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Journal of Food Engineering 78 (2007) 978–983

www.elsevier.com/locate/jfoodeng

Use of the generalized Maxwell model for describing


the stress relaxation behavior of solid-like foods
a,b,*
M.A. Del Nobile , S. Chillo b, A. Mentana b, A. Baiano b

a
Department of Food Science, University of Foggia, Via Napoli, 25-71100 Foggia, Italy
b
Istituto per la Ricerca e le Applicazioni Biotecnologiche per la Sicurezza e la Valorizzazione dei Prodotti Tipici e di Qualità,
Università degli Studi di Foggia, Via Napoli, 25-71100 Foggia, Italy

Received 5 March 2005; accepted 2 December 2005


Available online 2 February 2006

Abstract

A comprehensive study on the ability of the generalized Maxwell model to describe the stress relaxation behavior of food matrices is
presented in this work. Five different food matrices were chosen as representative of a wide range of foods: agar gel, meat, ripened cheese,
‘‘mozzarella’’ cheese and white pan bread. The above foods matrices were selected on the base of their macro-structure and compressive
stress strain behavior. Stress relaxation tests were run on the above food matrices at room temperature. The relaxation times distribution
function used in this investigation to describe the viscoelastic behavior of the investigated foods was obtained by summing two normal
distribution functions with the means equal to zero. Results show that the proposed model satisfactorily fits the experimental data. More-
over, it was also found a substantial difference between the relaxation times distribution curves of the investigated bulky and spongy
foods.
 2005 Elsevier Ltd. All rights reserved.

Keywords: Modeling; Generalized maxwell model; Stress relaxation; Mechanical properties

1. Introduction force is removed, the material could remain permanently


deformed.
Food products are complex matrices showing a wide To quantitatively determine the viscoelastic behavior of
range of different mechanical behaviors (Gunasekaran & a matrix, transient (quasi-static) and dynamic tests can be
Mehmet, 2000) even if some of them could be described performed. The more typical transient tests are represented
with a certain approximation on the base of simplified by creep and stress relaxation experiments. In creep tests, a
models such as the ideal solid (elastic), the ideal liquid (vis- constant stress is applied to a specimen and the corre-
cous), the ideal plastic (elastic properties below a specific sponding strain is measured as a function of time. The
applied stress and viscous behavior above this value) and considered parameters are the ‘‘compliance’’ (that is the
combination of two or more of them. Most food products strain–stress ratio) and the ‘‘relaxation time’’. In stress
are neither pure liquids nor pure solids, simultaneously relaxation tests, a constant strain is applied and the stress
showing viscous and elastic behaviors. For instance, when required to maintain the deformation is measured as a
a force is applied to a viscoelastic food matrix it needs a function of time. When a stress relaxation test is per-
certain time to acquire its new dimensions and, when the formed, different behaviors can be observed: ideal elastic
materials do not relax whereas ideal viscous materials
*
instantaneously show a relaxation. Viscoelastic solids grad-
Corresponding author. Address: Department of Food Science, Uni-
versity of Foggia, Via Napoli, 25-71100 Foggia, Italy. Tel.: +39 881 589
ually relax and reach an equilibrium stress greater than 0,
242; fax: +39 881 740 211. whereas for viscoelastic fluids, instead, the residual stress
E-mail address: ma.delnobile@unifg.it (M.A. Del Nobile). vanishes to zero (Steffe, 1992). The dynamic experiments

0260-8774/$ - see front matter  2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jfoodeng.2005.12.011
M.A. Del Nobile et al. / Journal of Food Engineering 78 (2007) 978–983 979

differ from transient tests because a sinusoidal stress or Hookes body and two Maxwell’s bodies (Lachowicz, Sobc-
strain is applied instead of a constant stress or strain. zak, Gajowiecki, & Zych, 2003). The compression stress
In order to describe the viscoelastic behavior of a mate- relaxation data obtained for potatoes exposed to pulsified
rial, massless mechanical models are used. These models electric field were modeled with a five parameter general-
are composed of springs (considered ideal solids, they ized Maxwell model (Finca & Dejmek, 2003). Hassa
account for the elastic behavior of viscoelastic materials) et al. (2005) compared three popular stress relaxation mod-
and dashpots (representing ideal fluids, they account for els, namely the generalized Maxwell, Nussinovitch, and
the viscous behavior) combined in many different ways. Peleg model, in order to describe the viscoelastic properties
Three are the most commonly mechanical analogs used: of eight date cultivars at their khalal (balah) and rutab
the Kelvin–Voigt model, the Maxwell model (Bruno & stages of maturity. They found that all considered models
Moresi, 2004; Correia & Mittal, 2002), and the standard were valid for quantifying the relaxation behavior of the
linear solid one. products but the generalized Maxwell model was the best
The Kelvin–Voigt model, composed of a spring and a in predicting experimental data.
dashpot in parallel, represents the start point for the devel- The standard linear solid model, also called Zener
opment of mechanical analogs describing the creep behav- model, can consist in two different mechanical analogs: a
ior. In fact, the Kelvin model is not sufficient to describe spring in series with a Kelvin model or a spring in parallel
creeps in biological materials that are better modeled by with a Maxwell model.
the Burgers model (a Kelvin and a Maxwell element in ser- In addition to the used model, the equilibrium modulus,
ies) (Steffe, 1992). A model consisting of one Maxwell ele- the decay modulus, time of relaxation, and specific viscos-
ment in series with two Kelvin–Voight elements is able to ity in the relaxation model are affected by the specimen ori-
describe a liquid-like viscoelastic behavior (Mitchell & entation and its location with the product (Wang, 2003).
Blanshard, 1976). In this study the possibility to use the generalized
Stress relaxation data are very importance since they Maxwell model for describing the stress relaxation behav-
supply information about phenomena involving food prod- ior of food matrices is addressed. Five different food matri-
ucts such as fruit ripening (Hassa, Alhamdan, & Elansari, ces were selected with the criteria to be representative of a
2005), fruit firmness (Blahovec, 1996), staling of cereal wide class of foods. Stress relaxation tests were run at room
products (Limanond, Castell-Perez, & Moreira, 2002), temperature and the posed model was fit to the experimen-
checking phenomenon (Kim & Okos, 1999). tal data to establish if the generalized Maxwell model can
The Maxwell model, consisting of a Hookean spring be used to describe the viscoelastic behavior of foods.
and a Newtonian dashpot in series (Mohsenin & Mittal,
1977), is suitable for understanding stress relaxation data, 2. Materials and methods
but does not consider the equilibrium stress. For this rea-
son, the viscoelastic behavior of food can be better Five different matrices were selected as representative of
described by using a generalized Maxwell model consisting a wide class of food products: agar gel and four commer-
of several elements in parallel with a spring (Steffe, 1992). cially available foods such as ‘‘mozzarella’’ cheese, meat,
In a similar model, if the system is subjected to a constant ripened cheese and white pan bread. The mean composi-
strain, the total stress is the sum of the stress of each ele- tion for each of the considered products (Carnovale &
ment. Since each element may have a different relaxation Marletta, 1997) is reported below:
time, a relaxation spectra can be obtained for a viscoelastic
material. Models containing more exponential components ‘‘mozzarella cheese’’—water 58.8%, proteins 18.7%, lip-
and a residual terms have been used to describe the stress ids 19.5%, sugars 0.7%, mineral salts and vitamins;
relaxation behavior of Cheddar cheese (Hort, 1997) and meat (beef)—76.9% water, proteins 20.7%, lipids 1.0%,
‘‘pasta filata’’ cheese (Masi, 1989). Mancini, Moresi, and mineral salts;
Rancini (1999) were able to describe the viscoelastic behav- ripened cheese—water 31.5%, proteins 33.9%, lipids
ior of several alginate gels differing for the effective alginate 28.5%, sugars 3.7%, mineral salts and vitamins;
concentration by means of a generalized Maxwell model white pan bread—water 33.5%, proteins 9%, lipids 8.7%,
consisting of five elements. A model including one spring sugars 48.2%, mineral salts and vitamins.
and two Maxwell elements was successfully use to describe
the stress relaxation of lipids such as beeswax, candelilla The preparation of the food matrices, performed imme-
wax, carnauba wax and a high-melting milkfat fraction diately before dynamic-mechanical analyses, consisted in
(Shellhammer, Rumsey, & Krochta, 1997). Limanond cutting 13 mm-diameter specimens by means of a cylindri-
et al. (2002) modeled the kinetics of corn tortilla staling cal mould. The external portion of each cylindrical sample
through stress relaxation data and found that a seven- was covered with some grease to avoid dehydration during
element generalized Maxwell model fits the data better the dynamic-mechanical analysis.
than the three and five ones. The viscoelastic properties Agar gel was prepared by dissolving agar (Oxoid, Milan,
of some pork ham muscles were better fitted to a general- Italy) in distilled water (final concentration 1.0% w/v). The
ized Maxwell model consisting of a parallel coupling of a obtained solution was then heat treated at 121 C for
980 M.A. Del Nobile et al. / Journal of Food Engineering 78 (2007) 978–983

15 min. Cylindrical specimens (11 mm-diameter) were ria of choosing food matrices representative of a wide
obtained by injection in a mould and cooling at room tem- range of foods. In fact, three food matrices were selected
perature. Before analyses, these specimen were refrigerated as representative of bulky foods (that is, agar, meat and
at 4 C for 2 h. Gels represent good systems for basic rhe- ripened cheese); whereas, the other two were chosen as rep-
ological studies since they are usually isotropic and resentative of spongy foods (that is, white pan bread and
homogeneous. ‘‘mozzarella’’ cheese). Fig. 1 shows the stress–strain curves
relative to the investigated bulky foods, whereas Fig. 2
2.1. Elastic modulus determination shows the stress–strain curves relative to the investigated
spongy foods. The curves shown in the figures are the best
The investigated food matrices were submitted to com- fit of Eq. (1) to the experimental data. As expected the con-
pression tests by means of a dynamic mechanical analyser cavity of the stress–strain curve is positive for the bulky
(DMA-Q 800, TA Instruments, New Castle, DE, USA) food matrices whereas a downward concavity was found
equipped with parallel plates (B15 mm) to obtain the for the stress–strain curves of the spongy foods. In fact,
stress–strain curves. Tests were carried out at room temper- spongy foods are more elastic than the bulky ones, due
ature according to the following conditions. Preload force: to the presence of pores containing gas instead of intersti-
104 N for agar; 103 N for mozzarella, ripened cheese tial spaces containing fluids that, for the effects of the com-
and white pan bread; 102 N for meat. Crosshead speed: pression, definitively leave the sample. The values of the
0.5 N/min for agar and mozzarella; 1 N/min for meat, rip- elastic modulus obtained according to the procedure
ened cheese and white pan bread. The elastic modulus reported above are listed in Table 1. As can be inferred
could be evaluated from the initial slope of the stress–strain
curve. However, since the samples surfaces are not per-
fectly parallel, the estimation of the storage modulus is
generally affected by an error that might be quite signifi-
cant. For this reason, a mathematical model capable to
describe the entire stress–strain curve was used:
rT ðeT Þ ¼ EC  eT  expðeT  KÞ ð1Þ
where eT and rT (MPa) are the true strain and the true
stress, respectively (Mancini et al., 1999), EC (MPa) is the
elastic modulus (i.e., the tangent to the stress strain curve
at the origin), K is a constant and have to be regarded as
fitting parameter.

2.2. Stress relaxation tests

Compression tests were also performed in order to eval- Fig. 1. Compressive stress strain test conducted at room temperature: (s)
agar; (n) meat; (h) cheese. The curves shown in the figure were obtained
uate the stress relaxation behavior of the chosen five matri- by fitting Eq. (1) to the experimental data. (—–) agar; (- - - -) meat; (— —)
ces. Tests were carried out at room temperature according ripened cheese.
to the following conditions. Preload force: 104 N for agar;
103 N for mozzarella, meat, ripened cheese and white pan
bread. Instantaneous strain: 6.0% for mozzarella and white
pan bread; 6.5% for agar; 7.5% for meat and ripened
cheese. Relaxation time: 10 min. The stress relaxation value
was calculated as the time-dependent stress divided by the
constant strain.
All the tests were replicated three times, thus the mean
values and the corresponding standard deviations are
reported in the following.

3. Results and discussion

3.1. Food matrices selection

As reported above the suitability of the generalized


Fig. 2. Compressive stress strain test conducted at room temperature: ()
Maxwell model to be used to describe the stress relaxation ‘‘mozzarella’’ cheese; (j) white pan bread. The curves shown in the figure
behavior of foods was addressed by using five different were obtained by fitting Eq. (1) to the experimental data. (—–)
food matrices. The selection was carried out with the crite- ‘‘mozzarella’’ cheese; (- - - -) white pan bread.
M.A. Del Nobile et al. / Journal of Food Engineering 78 (2007) 978–983 981

Table 1
Elastic modulus and relaxation times distribution curve parameters of the investigated food matrices
EC (MPa) d1 G1 (MPa) d2 G2 (MPa)
3 4 3 3
Agar 13.7 · 10 (5.66 · 10 ) 80.6 (34.4) 12.9 · 10 (7.52 · 10 ) 1820 (614) 20.1 · 103 (2.47 · 103)
Meat 6.49 · 103 (5.69 · 105) 45.0 (7.11) 1.18 · 103 (4.95 · 104) 1490 (628) 2.01 · 103 (6.99 · 104)
Ripened cheese 0.102 (0.0293) 30.4 (9.82) 0.464 (0.0469) 1190 (262) 0.740 (0.164)
‘‘Mozzarella’’ cheese 11.9 · 103 (1.44 · 103) 17.2 (6.10) 12.7 · 103 (2.17 · 103) 197 (42.3) 15.3 · 103 (2.73 · 103)
White pan bread 19.6 · 103 (3.39 · 103) 5.57 (2.11) 5.44 · 103 (2.12 · 103) 315 (47.4) 20.6 · 103 (6.45 · 103)

from this table, the elastic modulus values of the investi- decrease in the stress after which the stress level off to con-
gated food span in a wide range of values, corroborating stant value. This behavior was in accord with that found by
the idea that the selected group of foods can be indeed con- Mancini et al. (1999), who pointed out an asymptotically
sidered as representative of a wide range of food matrices. decaying trend for the alginate gels tested. As can be
inferred from the above figures, the final stress values
3.2. Stress relaxation tests obtained for spongy matrices (‘‘mozzarella’’ cheese and
white pan bread) were lower than those calculated for
As reported in the literature (Rosen, 1982) the general- bulky materials. The curves shown in the above figure were
ized Maxwell model is given by the following expression: obtained by fitting Eq. (4) to the experimental data. As can
Z 1  t be inferred from the data shown in Figs. 3–5 the general-
rðtÞ
EðtÞ ¼ ¼ EðkÞ  exp   dk ð2Þ ized Maxwell model excellently fits the experimental data.
e0 0 k
where E(t) (MPa) is the elastic modulus at time t(s), r(t)
(MPa) is the stress at time t(s), e0 is the imposed strain,
E(k) (MPa) is the continuous distribution function of relax-
ation times, k(s) is the relaxation time. In principle any
expression can be used for describing the continuous distri-
bution function of relaxation times, in this investigation the
following expression was used:
( "   2 #)
1 1 k
EðkÞ ¼ G1  pffiffiffiffiffiffiffiffiffi exp  
d1  2  p 2 d 1
( "   2 #)
1 1 k
þ G2  pffiffiffiffiffiffiffiffiffi exp   ð3Þ
d2  2  p 2 d2

Eq. (3) was obtained by summing two normal distribu-


tion functions with the means equal to zero and a standard
deviations equal to di, each of which was multiplied by a Fig. 3. Compressive stress plotted as a function of time in a stress
constant (Gi). The parameters appearing in Eq. (3) account 
relaxation test conducted at room temperature. ( ) agar, (}) ‘‘mozza-
for the height (Gi) and wideness (di) of the relaxation time rella’’ cheese, (j) white pan bread.
distribution curves. By substituting Eq. (3) in Eq. (2) the
following expression is obtained:
Z 1 ( "  2 #)
1 1 k
EðtÞ ¼ G1  pffiffiffiffiffiffiffiffiffi exp  
0 d 1  2  p 2 d 1
Z (
 t 1
1
 exp   dk þ G2  pffiffiffiffiffiffiffiffiffi
k 0 d2  2  p
"  2 #)
1 k  t
 exp    exp   dk ð4Þ
2 d2 k

The quadrature of a function such as that appearing in


Eq. (4) was made by using the extended Simpson’s rule
(Press, Flannery, Teukolsky, & Vetterling, 1989, Chapter
4).
Figs. 3–5 show the stress relaxation texts for the five Fig. 4. Compressive stress plotted as a function of time in a stress
investigated foods. As expected there is first a sharp relaxation test conducted at room temperature on meat samples.
982 M.A. Del Nobile et al. / Journal of Food Engineering 78 (2007) 978–983

Fig. 5. Compressive stress plotted as a function of time in a stress Fig. 7. The relaxation times distribution curve of meat.
relaxation test conducted at room temperature on ripened cheese samples.

The values of the parameters appearing in Eq. (4) are listed


in Table 1. Bulky and spongy foods particularly differed
each other for the di values that were higher for the first
ones.
The values of the generalized Maxwell model’s parame-
ters listed in Table 1 were used to calculate the relaxation
time distribution curve for the investigated foods, the
results are shown in Figs. 6–9. As can be inferred from
the above figures for each of the investigated foods the con-
tinuous distribution curve of relaxation times is given by
the superposition of two well districted contributions: the
first part describe the short time response of the food matri-
ces, and is narrow and high; the second describe the long
time response of the food matrices, and is wide and low. Fig. 8. The relaxation times distribution curve of ripened cheese.
As one would expect the relaxation times distribution curve
strongly depends on the food structure. In fact, for spongy
foods, such as ‘‘mozzarella’’ cheese and white pan bread,
the relaxation times distribution curve vanish to zero at
relaxation time ranging between 600 and 1000 s; whereas,
for bulky food matrices, such as meat, ripened cheese
and agar, the relaxation times distribution curve vanish
to zero at relaxation time ranging between 2000 and

Fig. 9. The relaxation times distribution curve of (—–) ‘‘mozzarella’’


cheese and (- - - -) white pan bread.

5000 s. Since spongy foods are more elastic than the bulky
ones, the release of the stress is faster in the former than in
the latter. If the applied strain is not higher than the critical
strain, spongy foods recover the initial shape whereas
bulky foods show a permanent deformation. Indepen-
dently from food structure, stress relaxation of high mois-
Fig. 6. The relaxation times distribution curve of agar. ture foods such as ‘‘mozzarella’’ cheese, meat and agar gel
M.A. Del Nobile et al. / Journal of Food Engineering 78 (2007) 978–983 983

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