Journal of Food Engineering 108 (2012) 283–289

Contents lists available at SciVerse ScienceDirect

Journal of Food Engineering

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

Effect of temperature on dynamic and steady-state shear rheological properties

of siriguela (Spondias purpurea L.) pulp
Pedro E.D. Augusto a,b,⇑, Marcelo Cristianini a, Albert Ibarz c
a
Department of Food Technology (DTA), School of Food Engineering (FEA), University of Campinas (UNICAMP), Brazil
b
Technical School of Campinas (COTUCA), University of Campinas (UNICAMP), Brazil
c
Department of Food Technology (DTA), School of Agricultural and Forestry Engineering (ETSEA), University of Lleida (UdL), Lleida, Spain

a r t i c l e i n f o a b s t r a c t

Article history: The present work has evaluated the dynamic and steady-state shear rheological properties of siriguela
Received 21 February 2011 (Spondias purpurea) pulp as function of temperature (0–80 °C), as well as the applicability of the Cox-
Received in revised form 3 August 2011 Merz rule. The product flow behavior could be well described by the Herschel–Bulkley’s model
Accepted 21 August 2011
(R2 > 0.98), whose parameters were modeled as function of temperature (R2 > 0.91). The product has
Available online 30 August 2011
shown a weak gel behavior, with storage modulus higher than loss modulus in the evaluated frequency
range. The storage and loss modules could be well described by a power function of the oscillatory fre-
Keywords:
quency (R2 > 0.93), whose parameters were modeled as function of temperature (R2 > 0.97). Moreover, a
Food properties
Rheology
power modified Cox-Merz rule could describe the rheological properties of S. purpurea pulp (R2 > 0.96).
Viscoelasticity The obtained data are potentially useful for future studies on food properties and process design.
Viscosity Ó 2011 Elsevier Ltd. Open access under the Elsevier OA license.

1. Introduction The rheological characterization of food is important for unit

Spondias purpurea L. is a native fruit of Central America, dis-
persed in Mexico, Guatemala and the Caribbean, and in some coun-
tries of South America, mainly in the northeast region of Brazil
(Sampaio et al., 2008; Augusto et al., 2000). The species belongs
to the family Anacardiaceae, the same as mango (Mangifera índica),
cashew apple (Anacardium occidentale) (Sampaio et al., 2008), cajá
(Spondias mombin L.) and umbu (Spondias tuberosa Arruda Camara)
(Bicas et al., 2011).
It is a small red fruit, with a pleasant aroma and taste which is
consumed in natura or as juice and other products such as jams and
different candies. The S. purpurea L. is called by different names,
which are function of the geographic region, such as red mombin,
siriguela, seriguela, ceriguela, ciriguela, jocote, jocote de corona,
ciruela, ciruela Mexicana, jobillo, spanish plum and hog plum (Bi-
cas et al., 2011; Furtado et al., 2010; Ceva-Antunes et al., 2006;
Parada et al., 2006; Martins et al., 2003; Augusto et al., 2000).
The consumer demand for native and exotic products is grow-
ing, in special for food products, creating the need for better under-
standing of its processing and properties. Moreover, Furtado et al.
(2010) and Ceva-Antunes et al. (2006) observed that the native
fruit commercialization plays an important role in social and
employment perspectives in development countries like in Brazil.
⇑ Corresponding author at: Technical School of Campinas (COTUCA), University of
Campinas (UNICAMP), R. Culto à Ciência, 177 Botafogo, CEP: 13020-060 Campinas,
SP, Brazil.
E-mail address: pedro@cotuca.unicamp.br (P.E.D. Augusto).
operations design, process optimization and high quality products
assurance (Ibarz and Barbosa-Cánovas, 2003; Rao, 1999). Although
the rheological characterization of exotic fruits is being studied for
various authors, there is no work in literature related to the rheo-
logical characterization of S. purpurea L. pulp, even though it is
essential for processing design.
The present work has evaluated and modeled the rheological
properties of siriguela (S. purpurea L.) pulp as function of
temperature.
2. Material and methods
A pasteurized frozen commercial siriguela (S. purpurea L.) pulp
was used in order to guarantee the standardization and repeatabil-
ity. After washing, the fruits are pulped, pasteurized, packaged in
small plastic bags and then frozen. Further information related to
siriguela fruits and pulp can be obtained in the works of Sampaio
et al. (2008) and Martins et al. (2003).
Samples were thawed and carefully homogenized before the
rheological measurements were taken. Its soluble solids content
was determined by using a refractometer (digital refractometer
r2 mini, Reichert Analytical Inst., Japan), after filtering the samples
in cotton, being 10.9 ± 0.1°Brix (mean of three replicates ± stan-
dard deviation). The sample total solid content was measured
using the pulp moisture, determined by an infra-red moisture ana-
lyzer (IV2002, Gehaka, Brazil). The sample total solid content was
15.8 ± 0.4% (mean of three replicates ± standard deviation).

0260-8774 Ó 2011 Elsevier Ltd. Open access under the Elsevier OA license.
doi:10.1016/j.jfoodeng.2011.08.015
284 P.E.D. Augusto et al. / Journal of Food Engineering 108 (2012) 283–289
Nomenclature
a behavior index in power modified Cox-Merz rule (Eq.
(11)) [-]
b magnitude index in power modified Cox-Merz rule (Eq.
(11)) [-]
c_ shear rate [s1]
ga apparent viscosity (= r/c_ ) [Pa s]
g⁄ complex viscosity [Pa s]
r shear stress [Pa]
r0 yield stress, Herschel–Bulkley’s model [Pa]
x oscillatory frequency [Hz]
A0 Arrhenius’s pre-exponential parameter model
Ea activation energy in Arrhenius’s model [J mol1]
2.1. Rheology procedures
Rheological measurements were carried out with a controlled
stress (r) rheometer (AR2000ex, TA Instruments, USA), using a
grooved plate–plate geometry (40 mm of diameter). The gap
dimension (1.0 mm) was determined by using a gap-independency
procedure, as described by Tonon et al. (2009).
The rheological properties were evaluated from 0 to 80 °C, and
temperature was controlled by a Peltier system in each procedure.
Geometry material thermal expansion was considered in order to
guarantee the appropriated gap dimension. Moreover, at the tem-
peratures of 60 and 80 °C, a solvent trap was used in order to min-
imize water vaporization from the product (it was observed that it
was not necessary in temperatures below 60 °C).
The rheological evaluation was carried out with new samples,
i.e., with non-mechanical history. Thus, samples were placed in
the rheometer and kept at rest for 5 min before shearing.
The experiments were carried out in three replicates, and the
regressions were done for each replicate. The parameters of each
model were obtained by non-linear regression using the software
CurveExpert Professional v.1.0.1 using a significant probability le-
vel of 95%.
2.1.1. Steady-state shear properties
The steady-state shear experiments were carried out in the
shear rate (c_ ) range of 0.01–100 s1. After rest, samples were sub-
mitted to shearing at 300 s1 for 5 min to avoid any thixotropy
(data not shown). Then, a logarithmic decreasing stepped protocol
(100–0.01 s1) was used in order to guarantee the stead-state con-
dition. The products flow behavior was modeled using the Her-
schel–Bulkley’s model (Eq. (1)). Herschel–Bulkley’s model
comprises Newton, Bingham and Ostwald-de-Waele (power law)
models. It is commonly used to describe the rheological properties
of food products.
r ¼ r0 þ k  c_ n
2.1.2. Viscoelastic properties
Oscillatory stress sweeps between 0.01 and 100 Pa were per-
formed at a frequency of 1 Hz to determine the products’ linear vis-
coelastic range. Then, frequency sweep measurements were
carried out at 1.0 Pa, a shear stress value within the linear visco-
elastic range. The oscillatory frequency (x) was then varied from
0.01 to 100 Hz. The storage modulus (G0 ), loss modulus (G00 ) and
complex viscosity (g⁄) were thus obtained, as function of frequency
(x).
The storage (G0 ) and loss (G00 ) modules were modeled as a power
function of oscillatory frequency (x) (Eqs. (2) and (3)), as com-
G0 storage modulus [Pa]
G00 loss modulus [Pa]
k consistency coefficient, Herschel–Bulkley’s model
[Pa sn]
k0 , k00 consistency coefficient in power law model of viscoelas-
0 00
ticity properties (Eqs. (2) and (3)) [Pa sn , Pa sn ]
n flow behavior index, Herschel–Bulkley’s model [-]
n0 , n00 behavior index in power law model of viscoelasticity
properties (Eqs. (2) and (3)) [-]
TK absolute temperature [K]
TC temperature [°C]
monly used for describing the viscoelastic behavior of food and dis-
persions (Rao, 1999):
0 0
G0 ¼ k  xn ð2Þ
00 00
G00 ¼ k  xn ð3Þ
2.2. Applicability of the Cox-Merz rule
The Cox-Merz rule states that the apparent viscosity (ga = r/c_ )
at a specific shear rate (c_ ) is equal to the complex viscosity (g⁄)
at a specific oscillatory frequency (x), when c_ = x (Eq. (4); Rao,
2005). When this rule is valid, the rheological food properties can
be determined by either oscillatory or steady-state shear experi-
ments, which are useful due to limitations in each kind of experi-
ment (Gunasekaran and Ak, 2000).
Thus, the obtained results from the steady-state shear and vis-
coelastic analysis were used for the evaluation of the Cox-Merz
rule applicability:
ga ðcÞ ¼ g  ðxÞjc_ ¼x ð4Þ
3. Results and discussions
3.1. Steady-state shear properties
Fig. 1 shows the flow curves (r versus c_ ) of siriguela (S. purpurea
L.) pulp at 0, 20, 40, 60, and 80 °C. As expected, the S. purpurea pulp
showed a shear-thinning behavior (n < 1) with a representative
yield stress (r0).
The yield stress is the minimum shear stress required to initiate
product flow, being related to the material’s internal structure
which must be broken (Genovese and Rao, 2005; Tabilo-Munizaga
and Barbosa-Cánovas, 2005). At stress below the yield stress, the
ð1Þ material deforms elastically, behaving like an elastic solid; above
the yield stress, it starts flowing, behaving like a viscous liquid
(Bayod et al., 2007). The presence of a yield stress is a typical char-
acteristic of multiphase materials (Sun and Gunasekaran, 2009), as
fruit pulps and juices, which are formed by a dispersion of insolu-
ble components (materials of cellular walls) in a water solution
(serum, containing sugars, minerals, proteins, and soluble
polysaccharides).
Table 1 shows the values of the Herschel–Bulkley model param-
eters for S. purpurea pulp in the evaluated temperature range. The
R2 values were always higher than 0.98. The obtained values of
yield stress (r0), flow behavior index (n), and consistency coeffi-
cient (k) are close to those described in the literature for fruit prod-
ucts (Table 2; 20–30 °C).
 P.E.D. Augusto et al. / Journal of Food Engineering 108 (2012) 283–289 285

100 each parameter A is modeled by a pre-exponential factor – A0,

o o o o o
0C 20 C 40 C 60 C 80 C and the activation energy – Ea; R is the constant of the ideal gases,
and TK is the absolute temperature):
75  
Ea
A ¼ A0  exp ð5Þ
R  TK
σ (Pa)

50 The consistency coefficient (k, Fig. 2) could be well modeled by

the Arrhenius Equation (Eq. (6); R2 = 0.91). Although being in the
same order of magnitude, the siriguela (S. purpurea) pulp activation
25 energy value (Ea = 17509.2 J mol1) was higher than those de-
scribed for other fruit products as tomato derivates (Table 3). Thus,
the S. purpurea pulp internal structure is less affected by tempera-
0
ture than those products. Even though, its activation energy (Ea)
0 25 50 75 100 value is closed to those described in the literature for fruit products
. (Table 3), such as tomato paste, jabuticaba pulp and Juniperus drup-
γ (s-1)
acea fruit juice.
Fig. 1. Flow curves of S. purpurea L. pulp at 0, 20, 40, 60, and 80 °C. Mean of three Massa et al. (2010) observed that the Brownian motion in-
replicates; vertical bars represent the standard deviation in each value. creased with the temperature, resulting in a less developed struc-
ture at higher temperatures, which explains the lower consistency
coefficient values:
Table 1  
17509:2
Values for the parameters of Herschel–Bulkley model the S. purpurea L. pulp (mean of k ¼ 20:92  exp ð6Þ
three replicates ± standard deviation; R2 higher than 0.98 in each regression). R  TK
T (°C) r0 (Pa) k (Pa sn) n The flow behavior index (n) is generally assumed to be rela-
0 11.24 ± 0.53 21.54 ± 0.95 0.25 ± 0.01 tively constant with temperature (Rao, 1999). However, as can be
20 13.26 ± 0.15 15.22 ± 0.20 0.30 ± 0.00 seen in Fig. 2, the flow behavior index showed a rising trend in
40 12.56 ± 0.25 11.22 ± 0.13 0.34 ± 0.01 relation to temperature, which could be well modeled by a linear
60 1.50 ± 0.04 3.01 ± 0.07 0.44 ± 0.00 function (Eq. (7); R2 = 0.97):
80 1.37 ± 0.12 1.71 ± 0.19 0.48 ± 0.01
n ¼ 0:241 þ 0:03  T C ð7Þ
The yield stress (r0) modeling is not often carried out in litera-
The S. purpurea pulp is characterized by a high consistency, ture works, as it behavior is the less pronounced. In some products
which can be observed by the magnitudes of r0 (13.3 Pa) and k it tends to remain constant (as, for example, in 21°Brix peach puree
(15.2 Pa sn) at 20 °C. As can be seen in Table 2, it is closed to the between 5 and 55 °C; Massa et al., 2010), while in others it shows a
values reported for other fruit pulps as peach (r0 = 25.3 Pa; monotonous falling behavior (as, for example, in butia pulp be-
k = 11.3 Pa sn), umbu (r0 = 8.1 Pa; k = 37.7 Pa sn) and mango tween 10 and 60 °C; Haminiuk et al., 2006). In some products,
(r0 = 6.2 Pa; k = 11.3 Pa sn). however, it shows a non-identifiable behavior (as, for example, in
As expected, the increase in temperature reduces the yield potato puree between 25 and 65 °C; Canet et al., 2005). In fact, it
stress (r0) and consistency coefficient (k), increasing the flow is important to observe that the property behavior in relation to
behavior index (n). Although the temperature reduces the shear- temperature is function not only of the product itself, but also of
thinning behavior (i.e., increasing in n), the pulp shear-thinning the studied temperature range.
behavior is still representative even at 80 °C (n80 °C = 0.48). Although having a falling behavior with temperature increasing,
The most used approach to modeling the temperature influence the yield stress (r0) could not be modeled by the Arrhenius Equa-
on the rheological properties of food is to consider its effect on the tion. This behavior is different than those observed in tomato juice
viscosity or apparent viscosity. However, the most important ap- (Augusto et al., in press-a), where the yield stress was modeled
proach for the evaluation of non-Newtonian fluids is modeling using the Arrhenius Equation (the other works listed in Table 2
each Herschel–Bulkley model’s parameter separately. Thus, the have not modeled each Herschel–Bulkley model’s parameter
Herschel–Bulkley parameters were modeled as function of separately).
temperature. As can be observed in Fig. 2, the yield stress has shown a falling
The effect of temperature on the consistency coefficient (k) are sigmoidal trend in relation to temperature, in contrast with the
generally modeled using the Arrhenius Equation (Eq. (5), where continuous decrease of the exponential function (Arrhenius Equa-

Table 2
Values for the parameters of Herschel–Bulkley model for fruit products.

Product T (°C) r0 (Pa) k (Pa sn) n References

S. purpurea L. pulp 20 13.26 15.22 0.30 Present work
Peach puree (12–21°Brix) 25 1.11–25.3 2.46–11.3 0.32–0.34 Massa et al. (2010)
Butia pulp 20 32.54 0.15 0.86 Haminiuk et al. (2006)
Apple, apricot and banana based babyfood 20 3.38–7.41 4.76–13.7 0.18–0.38 Ahmed et al. (2007)
Umbu pulp (10–25°Brix) 20 3.18–8.06 14.00–37.74 0.29–0.31 Pereira et al. (2007) and Pereira et al. (2008)
Peach juice (10% fiber) 20 3.26 13.1 0.46 Augusto et al. (2011)
Mango pulp 20 3.81–6.24 8.82–11.33 0.31–0.34 Ahmed et al. (2005)
Concentrated tamarind juice (71°Brix) 30 1.46 4.32 0.59 Ahmed et al. (2007)
Açai pulp 25 4.35 0.17 0.78 Tonon et al. (2009)
Jabuticaba pulp 25 1.55 0.48 0.60 Sato and Cunha (2009)
Tomato juice 20 0.94 0.19 0.56 Augusto et al. (in press-a)
286 P.E.D. Augusto et al. / Journal of Food Engineering 108 (2012) 283–289

T (K)
273.15 293.15 313.15 333.15 353.15
25
Experimental (stress)
Power sigmoidal
20 Experimental (k)
σ (Pa); k (Pa.sn)

Arrhenius

15
o

10

0
0.6 0 20 40 60 80
T(ºC)

0.4

o
n

0.2

Experimental
Fig. 3. Mechanical spectra of S. purpurea L. pulp at 0 and 80 °C. Mean of three
Linear replicates; vertical bars represent the standard deviation in each value.
0.0
0 20 40 60 80
o 3.2. Viscoelastic properties
T( C)

Fig. 2. Parameters of the Herschel–Bulkley model as function of temperature. Mean Fig. 3 shows the mechanical spectra of S. purpurea L. pulp at 0
of three replicates; vertical bars represent the standard deviation in each value. and 80 °C. The siriguela (S. purpurea L.) pulp storage modulus val-
ues (G0 ) were always higher than those of the loss modulus (G00 ),
which indicates that the pulp has dominant elastic properties over
Table 3
the viscous ones. Thus, the product can be classified as a weak gel
Activation energy (Ea) of the Arrhenius model (A = A0 exp(Ea/RT)) for the consistency
index (k) in fruit products.
(Rao, 1999). Similar behavior has been reported for other food
products such as peach puree (Massa et al., 2010), açai pulp (Tonon
Product Ea (k) (J mol1) References
et al., 2009), jabuticaba pulp (Sato and Cunha, 2009), umbu pulp
S. purpurea L. pulp 17509.2 Present work (Pereira et al., 2008), baby foods (Ahmed and Ramaswamy,
Tomato juice 7353.3 Augusto et al. (in press-a) 2006), potato puree (Alvarez et al., 2004), tomato juice (Augusto
Tomato paste 8600–13000 Dak et al. (2008)
Reconstituted tomato 7360–3630 Barbana and El-Omri (in press)
et al., in press-b) and concentrates (Bayod et al., 2008; Valencia
concentrates et al., 2002; Yoo and Rao, 1996).
Jabuticaba pulp 13000 Sato and Cunha (2007) As expected, the values of G0 and G00 had shown a rising ten-
Juniperus drupacea 60380–78230 Akbulut et al. (2008) dency with the oscillatory frequency, the opposite behavior of
fruit juice
the complex viscosity (g⁄). Thus, it was possible to model the stor-
age and loss modules as a power function of the oscillatory fre-
tion). Until 40 °C, the yield stress shows quasi-constant values (11– quency (Eqs. (2) and (3)). Table 4 shows the values for the power
13 Pa) followed by a great decrease in temperatures between 40 law model (Eqs. (2) and (3)) as a function of temperature. The R2
and 60 °C. Then, it tends to stay back in a constant value (1– values were always higher than 0.93 in each replicate. The ob-
2 Pa). This trend could be well modeled by a power sigmoidal func-
tion (Eq. (8); R2 = 0.98), and shows that an important transforma-
tion is carried out in siriguela (S. purpurea) pulp between 40 and Table 4
60 °C, as the yield stress value changes are more important in this Values for the power law model for storage (G0 ) and loss (G00 ) modules of S. purpurea L.
pulp as a function of oscillatory frequency (x) (1 Pa, mean of three replicates ± stan-
temperature range when compared to temperatures below 40 °C dard deviation; R2 higher than 0.93 in each regression).
and above 60 °C. The viscoelastic analysis corroborates this obser- 0 00

vation (Fig. 3). Bhattacharya (1999) had studied the mango pulp T (°C) k0 (Pa sn ) n0 k00 (Pa sn ) n00

yield stress in temperatures of 5, 30, 55 and 80 °C, observing a 0 303.0 ± 6.2 0.16 ± 0.01 74.4 ± 1.5 0.28 ± 0.01
great fall in yield stress value between 55 and 80 °C: 20 286.3 ± 4.3 0.14 ± 0.01 66.4 ± 0.8 0.27 ± 0.00
40 294.7 ± 15.2 0.15 ± 0.01 71.3 ± 4.4 0.23 ± 0.01
12:36 60 92.7 ± 6.4 0.16 ± 0.02 23.3 ± 1.6 0.28 ± 0.01
r0 ¼ ð8Þ 80 37.1 ± 2.8 0.14 ± 0.01 11.7 ± 0.6 0.30 ± 0.02
1 þ ð0:018  T C Þ20:77
 P.E.D. Augusto et al. / Journal of Food Engineering 108 (2012) 283–289
tained values are in accordance with those reported in the litera-
ture by other food products.
Ahmed and Ramaswamy (2006) have evaluated the viscoelastic
behavior of vegetable based baby food. The values of k0 and k00 ran-
0 00
ged from 131.0–13500 Pa sn to 19.7–1750 Pa sn , respectively (20–
0 00
25 °C). The values of n and n were in the range from 0.06–0.14 to
0.16–0.22, respectively.
The viscoelastic behavior of tomato products (concentrates and
ketchups; 24–27% of total solids, 22–27°Brix) have been evaluated
by Bayod et al. (2008) and Yoo and Rao (1996). The values of k0 and
0 00
k00 ranged from 1660–16982 Pa sn to 106.6–3802 Pa sn , respec-
0 00
tively (20–25 °C). The values of n and n were in the range from
0.12–0.25 to 0.10–0.33, respectively.
Augusto et al. (2011) studied the effect of fiber addition on the
rheological properties of peach juice (10–12.5% fiber; 0–40 °C). The
0
values of k0 and k00 ranged from 263.9–1567.1 Pa sn to 59.8–
n00 0 00
616.6 Pa s , respectively. The values of n and n were in the range
from 0.14–0.28 to 0.24–0.54, respectively.
The values of n00 were always higher than n0 (Table 4), which
demonstrate that the viscous behavior of S. purpurea pulp becomes
more important in high frequencies. Moreover, the viscous behav-
ior becomes more important in high temperatures, as can be seen
by the convergence of k0 and k00 (Table 4, Fig. 4).
When the parameters of the power law model for storage (G0 )
and loss (G00 ) moduli (Eqs. (2) and (3)) were evaluated in relation
to the temperature, a different behavior was observed. The values
of n0 and n00 have shown to be relatively constant with temperature,
Fig. 4. Temperature dependency of the parameters of the power law model for
storage (G0 ) and loss (G00 ) modules as a function of oscillatory frequency (x). Mean
of three replicates; vertical bars represent the standard deviation in each value;
dashed lines are the models.
287
as expected for the flow behavior index (n; Rao, 1999). It can be
clearly seen in Fig. 4, where the mean values for the n0 and n00
are, respectively, 0.15 and 0.27.
The k0 and k00 values, though, have shown a sigmoidal decay
behavior with temperature, as observed for the yield stress (r0).
As can be seen in Fig. 4, both k0 and k00 showed almost constant val-
ues in the temperature range between 0 and 40 °C. It indicates that
the S. purpurea pulp viscoelastic properties are low dependent of
temperature at this range, reflecting low internal structure
changes. In fact it is the same behavior observed for the yield stress
(r0, Fig. 2). Once more, it is observed that the most important
changes in the k0 and k00 values are carried out between 40 and
60 °C, corroborating the yield stress (r0) discussion. This behavior
could be well modeled by a power sigmoidal function (Eqs. (9) and
(10); R2 > 0.97). It is interesting to observe that, even for k0 and k00 ,
the parameters related to the sigmoidal shape are quite the same
(the proportional and power parameters in temperature). It dem-
onstrates that the decrease in the magnitudes of G0 and G00 in rela-
tion to temperature follows the same trend:
0 299:8
k ¼ ð9Þ
1 þ ð0:018  T C Þ8:52
00 72:17
k ¼ ð10Þ
1 þ ð0:018  T C Þ7:63
The observed behavior is different than those observed in other
products, although there are just few studies which have modeled
the values of k0 , k00 , n0 and n00 as function of temperature.
Ahmed et al. (2007) and Ahmed and Ramaswamy (2006) de-
scribed that the temperature effect was not systematic in the eval-
uation of k0 , k00 , n0 and n00 of baby food (20–80 °C).
Augusto et al. (2011) have modeled the values of n0 and n00 as a
quadratic function (2nd order polynomial function) in relation to
temperature in peach juices with fibers (0–40 °C). The values of
k0 and k00 were modeled using the Arrhenius Equation.
It is important to highlight that the property behavior in rela-
tion to temperature is function not only of the product itself, but
also of the studied temperature range.
3.3. Applicability of the Cox-Merz rule
When the applicability of the Cox-Merz rule was evaluated, it
was not possible to use it straight. As commonly observed in food
products, the complex viscosity (g⁄) magnitudes were always high-
er than the apparent viscosity (ga) magnitudes (Fig. 5).
Although the Cox-Merz rule has been confirmed experimentally
for several polymers dispersions and solutions, in complex systems
as food products it is generally necessary to modify the original
rule (Rao, 2005; Gunasekaran and Ak, 2000). The non-fitting of
the Cox-Merz rule for complex dispersions is attributed to struc-
tural decay due to the extensive strain applied (Ahmed and
Ramaswamy, 2006), presence of high-density entanglements or
to the development of structure and intermolecular aggregation
in solution (Da Silva and Rao, 1992). Thus, the rheological proper-
ties of the S. purpurea pulp differ from those of the polymer solu-
tions and are more similar to structured systems (Ahmed and
Ramaswamy, 2006).
The rheological oscillatory and steady-state shear rheological
properties of foods are generally correlated by modifications to
the Cox-Merz rule (Rao, 2005; Gunasekaran and Ak, 2000). Bistany
and Kokini (1983) have proposed a power modification of the ori-
ginal rule (Eq. (11), which has been used for the evaluation of dif-
ferent food products. Table 5 shows the values for the parameters
of this modified Cox-Merz rule for S. purpurea pulp, with R2 always
higher than 0.96:
288 P.E.D. Augusto et al. / Journal of Food Engineering 108 (2012) 283–289

3.4. General discussion

As consumer demand for native and exotic products is growing,

Fig. 5. Oscillatory and steady-state shear rheological properties of S. purpurea L.
pulp at 0 and 80 °C. Complex viscosity (g⁄) as function of oscillatory frequency (x)
(white symbols); and apparent viscosity (ga) as function of shear rate (c_ ) (black
symbols).
Table 5
Values for the parameters of the modified Cox-Merz rule (Eq. (11)) for S. purpurea L.
pulp.
it is necessary to conduct scientific studies in order to better
understand their processing and properties.
The rheological characterization of fruit pulps and juices is
essential for their processing and product design and optimization.
We highlighted the need for carry other works related with phys-
ical properties of those fruit products.
The present work has evaluated the rheological properties of a
commercial siriguela (S. purpurea L.) pulp as function of tempera-
ture. The product flow behavior was described by the Herschel–
Bulkley’s model. The siriguela pulp viscoelastic behavior was de-
scribed as a weak gel, and its storage and loss modules were de-
scribed using a power function of the oscillatory frequency. A
power modified Cox-Merz rule was used for describe the pulp rhe-
ology, i.e., it was shown that the pulp rheological properties can be
determined by either oscillatory or steady-state shear
experiments.
The obtained data are potentially useful for future studies on
food properties and process design. However, other studies are
needed for understanding the influence of each unit operation
(as pulping or thermal processing) on the siriguela (S. purpurea
L.) pulp rheological pulp.

T (°C) a b R2 4. Conclusions
0 1.417 0.109 0.99
20 1.317 0.220 0.99 The present work has evaluated the steady and dynamic shear
40 1.216 0.492 0.99
rheological properties of siriguela (S. purpurea L.) pulp as function
60 2.101 0.072 0.96
80 2.166 0.037 0.96 of temperature. The product flow behavior could be well described
by the Herschel–Bulkley’s model, whose parameters were modeled
as function of temperature. The storage and loss modules could be
well described by a power function of the oscillatory frequency,
b  ½ga ðcÞa ¼ g  ðxÞjc_ ¼x ð11Þ
whose parameters were modeled as function of temperature.
It can be seen that the obtained values are in accordance to Moreover, a power modified Cox-Merz rule could describe the rhe-
those described by other fruit products as potato puree, fruit based ological properties of S. purpurea pulp. The obtained data is poten-
baby foods, ketchup and tamarind juice (Table 6), although S. pur- tially useful for future studies on food properties and process
purea pulp b values are proportionally small. In the evaluated mod- design.
ified Cox-Merz rule, the b value is related to the magnitude
difference between the apparent (ga) and the complex (g⁄) viscos- Acknowledgments
ities, while the a value is related to the behavior difference. Thus,
the small b values indicate that both S. purpurea pulp apparent The authors thank the São Paulo Research Foundation (FAPESP)
(ga) and the complex (g⁄) viscosities magnitudes are closed, which for funding Project No. 2010/05241-8.
in fact can be seen in Fig. 5. Moreover, as observed by Ahmed et al.
(2007) and Alvarez et al. (2004), the values of a and b have not
shown a particular trend in relation to temperature. References
The obtained results indicate that the rheological properties of
Ahmed, J., Ramaswamy, H.S., 2006. Viscoelastic and thermal characteristics of
S. purpurea pulp can be determined by either oscillatory or stea- vegetable puree-based baby foods. Journal of Food Process Engineering 29, 219–
dy-state shear experiments. 233.
Ahmed, J., Ramaswamy, H.S., Hiremath, N., 2005. The effect of high pressure
treatment on rheological characteristics and color of mango pulp. International
Journal of Food Science & Technology 40 (8), 885–895.
Table 6 Ahmed, J., Ramaswamy, H.S., Sashidhar, K.C., 2007. Rheological characteristics of
Values for the parameters of the modified Cox-Merz rule (Eq. (11)) for fruit products. tamarind (Tamarindus indica L.) juice concentrates. LWT-Food Science and
Technology 40, 225–231.
Product T (°C) a b References Akbulut, M., Çoklar, H., Özen, G., 2008. Rheological characteristics of Juniperus
S. purpurea L. 0–80 1.22–2.17 0.04–0.49 Present work drupacea fruit juice (pekmez) concentrated by boiling. Food Science and
pulp Technology International 14 (4), 321–328.
Alvarez, M.D., Fernández, C., Canet, W., 2004. Rheological behavior of fresh and
Potato puree 25–65 0.90–1.35 2.15–39.83 Alvarez et al. (2004)
frozen potato puree in steady and dynamic shear at different temperatures.
Apple baby 5–80 1.15–1.20 4.64–6.99 Ahmed et al. (2007)
European Food Research Technology 218, 544–553.
food
Augusto, F., Valente, A.L.P., Tada, E.S., Rivellino, S.R., 2000. Screening of Brazilian
Apricot baby 5–80 1.16–1.44 0.41–1.26 Ahmed et al. (2007) fruit aromas using solid-phase microextraction–gas chromatography–mass
food spectrometry. Journal of Chromatography A 873, 117–127.
Banana baby 5–80 1.15–1.33 1.91–11.80 Ahmed et al. (2007) Augusto, P.E.D., Falguera, V., Cristianini, M., Ibarz, A., in press-a. Rheological
food behavior of tomato juice: steady-state shear and time-dependent modeling.
Ketchup 25 0.94 13.97 Bistany, Kokini (1983) Food and Bioprocess Technology. doi:10.1007/s11947.010.0472.8.
Tamarind 10–90 0.67–1.06 0.86–30.82 Ahmed et al. (2007) Augusto, P.E.D., Falguera, V., Cristianini, M., Ibarz, A., 2011. Influence of fiber
juice addition on the rheological properties of peach juice. International Journal of
Food Science and Technology 46, 1086–1092.
 P.E.D. Augusto et al. / Journal of Food Engineering 108 (2012) 283–289
Augusto, P.E.D., Falguera, V., Cristianini, M., Ibarz, A., in press-b. Viscoelastic
properties of tomato juice: applicability of the Cox–Merz Rule. Food and
Bioprocess Technology, (doi:10.1007/s11947-011-0655-y).
Barbana, C., El-Omri, A., in press. Viscometric behavior of reconstituted tomato
concentrate. Food and Bioprocess Technology. doi: 10.1007/s11947-009-0270-3.
Bayod, E., Månsson, P., Innings, F., Bergenståhl, B., Tornberg, E., 2007. Low shear
rheology of concentrated tomato products. Effect of particle size and time. Food
Biophysics 2, 146–157.
Bayod, E., Willers, E.P., Tornberg, E., 2008. Rheological and structural
characterization of tomato paste and its influence on the quality of ketchup.
LWT-Food Science and Technology 41, 1289–1300.
Bhattacharya, S., 1999. Yield stress and time-dependent rheological properties of
mango pulp. Journal of Food Science 64 (6), 1029–1033.
Bicas, J.L., Molina, G., Dionisio, A.P., Barros, F.F.C., Wagner, R., Marostica Jr., M.R.,
Pastore, G.M., 2011. Volatile constituents of exotic fruits from Brazil. Food
Research International 44, 1843–1855.
Bistany, K.L., Kokini, J.L., 1983. Dynamic viscoelastic properties of foods in texture
control. Journal of Rheology 27 (6), 605–620.
Canet, W., Alvarez, M.D., Fernández, C., Luna, P., 2005. Comparisons of methods for
measuring yield stresses in potato puree: effect of temperature and freezing.
Journal of Food Engineering 68, 143–153.
Ceva-Antunes, P.M.N., Bizzo, H.R., Silva, A.S., Carvalho, C.P.S., Antunes, O.A.C., 2006.
Analysis of volatile composition of siriguela (Spondias purpurea L.) by solid
phase microextraction (SPME). LWT-Food Science and Technology 39, 436–442.
Da Silva, J.A.L., Rao, M.A., 1992. Viscoelastic Properties of Food Hydrocolloid
Dispersions. In: Rao, M.A., Steffe, J.F. (Eds.), Viscoelastic Properties of Foods.
Elsevier Science Publishers Ltd., London.
Dak, M., Verma, R.C., Jaaffrey, S.N.A., 2008. Rheological properties of tomato
concentrate. International Journal of Food Engineering 4 (7) (article11).
Furtado, G., Silva, F., Porto, F.S., Santos, A.G., 2010. Secagem de polpa de ceriguela
pelo método de camada de espuma. Revista Brasileira de Produtos
Agroindustriais 12 (1), 9–14.
Genovese, D.B., Rao, M.A., 2005. Components of vane yield stress of structured food
dispersions. Journal of Food Science 70, E498–E504.
Gunasekaran, S., Ak, M.M., 2000. Dynamic oscillatory shear testing of foods –
Selected applications. Trends in Food Science and Technology 11, 115–127.
Haminiuk, C.W.I., Sierakowski, M.R., Maciel, G.M., Vidal, R.M.B., Branco, I.G., Masson,
M.L., 2006. Rheological properties of butia pulp. International Journal of Food
Engineering 2 (1). Article 4.
Ibarz, A., Barbosa-Cánovas, G.V., 2003. Unit Operations in Food Engineering. CRC
Press, Boca Raton.
289
Martins, L.P., Silva, S.M., Alves, R.E., Filgueiras, H.A.C., 2003. Fisiologia do dano pelo
frio em ciriguela (Spondias purpurea L.). Revista Brasileira de Fruticultura 25 (1),
23–26.
Massa, A., González, C., Maestro, A., Labanda, J., Ibarz, A., 2010. Rheological
characterization of peach purees. Journal of Texture Studies 41, 532–548.
Parada, R.Y., Castro, S., Serrano, R.D., Castillo, B.E., Ayala, J., Vides, E., Romero, J.,
2006. First report of a phytoplasma associated with Spondias purpurea (Jocote
de Corona) in El Salvador. Journal of General Plant Pathology 72 (1), 40–42.
Pereira, E.A., Brandão, E.M., Borges, S.V., Maia, M.C.A., 2007. Effect of xanthan gum
addition on the rheological properties of umbu fruit pulp. Boletim do CEPPA 25
(2), 285–294.
Pereira, E.A., Brandão, E.M., Borges, S.V., Maia, M.C.A., 2008. Influence of
concentration on the steady and oscillatory shear behavior of umbu pulp.
Revista Brasileira de Engenharia Agrícola e Ambienta 12 (1), 87–90.
Rao, M.A., 1999. Flow and Functional Models for Rheological Properties of Fluid
Foods. In: Rao, M.A. (Ed.), Rheology of Fluid and Semisolid Foods: Principles and
Applications. Aspen Publishers, Gaithersburg.
Rao, M.A., 2005. Rheological Properties of Fluid Foods, 3rd ed.. In: Rao, M.A., Rizvi,
S.S.H., Datta, A.K. (Eds.), Engineering Properties of Foods. CRC Press, Boca Raton.
Sampaio, S.A., Bora, P.S., Holschuh, H.J., 2008. Postharvest respiration and
maturation of some lesser-known exotic fruits from Brazil–ciriguela (Spondias
purpurea L.). Revista Ceres 55 (2), 141–145.
Sato, A.C.K., Cunha, R.L., 2007. Influência da temperatura no comportamento
reológico da polpa de jabuticaba. Ciência e Tecnologia de Alimententos 27 (4),
890–896.
Sato, A.C.K., Cunha, R.L., 2009. Effect of particle size on rheological properties of
jaboticaba pulp. Journal of Food Engineering 91, 566–570.
Sun, A., Gunasekaran, S., 2009. Yield stress in foods: measurements and
applications. International Journal of Food Properties 12, 70–101.
Tabilo-Munizaga, G., Barbosa-Cánovas, G.V., 2005. Rheology for the food industry.
Journal of Food Engineering 67, 147–156.
Tonon, R.V., Alexandre, D., Hubinger, M.D., Cunha, R.L., 2009. Steady and dynamic
shear rheological properties of açai pulp (Euterpe oleraceae Mart.). Journal of
Food Engineering 92, 425–431.
Valencia, C., Sánchez, M.C., Ciruelos, A., Latorre, A., Franco, J.M., Gallegos, C., 2002.
Linear viscoelasticity of tomato sauce products: influence of previous tomato
paste processing. European Food Research Technology 214, 394–399.
Yoo, B., Rao, M.A., 1996. Creep and dynamic rheological behavior of tomato
concentrates: effect of concentration and finisher screen size. Journal of Texture
Studies 27, 451–459.