted ternal amount of energy to form activation complex between water-dry
hydrations. The main differences among these studies are related to the sites before obtaining the final product (wet grains) [40]. These values
fact that ultrasound was applied at lower actual acoustic density than decreased in experiments with increasing acoustic density – confirming
the minimum level of the present study, besides the stricter and lower the findings in literature [27,50]. Moreover, the enthalpy values tended
range of temperature assessed. On the other hand, activation energy to decrease with increasing temperature. The increase in temperature
decreased from 90.36 kJ mol−1 up to 27.27 kJ mol−1 with increasing improves the complex formation by adding energy in the form of heat,
the acoustic density (applied from 0.061 to 0.102 W mL−1). Similar similarly as observed for other cereal as rice, barley and wheat
behavior was also presented for Ea related with k1. At the highest [27,50,61].
acoustic density applied, the activation energy was even lower than for The calculated activation entropy fluctuated between negative and
experiments without ultrasound – following the same trend reported by positive values, which can be a result of propagation of deviations
the abovementioned literature [27,40,50]. during calculation, once this parameter is calculated using ΔG# and
As observed before, ultrasound can create new active site for ΔH# (Eq. 10). Being the discussion through entropy and Gibbs free
binding water. It occurs analogously to what is observed during mate- energy similar, this latter was chosen for interpretation: Gibbs free
rial swelling in water sorption processes. At high moisture content, the energy represents the driving force, given by the difference between
material swells as it absorbs water and high-energy sites are opened up enthalpy (available energy) and entropy (unavailable energy), for the

6
B. Guimarães, et al. Chemical Engineering & Processing: Process Intensification 155 (2020) 108045

water) structure [40].

3.3. Germination

Controlling wheat germination permits the development of nu-


trients and ingredients to enhance functional and technological prop-
erties in food products or even when solely consumed [8,62].
Hydrated wheat grains were subjected to germination under con-
trolled conditions. Fig. 5 shows the percentage of germinated grains
over the incubation time for the different experiments evaluated and an
image corresponding to the initial radicles appearance. It could be seen
that experiments performed at 20 °C under 0.102 W mL−1 and at 25 °C
without ultrasound showed the lowest germination percentage at the
initial days of incubation. On the other hand, slightly higher germina-
tion percentage was obtained for 15 °C.
Miano and Augusto [22] described the mechanisms of the grains
hydrations as a 3-stage kinetics. The stage I concerns the initial water
uptake by physical mechanisms in order to activate its metabolism.
Then, in the stage II, the grains started to pass by metabolic preparation
for germinating such as enzyme development and to digest the reserve
molecules to be used by the embryo for germination, which is the stage
III. Because the processing time was longer for the lowest temperature,
the grains were supposed to remain more time in the stage II. In ad-
dition, Miano and Augusto [22] also highlights the possible existence of
both live and dead grains that absorbs water equally during hydration.
Thus, their heterogeneity in the germination step could lead to the high
standard deviation and no clear trend observed among some treat-
ments.
After 1 day of incubation, it was possible to notice the appearance of
radicle in some grains. However, in the second day, Fig. 6 showed the
majority of grains were germinated and the radicles tended to develop
over the following days. Based on the results of Figs. 5 and 6, some
germination parameters could be obtained for the two levels of acoustic
density at the three temperatures, being presented in Table 6. From the
fourth to the eighth day, the germination percentage almost did not
vary, reaching a maximum of ∼86 % with low variations among the
treatments. The obtained values for %GER were similar to the ones
found for some seeds [63], beans [64] and grains [65].
Although ultrasound application and temperature did not affect the
final percentage of germinated grains, they affected the hydration ki-
netics, or germination velocity, in some cases. Moreover, regarding the
quality aspects of the malt (total vitreous grain content, grain friability,
wort characteristics as diastatic power, viscosity, etc.), it is encouraged
to work under lower processing temperatures to meet the industrial
requirements [66]. On the other hand, the addition of aiding technol-
ogies as ultrasound may be an outcome for accelerating the process.
Besides the germination (%GER) at the fourth (4th) and eighth (8th)
day, Table 6 also presented the average time for the germination to
occur (ATG). The average time required for the maximum germination
was ∼5 days, as observed for ATG values. For wheat brewing purposes,
prolonging the germination is able to produce good quality malt as a
Fig. 4. Influence of the acoustic density on the hydration experiments per- consequence of the protein degradation over the grains growth [67].
formed at (a) 15 °C, (b), 20 °C and (c) 25 °C. Lines represented the best fitted However, the effects of ultrasound application and hydration tem-
model (Weibull Model). The horizontal dashed line represents the moisture of perature on the activity and actuation mechanisms of the proteases
0.75 g of water per 100 g of dry matter. should be specifically addressed.
In some cases, the germination was lower in comparison with some
hydration process to occur under specific conditions [61]. This mea- studies which reported an improvement in the germination of seeds and
surement is related to the to the spontaneity of the transition state beans by the use of ultrasound technology [18,24,65,68]. This im-
formation [40]. The activation Gibbs free energy remained positive, provement is closely dependent on the time-intensity of sonication as
characterizing a non-spontaneous reaction with slightly higher sensitive well as the application system and grain characteristics. In the studies
to temperature than acoustic density for the range of variables studied. which an enhanced germination was noticed, the acoustic density was
ΔG# increased with increasing temperature and increasing acoustic in the range of 0.013 up to 0.041 W/mL, for different exposure time.
density, similarly to the findings for wheat, barley and common beans Above this range, ultrasound seemed to cause damage to the plant
[27,40,41]. In this sense, the formation of the intermediate complex tissue that are responsible by the radicle development, besides the en-
dried grain-water is considered as not spontaneous, which is associated zymes inactivation [69]. These last authors observed that germination
with the high degree of organization in activated complex (dry matter – was hindered by using acoustic density of about 0.100 W mL−1) when

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B. Guimarães, et al. Chemical Engineering & Processing: Process Intensification 155 (2020) 108045

Table 2
Fitting parameters of Peleg Model (Eq. (2)) to the hydration data.
Temperature Acoustic density k1 k2 R0 Xeq 2
Radj RMSE
(ºC) (W mL−1) (g of dry matter h g−1·of (g of dry matter g−1 of (g of water g−1 of dry matter (g of water g−1 of dry
water) water) h−1) matter)

15 0 8.4598 ± 1.5024a 1.4904 ± 0.0491bcd 0.1206 ± 0.0202d 0.8174 ± 0.0117bcd > 0.9889 < 0.0185
0.061 9.3230 ± 0.5434a 1.5054 ± 0.0262abc 0.1075 ± 0.0061d 0.8174 ± 0.0117cde > 0.9804 < 0.0170
0.084 8.1723 ± 0.4216a 1.4829 ± 0.0162bcd 0.1226 ± 0.0065d 0.8274 ± 0.0074bcd > 0.9911 < 0.0161
0.102 5.1341 ± 0.2474b 1.5147 ± 0.0176abc 0.1951 ± 0.0092c 0.8133 ± 0.0077cde > 0.9882 < 0.0181
20 0 5.0031 ± 0.4920b 1.5690 ± 0.0178a 0.2011 ± 0.0192bc 0.7904 ± 0.0072e > 0.9842 < 0.0201
0.061 4.4867 ± 0.1747bc 1.5285 ± 0.0055ab 0.2231 ± 0.0089bc 0.8072 ± 0.024de > 0.9896 < 0.0165
0.084 4.6568 ± 0.0581bc 1.4534 ± 0.0072cde 0.2144 ± 0.0027bc 0.8411 ± 0.0034bc > 0.9941 < 0.0127
0.102 4.3894 ± 0.1152bc 1.4617 ± 0.0137bcd 0.2279 ± 0.0059bc 0.8372 ± 0.0064bcd > 0.9959 < 0.0107
25 0 4.7943 ± 0.1102bc 1.4549 ± 0.0148cde 0.2087 ± 0.0048bc 0.8404 ± 0.0070bc > 0.9965 < 0.0099
0.061 3.4626 ± 0.0297c 1.5054 ± 0.0066abc 0.2888 ± 0.0025a 0.8173 ± 0.0029cde > 0.9968 < 0.0094
0.084 4.2549 ± 0.2176bc 1.3858 ± 0.0152e 0.2354 ± 0.0123b 0.8746 ± 0.0078a > 0.9986 < 0.0065
0.102 3.3492 ± 0.2977c 1.4348 ± 0.0457de 0.3003 ± 0.0281a 0.8504 ± 0.0220ab > 0.9932 < 0.0136

Means and standard deviation followed by the same lowercase letters in the same column represent no significant difference by the Tukey test at 95 % of confidence.

Table 3
Fitting parameters of Weibull Model (Eq. (5)) to the hydration data.
Temperature Acoustic density α β Xeq 2
Radj RMSE
(ºC) (W mL−1) (dimensionless) (h) (g of water g−1 of dry matter)

15 0 0.7352 ± 0.0981abc 8.1923 ± 0.5723bc 0.7675 ± 0.0162b > 0.9873 < 0.0190
0.061 0.6432 ± 0.0634abcd 12.2135 ± 1.6942a 0.8189 ± 0.0310ab > 0.9952 < 0.0119
0.084 0.6793 ± 0.0506abcd 9.4047 ± 1.6589b 0.8028 ± 0.0292ab > 0.9931 < 0.0139
0.102 0.6198 ± 0.0239 cd 6.3772 ± 1.0896c 0.8111 ± 0.0290ab > 0.9907 < 0.0152
20 0 0.6491 ± 0.0082bcd 5.5988 ± 0.7975de 0.7769 ± 0.0148b > 0.9782 < 0.0220
0.061 0.5953 ± 0.0139d 6.0684 ± 0.6586cde 0.8275 ± 0.0175ab > 0.9947 < 0.0110
0.084 0.6952 ± 0.0317abcd 4.9633 ± 0.4654de 0.7998 ± 0.0158ab > 0.9947 < 0.0115
0.102 0.6840 ± 0.0061abcd 4.7140 ± 0.1096de 0.8000 ± 0.0039ab > 0.9949 < 0.0112
25 0 0.7656 ± 0.0169ab 4.3834 ± 0.1135de 0.7664 ± 0.0046b > 0.9933 < 0.0128
0.061 0.6499 ± 0.0170bcd 3.7165 ± 0.1789e 0.7882 ± 0.0065ab > 0.9991 < 0.0045
0.084 0.7950 ± 0.0077a 3.8059 ± 0.1832e 0.7802 ± 0.0035b > 0.9974 < 0.0082
0.102 0.6359 ± 0.0937bcd 4.4891 ± 1.0547de 0.8551 ± 0.0597a > 0.9959 < 0.0101

Means and standard deviation followed by the same lowercase letters in the same column represent no significant difference by the Tukey test at 95 % of confidence.

Table 4 using ultrasonic bath. On the other hand, this impairment was not
Fitting parameters of the Arrhenius-type equation to the β and k1 values. observed in the present study for probe-type system using similar
Parameters Acoustic density A Ea RMSE 2 acoustic density. The system of ultrasound application is highly related
Radj
(W mL−1) (units of β or k1) (kJ mol−1) with the sonochemical effects produced in the material. Ultrasound
baths have transducers distributed along the bottom surface while the
β 0.000 2.91 × 10−8 46.58 0.1646 0.9785 ultrasonic probe has one main point of higher application. Thus, the
0.061 5.02 × 10−16 90.36 0.2495 0.9903
0.084 6.40 × 10−13 72.59 0.4243 0.9382
temperature rise distribution caused by probe-type ultrasound appli-
0.102 0.71 × 10−4 27.27 0.2890 0.7645 cation is less homogeneous in the reactor, as evidenced in Fig. 1. Also,
k1 0.000 2.14 × 10−8 47.34 0.6088 0.7376 probe-type ultrasound is supposed to promote higher degree of agita-
0.061 1.30 × 10−14 81.91 0.4911 0.9261 tion over time, leading the particles in suspension to a more homo-
0.084 1.23 × 10−9 54.11 0.5414 0.8103
geneous exposure to ultrasound. Apart of the intrinsic characteristics of
0.102 2.59 × 10−5 29.25 0.1196 0.9466
the wheat itself, these two reasons (zones of lower acoustic density and
particles movement) might be a reason why ultrasound was able to

Table 5
Activation enthalpy (ΔH#), Gibbs free energy (ΔG#) and entropy (ΔS#) for β and k1 values at different temperatures and acoustic density applied.
Parameters T (ºC) β k1

−1
Acoustic density (W mL ) Acoustic density (W mL−1)

0.000 0.061 0.084 0.102 0.000 0.061 0.084 0.102

ΔH# 15 44.19 87.96 70.20 24.88 44.94 79.51 51.71 26.86


(kJ mol−1) 20 44.15 87.92 70.16 24.84 44.90 79.47 51.67 26.82
25 44.10 87.88 70.11 24.79 44.86 79.43 51.63 26.78
ΔG# 15 54.42 53.46 54.09 55.02 54.34 54.11 54.42 55.54
(kJ mol−1) 20 56.33 56.14 56.63 56.75 56.61 56.87 56.78 56.92
25 57.94 58.35 58.29 57.88 57.72 58.53 58.01 58.61
ΔS# 15 −0.04 0.12 0.06 −0.10 −0.03 0.09 −0.01 −0.10
(kJ mol−1 K−1) 20 −0.04 0.11 0.05 −0.11 −0.04 0.08 −0.02 −0.10
25 −0.05 0.10 0.04 −0.11 −0.04 0.07 −0.02 −0.11

8
B. Guimarães, et al. Chemical Engineering & Processing: Process Intensification 155 (2020) 108045

Fig. 5. Germination (%) of wheat grains over the incubation time. Dots and error bars represent the calculated germination percentage and standard deviation,
respectively, in triplicate. Figure at left showed the radicles appearance at the first germination day.

Fig. 6. Visual aspect of the wheat grains during 5 days of germination.

accelerate hydration process without significant losses in the germina- were assessed at different temperatures (15–25 °C) and actual acoustic
tion percentage observed for non-sonicated wheat. density (0.061–0.102 W mL−1). The last parameter was characterized
by the calorimetric method, reaching the higher exposures to ultra-
sound just below the sonotrode. Yields of power conversion were found
4. Conclusions
between 12.3 and 20.5 %. The Peleg and Weibull Models were fitted to
the experimental data with high accuracy, although slightly higher
Conventional and ultrasound-assisted hydration of wheat grains

9
B. Guimarães, et al. Chemical Engineering & Processing: Process Intensification 155 (2020) 108045

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