Upload
julio-mauricio-vidaurre-ruiz
View
219
Download
0
Embed Size (px)
Citation preview
8/12/2019 Vida Util Harina Yuca Permeabilidad Empaque
1/7
Shelf life prediction of packaged cassava-flour-based baked product
by using empirical models and activation energy for water vapor
permeability of polyolefin films
Ratchaneewan Kulchan a, Waraporn Boonsupthip b, Panuwat Suppakul c,*
a Thai Packaging Centre, Thailand Institute of Scientific and Technological Research, 196 Phaholyothin Rd., Ladyao, Chatuchak, Bangkok 10900, Thailandb Department of Food Science and Technology (Food Engineering Major), Faculty of Agro-Industry, Kasetsart University, 50 Phaholyothin Rd., Ladyao,
Chatuchak, Bangkok 10900, Thailandc Department of Packaging and Materials Technology, Faculty of Agro-Industry, Kasetsart University, 50 Phaholyothin Rd., Ladyao, Chatuchak, Bangkok 10900, Thailand
a r t i c l e i n f o
Article history:
Received 14 February 2010
Received in revised form 18 April 2010
Accepted 20 April 2010
Available online xxxx
Keywords:
Cassava-flour-based baked product
Moisture sorption
Empirical model
Activation energy
Shelf life
Packaging
a b s t r a c t
Moisture sorption kinetics and isotherms of cassava-flour-based baked product were investigated. Empir-
ical models were testedto fit the experimental data. Texturalchanges of the product were investigated. In
addition, activation energies (Ep) for water vapor permeability (WVP) of polyolefin films were deter-
mined. Finally, the product was packaged in low-density polyethylene (LDPE) or oriented polypropylene
(OPP) pouches, and stored at 30 1 C and 50 2% RH to simulate actual storage conditions and to deter-
mine shelf life. This actual shelf life was compared to the predicted shelf life by using empirical models
and Epfor WVP. Moisture sorption kinetics was more rapid during the initial stage, while a lesser amount
of moisture was adsorbed as adsorption time increased. The higher the relative humidity used, the more
pronounced the effect. Thesigmoidal moisturesorption isotherms of this product canbe classified as type
II. The GAB model was found to be the best-fit model for this product. Once the product hardness or work
reached the maximum and began to reduce at moisture content (MC) 6%, the product texture began to
be detectedas becomingslightly soft. This implies that hardness andwork at themaximumlevel could beused to identify the critical MC which causes a loss of crispness to an unacceptable degree. The predicted
shelf lives estimated by employingEpfor WVP of LDPE and OPP, and the GAB model were close to the
actual shelf lives. Therefore, the estimation by empirical models and activation energy was found to be
applicable for rapid and accurate shelf life prediction.
2010 Elsevier Ltd. All rights reserved.
1. Introduction
Cassava (Manihot esculentaCrantz) flour is used as a key ingre-
dient in several dry crisp products such as potato chips and puffed
curls. In addition, Asian and Latin American peoples are interested
in its use as a partial substitute for wheat flour (Lopez et al., 2004;
Mohamed et al., 2006). To consumers, high crispness of such prod-
ucts indicates not only good quality but also freshness (Rohm,
1990). Unfortunately, few study results have been reported on
the creation and preservation of crispness for cassava-based flour
products (Chang et al., 2000). Such research has been especially
rare for multi-component systems.
Sorption characteristics of cassava-flour-based baked products
are crucial for the design, modeling and optimization of their
drying, packaging, storage and transport. Knowledge of sorption
isotherms is also important for predicting moisture sorption
properties of highly sensitive food products via empirical models.
These isotherms provide information on the moisture-binding
capacity of products at a determined relative humidity, and are a
useful means for analyzing the moisture plasticizing effect and
the effect on textural properties (Bell and Labuza, 2000; Al-Muh-
taseb et al., 2002). Chirife and Iglesias (1978) reviewed 23 isotherm
models and their use for fitting sorption isotherms of foods and
food products. None of these models accurately described the sorp-
tion isotherm over the entire range of relative humidity, since
water is related to the food matrix by different mechanisms in dif-
ferent activity regions. However, these kinetic models are still
important for use in the prediction of moisture sorption properties
of foodstuffs.
In the texture study, crispness was perceived as a combination
of the sound generated and the fracture of the product as it was
bitten completely through with the back molars (Duizer et al.,
1998). Different instrumental and sensory approaches have been
applied to study this quality attribute, and have generated a large
amount of experimental data (Roudaut et al., 2002). Unfortunately,
0260-8774/$ - see front matter 2010 Elsevier Ltd. All rights reserved.doi:10.1016/j.jfoodeng.2010.04.031
* Corresponding author. Tel.: +66 2 562 5058; fax: +66 2 562 5047.
E-mail address: [email protected](P. Suppakul).
Journal of Food Engineering xxx (2010) xxxxxx
Contents lists available at ScienceDirect
Journal of Food Engineering
j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / j f o o d e n g
ARTICLE IN PRESS
Please cite this article in press as: Kulchan, R., et al. Shelf life prediction of packaged cassava-flour-based baked product by using empirical models and
activation energy for water vapor permeability of polyolefin films. Journal of Food Engineering (2010), doi: 10.1016/j.jfoodeng.2010.04.031
http://dx.doi.org/10.1016/j.jfoodeng.2010.04.031mailto:[email protected]://www.sciencedirect.com/science/journal/02608774http://www.elsevier.com/locate/jfoodenghttp://dx.doi.org/10.1016/j.jfoodeng.2010.04.031http://dx.doi.org/10.1016/j.jfoodeng.2010.04.031http://www.elsevier.com/locate/jfoodenghttp://www.sciencedirect.com/science/journal/02608774mailto:[email protected]://dx.doi.org/10.1016/j.jfoodeng.2010.04.0318/12/2019 Vida Util Harina Yuca Permeabilidad Empaque
2/7
no conclusion can be soundly drawn for the relationship between
instrumental and sensory results. This is due to the fact that many
definitions of crisp were applied (Roudaut et al., 2002), and only
a few studies of sensory data have been reported to the public
(Hecke et al., 1995; Roudaut et al., 2002). The crispness of dry crisp
products is controlled by product composition and structure
(Roudaut et al., 2002). Process conditions affect the final moisture
content which governs crispness of the finished product ( Roudaut
et al., 2002). During storage, water adsorption from the atmo-
sphere or by mass diffusion from neighboring components can also
cause a loss of crispness (Nicholls et al., 1995).
Moisture-sensitive products may absorb moisture during long-
term storage, as the commonly used packaging materials are per-
meable to moisture. Moisture content can be used as the critical
data for judging the quality of products that have been degraded
by moisture. Water vapor permeability of packaging materials is
one of the important criteria for predicting the rate of moisture up-
take (Chen and Li, 2003). Recently there has been increased inter-
est in the development of a mathematical model for optimization
of flexible film packaging of moisture-sensitive foods (Del Nobile
et al., 2003; Azanha and Faria, 2005; Araromi et al., 2008; Siripatr-
awan, 2009).
This study is aimed at: (1) investigating the moisture sorption
kinetics and empirically modeling the moisture sorption isotherm
of cassava-flour-based baked product; (2) determining a critical
water activity of cassava-flour-based baked product based on
mechanical and sensory approaches; and (3) determining the acti-
vation energy for water vapor permeability of polyolefin films, and
applying this to the predicted shelf life of moisture-sensitive food
products.
2. Materials and methods
2.1. Sample preparation
A cassava-flour-based baked sample was prepared using cas-
sava flour (55.2%) (Cho Heng Rice Vermicelli Co., Ltd., Nakhon
Pathom, Thailand); coconut milk (18.4%); egg yolk (1.1%); and su-
crose (23%), obtained from various commercial retailers. Firstly, a
mixture of coconut milk and sucrose was heated at 90 C until
40% sample weight loss was reached. The obtained mixture, with
egg yolk and cassava flour then added, was kneaded into dough
using a domestic mixer (KM 410, Kenwood Limited, UK) at a min-
imum speed. The dough was stored in a tightly sealed container at
room temperature overnight. Then the dough, after adding water
(2.3%), was kneaded to obtain homogeneous distribution beforebeing divided roll dough into small balls (1 cmdia) using a
1 cm plain biscuit cutter. The balls were placed on a greased pan
and baked at 150 C for 20 min. After baking, they became porous
and expanded to 1.5 cm dia. The baked products were left to cool,
and kept in a tightly sealed container for further use.
2.2. Proximate analysis
The sample was analyzed for moisture, protein, carbohydrate,
starch, fat, ash and fiber using AOAC methods (Lane, 1998). All
determinations were carried out in triplicate.
2.3. Moisture sorption kinetics and isotherm
A standard gravimetric methodology (weighing samples equili-
brated in thermally stabilized desiccators) was used for determina-
tion of the adsorption kinetics. The baked product was crushed,
and completely dried in a vacuum oven at 70 C and 76 mm Hg
for 48 h, and then in a desiccator over P2O5 for 2 weeks. The driedsamples (in triplicate) were placed into desiccators with saturated
salt solutions at 30 C. The salt solutions included LiCl, MgCl2,
Mg(NO3)2, NaCl, and K2NO3 of known relative humidity (% RH):
11.3, 32.4, 51.4, 75.1, and 92.5% RH, respectively (Greenspan,
1977). Weights of samples as a function of time were measured;
moisture content was then measured by drying in an oven at
105 C for 3 h (Lane, 1998). Set of experiments was performed in
two replications. This was expressed on a dry-weight basis as g
H2O/100 g dry sample. Water activity (aw) was determined using
a water activity instrument (Testo 650, Testo, Inc., Germany). Mois-
ture adsorption curves of the samples were fitted to a mathemat-
ical model suggested byPeleg (1988):
Mt M0 t=k1k2t; 1
where,Mt= moisture after timet;M0= initial moisture; andk1 and
k2= parameters.
A standard gravimetric methodology was used for determina-
tion of the adsorption isotherms. The baked product was prepared
and conditioned, as described in Section2.3. The dried samples in
triplicate were equilibrated over saturated salt solutions inside
desiccators at 30 C for 4 weeks. The salt solutions included LiCl,
CH3COOK, MgCl2, K2CO3, Mg(NO3)2, KI, NaCl, KCl and K2NO3 of
known relative humidity (% RH): 11.3, 21.6, 32.4, 43.2, 51.4, 67.9,
75.1, 83.6 and 92.5, respectively (Greenspan, 1977). Moisture con-
tent was then measured by drying in an oven at 105 C for 3 h
(Lane, 1998). Set of experiments was performed in 4 replications.
This was expressed on a dry-weight basis as g H2O/100 g dry
sample. Water activity was determined using a water activityinstrument.
Nomenclature
A test area (m2)aw water activitya, b, c, d constants of the Peleg modelCB
constant of the BET modelCG,k constants of the GAB model
Ep apparent activation energy of water vapor permeabilityF, G,Hconstants of the Lewicki modelG
weight change (g)k, c constants of the Oswin modelk1, k2 parameters of Peleg kinetic modell thickness (mil)M0 initial moisture content
Mc critical moisture contentMt moisture after time (t)P water vapor permeability coefficient (g mil m2 d1
mmHg1)psat saturated vapor pressure at constant temperature,
mmHgDp vapor pressure difference (mmHg)RH0 relative humidity in test dishRH relative humidity in desiccatorT temperature (K)Tg,m mid-point glass transition temperature (C)t time (d)
2 R. Kulchan et al. / Journal of Food Engineering xxx (2010) xxxxxx
ARTICLE IN PRESS
Please cite this article in press as: Kulchan, R., et al. Shelf life prediction of packaged cassava-flour-based baked product by using empirical models and
activation energy for water vapor permeability of polyolefin films. Journal of Food Engineering (2010), doi:10.1016/j.jfoodeng.2010.04.031
http://dx.doi.org/10.1016/j.jfoodeng.2010.04.031http://dx.doi.org/10.1016/j.jfoodeng.2010.04.0318/12/2019 Vida Util Harina Yuca Permeabilidad Empaque
3/7
2.4. Moisture sorption isotherm modeling
Isotherm models from the literature (Berg and Bruin, 1981; To-
ledo, 1991) were selected for modeling the experimental data of
adsorption isotherms of cassava-flour-based baked samples. Those
models are expressed and rearranged as given in Table 1. The
parameters of the equations were estimated using Kyplot 2.0 for
Windows (Kyence Inc., Japan). The value of the root mean square
percentage error (%RMS) represents the fitting ability of a model
in association with the number of data points.
2.5. Determination of critical water activity of cassava-flour-based
baked product based on mechanical and sensory approaches
2.5.1. Sensory evaluation
Twelve panelists were trained to ensure the same perception of
crispness attribute, as defined by Duizer et al. (1998). Crispness
was rated on a nine-point category scale (1 = not crisp/soggy,
9 = very crisp). The panelists evaluated the samples in a random or-
der, three times over three sessions. A three-way variance analysis
products, panelists and replications (block factor) ensured no
interaction between products and panelists. This ensured a greater
understandability and homogeneity of panelists results regarding
the crispness evaluation.
2.5.2. Mechanical measurement
Mechanical measurement was performed with a texture ana-
lyzer (LLOYD Instrument TM LRX S/N 10313, Lloyd Instruments
Ltd., UK). A sample was placed on top of the lower hollow cylinder.
A flat cylindrical plunger (4.77 mm dia) was set to a crosshead
speed of 10 cm/min and a load of 50 kgf. Force and deformation
data were recorded. Each sample was measured in 1520 repli-
cates. Hardness (kgf) was defined as the maximum force at the
breaking point of the product, and work (kgf.mm) as the integral
area under the force and deformation curve (Li et al., 1998).
2.6. Determination of activation energy for water vapor permeability
of LDPE and OPP films
Water vapor permeability (WVP) was measured gravimetri-
cally, according to ASTM Standard Method E 9519. The test dish
was filled with desiccant within 6 mm of the specimen. The spec-
imen was then attached to the dish, and the edges of the specimen
sealed with melted paraffin wax to prevent the passage of vapor
into, out of, or around the specimen edges. Three test dishes were
used per sample. Each was weighed at once, placed in a separate
desiccator over saturated salt solution having known relative
humidity of 90 2% RH and conditioned in a temperature-
controlled chamber at 5 different temperatures (20 1 C,
2 5 1 C, 30 1 C, 35 1 C a n d 3 8 1 C). Test dishes were
weighed periodically. The relationship of gain weight and time
were plotted, with WVTR calculated as follows:
WVTR G
t
1
A 2
The water vapor permeability coefficient (P) can be expressed
as:
PWVTR
Dp l; 3
where:G = weight change (from the straight line), g; t= time, d;G/
t= slope of the straight line, g d1; A = test area (cup mouth area),
m2; WVTR = rate of water vapor transmission, g d1 m2;P= water
vapor permeability, g mil d1 m2 mmHg1; l = thickness, mil; and
Dp= vapor pressure difference, mmHg.
Plotting ln P versus 1/T gives a straight line. The slope of the
straight line representsEp/R. TheEpof the reaction can now be cal-
culated by multiplying the slope by the gas constant (R).
2.7. Shelf life simulation of moisture-sensitive products
The shelf life simulation of moisture-sensitive products was
developed based on Eq. (10):
t Gl
APDp; 4
where: t= time, d; G= mass of products (dry) [critical moisture
(Mc) initial moisture (M0)], g; A= area, m2; l= thickness, mil;
P= permeability coefficient, g mil d1 m2 mmHg1;
Dp psatRH0RH
100 ;mmHg:
Shelf life simulation was rendered into two cases. In the first
case, the water vapor permeability coefficient was in accordancewith a standard condition of storage at 38 C, as a worst-case sce-
nario. In the second case, the water vapor permeability coefficient
was in accordance with the actual condition of storage at 30 C.
This coefficient can be calculated by employing the activation en-
ergy for WVP.
2.8. Shelf life determination of moisture-sensitive products
The shelf life of cassava-flour-based baked products can be
determined experimentally. About 50 g of samples were packed
in 0.103 0.156 m of 50lm LDPE and 50 lm OPP pouches. Stor-
age conditions were 30 1 C and 50%RH. The pouches containing
the products were evaluated for moisture content, sensory hard-
ness, and work every 34 days, until products reached their criticalmoisture content. The results obtained from analytical and exper-
imental shelf life predictions were compared.
3. Results and discussion
3.1. Food properties
The chemical composition of the cassava-flour-based baked
sample was 84.78% 0.09% carbohydrate (approximately 60.08%
starch), 0.63% 0.07% protein, 10.24% 0.09% fat, 3.74% 0.05%
water, 0.32% 0.01% ash and 0.29% 0.03% fiber, on a wet basis.
This dry crisp sample was high in starch and fat contents. After
baking and cooling down, the sample was analyzed for aw and
moisture content. It was found that the sample properties were0.38 and 3.9%, respectively.
Table 1
Models describing the moisture sorption isotherms of cassava-flour-based baked
product.
Model Mathematical expression
BET (BrunauerEmmettTeller)
Brunauer et al. (1938)
me moCBaw=1 aw1 CB 1aw
GAB (GuggenheimAndersonde
Boer)Berg and Bruin (1981)
me moCGkaw=1 aw1 CG 1kaw
LewickiLewicki (1998) me F=1 awG F=1 aHw
OswinOswin (1946) me kaw=1 awc
PelegPeleg (1993) me aabw cadw
me, Equilibrium moisture content;mo, monolayer moisture content;a,b,c,CB,CG,d,F, G, H, k, constants specific to individual mathematical expression.
R. Kulchan et al. / Journal of Food Engineering xxx (2010) xxxxxx 3
ARTICLE IN PRESS
Please cite this article in press as: Kulchan, R., et al. Shelf life prediction of packaged cassava-flour-based baked product by using empirical models and
activation energy for water vapor permeability of polyolefin films. Journal of Food Engineering (2010), doi: 10.1016/j.jfoodeng.2010.04.031
http://dx.doi.org/10.1016/j.jfoodeng.2010.04.031http://dx.doi.org/10.1016/j.jfoodeng.2010.04.0318/12/2019 Vida Util Harina Yuca Permeabilidad Empaque
4/7
3.2. Moisture sorption kinetics and isotherm
Moisture sorption kinetic curves of cassava-flour-based baked
product are depicted in Fig. 1. Moisture adsorption was more rapid
in the initial stages, and declined with increasing time. Then, mois-
ture content of the product reached a plateau, indicating that it be-
came equilibrated with relative humidity in each condition. At
relative humidity of 11.3%, 32.4%, 51.4%, 75.1% and 92.5%, the re-
quired times to reach each equilibrium were 34, 60, 76, 100 and
384 h, respectively. Baucour and Daudin (2000) reported that, at
high relative humidity, the mass transfer is very slow, making it
difficult to reach equilibrium in the range 0.91.0 aw. Measured
sorption kinetic curve data were fitted to Eq. (1). The constants
k1 andk2, which were derived from the linear fit, are shown in
Table 2. The coefficients of determination were found to be high
in all cases (r2 > 0.90); this is an indication of a good fit to the
experimental data. Generally, food products stored at a higher
relative humidity tended to have lower k1 and k2 values, and vice
versa. As constants associated with mass transfer and maximum
moisture adsorption capacity, the lower the k1, the higher the ini-
tial moisture adsorption rate, and the lower the k2, the higher the
moisture adsorption capacity (Turhan et al., 2002). However in this
case, at 92.5% RH,k1 showed a higher value, which means a lower
degree of initial moisture adsorption rate. This is due to a slow
mass transfer at high relative humidity.
The moisture sorption isotherm curve of cassava-flour-based
baked product, represented in Fig. 2, can be classified as a type II
sigmoidal isotherm, which is obtained for soluble materials and
shows an asymptotic trend as water activity tends toward 1 ( Bell
and Labuza, 2000). Moisture sorption was more rapid in the initial
stages, and a lesser amount of moisture was adsorbed as adsorp-
tion time increased. The higher the relative humidity used, the
more pronounced the effect. The equilibrium moisture content of
the product dramatically soared above aw= 0.73.
Calculated model constants, coefficient of determination (r2),
and %RMS for each model for the product are represented in
Table 3. The GAB model is a semi-theoretical multilayer sorption
model with a physical meaning for each constant. In general, it isthe most accepted model for foods or edible materials. The product
presented a monolayer moisture content of 2.46% (dry basis). This
value indicates the maximum amount of water that can be ad-
sorbed in a single layer of the dry product, and is a measure of
the number of sorbing sites. This monolayer moisture content de-
fines the physical and chemical stability of foods. It has an effect on
lipid oxidation, enzyme activity, non-enzymatic browning, flavor
preservation, and product structure (Menkov, 2000). This value is
in the range of acceptability because the maximum monolayer
moisture content should not be more than 10% dry basis for food
products (Labuza et al., 1985).Araromi et al. (2008)also reported
that monolayer moisture content decreases with increasing tem-
perature. This is due to a decrease in the number of active sites
for water binding, which may be caused by changes in physical
or chemical structures in the food products as a result of changes
in temperature (Geankoplis, 1993). The trends are in line for
high-carbohydrate foods, as reported byLabuza (1968).
The BET model can be also used to determine the monolayer
water content of a product (2.39%, dry basis). However, this model
is applicable only betweenawvalues of 0 and 0.5 (Bell and Labuza,
2000). The Lewicki model was developed for applicability to a high
range of aw. It fits well with the moisture sorption data at high
humidity, and predicts that water content tends to infinity when
aw reaches 1.0. The Oswin model provides good descriptions of
the moisture isotherms throughout the entire range of water
Fig. 1. Moisture sorption curves of cassava-flour-based baked product at various
relative humidity as a function of time.
Table 2
Sorption kinetic model constants and coefficient of determination for cassava-flour-
based baked product at selected relative humidity.
Relative humidity (%) Cassava-flour-based baked product
k1 k2 r2
11.3 3.32 0.76 0.9286
32.4 1.86 0.30 0.9429
51.4 1.09 0.16 0.9391
75.7 0.64 0.09 0.9634
92.5 1.79 0.02 0.9650
Fig. 2. Moisture sorption isotherm of cassava-flour-based baked product.
Table 3
Sorption isotherm model constants, coefficient of determination and percentage of
root mean square error for cassava-flour-based baked product.
Sorption isotherm model Constant r2 %RMS
BET m0= 2.3867 0.9481 6.6812
CB= 4.6705
GAB m0= 2.4598 0.9976 3.1309
CG= 49.0599
k= 1.0904
Lewicki F= 1.6765 0.9888 4.7429
G= 1.5727
H= 3.9982
Oswin k= 4.3764 0.9668 13.9072
c= 1.1409
Peleg a= 335.0922 0.9991 3.6487
b= 16.6709
c= 13.6947
d= 1.1218
4 R. Kulchan et al. / Journal of Food Engineering xxx (2010) xxxxxx
ARTICLE IN PRESS
Please cite this article in press as: Kulchan, R., et al. Shelf life prediction of packaged cassava-flour-based baked product by using empirical models and
activation energy for water vapor permeability of polyolefin films. Journal of Food Engineering (2010), doi:10.1016/j.jfoodeng.2010.04.031
http://dx.doi.org/10.1016/j.jfoodeng.2010.04.031http://dx.doi.org/10.1016/j.jfoodeng.2010.04.0318/12/2019 Vida Util Harina Yuca Permeabilidad Empaque
5/7
activity. However in this case, the maximum %RMS value was ob-
tained for the Oswin model. The Peleg model can predict both sig-
moid and non-sigmoid isotherms. This model might be fitted as
well or better than the GAB model, but unfortunately its constants
had no physical meaning. In the case of the Peleg model, the value
ofr2 was highest and was similar to the GAB model. Nevertheless,
the %RMS value from the Peleg model produced a higher result
than that of the GAB model. Thus, the GAB model was found to
be the best estimator for predicting the equilibrium moisture con-
tent of the product, followed by the Peleg and Lewicki models. This
is in agreement withRohvein et al. (2004) and Siripatrawan and
Jantawat (2006)who reported that the GAB model is considered
to be the most versatile sorption model available in the literature,
since it has been shown to fit the experimental sorption data for
nearly all products and over the whole water activity range.
Fig. 3 reveals the experimental vs. predicted moisture content of
the product. The obtained points lie on the diagonal for low and
intermediate awlevels, indicating low interaction between compo-
nents in accordance with their separation in independent phases,
as observed during the product baking. At a high level of water
activity, it can also be observed that points fall on the diagonal,
as a result of the interaction between water molecules and the po-
lar groups of the product.
3.3. Relationship between texture and water activity
Crispness of the baked samples was determined using a sensoryapproach. Fresh samples were highly crispy, with a score of 7.8,
and were very moisture-sensitive. As the samples adsorbed more
water, the crispness acceptance sharply declined in a linear man-
ner with an increase in water activity (Fig. 4). It was noticed that
the product crispness was preserved to a satisfactory degree
(scoreP 5) when containing a small amount of water (aw< 0.54)
or moisture content (dry basis < 6%). These specific values of awand moisture content (0.54 or 6%) could be considered as critical
points of crispness loss. These critical water activity values corre-
sponded to those of other dry crisp starchprotein-matrix prod-
ucts, reported as approximately 0.5 (Roos et al., 1998; Hough
et al., 2001). The cassava baked sample also contained protein
and starch, which would be anticipated to form such a crispy ma-
trix during baking. This matrix was significantly softened by the
plasticization effect of water adsorbed above the critical level
(Martinez-Navarrete et al., 2004). It is interesting to point out that
the water activity at the critical level (0.54) is much higher than
that at the monolayer water content (2.5% dry basis or
aw 0.12). As demonstrated in previous work, at the critical water
activity the product was still in a glassy stage (Tg,m 132.8 C)
(Kulchan et al., 2010).
The product texture was also examined using a mechanical ap-
proach. The results showed that product hardness and work were
changed in a concave manner with increasing water activity
(Fig. 4). Each of them increased to a maximum point at
aw 0.54. As pointed out above, awat this value is the critical point
of crispness loss (score = 5). This suggested that the mechanical
hardness and work data at the maximum level could be used to
identify the critical aw of crispness loss in sensory data. The same
incidence was also reported for extruded flat bread (Roudaut
et al., 1998).
An increase in water content in the product resulted in a de-
crease of the glass transition temperature (Kulchan et al., 2010)
as well as crispness over the whole range ofaw, but for hardness
and work it occurred only ataw higher than 0.54. Such reductions
are caused by molecular mobility which is facilitated by water
Fig. 3. Comparison between experimental moisture content and those predicted by
various sorption isotherm models for cassava-flour-based baked product.
Fig. 4. Relationships between water activity and texture properties and moisture content of the cassava-flour-based baked product.
R. Kulchan et al. / Journal of Food Engineering xxx (2010) xxxxxx 5
ARTICLE IN PRESS
Please cite this article in press as: Kulchan, R., et al. Shelf life prediction of packaged cassava-flour-based baked product by using empirical models and
activation energy for water vapor permeability of polyolefin films. Journal of Food Engineering (2010), doi: 10.1016/j.jfoodeng.2010.04.031
http://dx.doi.org/10.1016/j.jfoodeng.2010.04.031http://dx.doi.org/10.1016/j.jfoodeng.2010.04.0318/12/2019 Vida Util Harina Yuca Permeabilidad Empaque
6/7
molecules (Roudaut et al., 2002). However at lower water activity
(from 0.23 to 0.54), hardness and work, on the contrary, sharply in-
creased with an increase in water activity. This is due to the fact
that at such low water activity (such as 0.23, which is close to
0.12 of the monolayer water) the product had only a small number
of water molecules. An addition of water could be just enough to
fill the free volume (at a microscopic level), leading to an increase
in product density (Benczedi 1999; Seow et al., 1999) and interac-
tions among water and other component molecules (Roudaut et al.,
2002). These phenomena cause strong increases in hardness and
work (a stronger puncture force was required). However, such an
increase in water had only a slight impact on glass transition tem-
perature, corresponding to a slight increase in molecular mobility
(Kulchan et al., 2010).
3.4. Activation energy of water vapor permeability of LDPE and OPP
films
Arrhenius plots of WVPs of LDPE and OPP films are depicted in
Fig. 5. It was found that WVPs of LDPE and OPP films are not highly
temperature-dependent. This resulted in low values of activation
energies for WVPs of LDPE and OPP films: 22.33 and
21.26 kJ mol1, respectively. This low Ep implies that temperature
fluctuation during storage does not have a significant impact on
WVP, and in turn shelf life estimation (and vice versa). Xiong
(2002) reported that activation energy of WVP of LDPE was
22.86 kJ mol1. In addition,George et al. (1997)reported that acti-
vation energies for WVPs of LDPE composite films reinforced with
20% (w/w) untreated and treated dicumyl peroxide (05% by
weight of polymer) pineapple-leaf fiber were 23.64 and
22.23 kJ mol1, respectively.
3.5. Shelf life simulation of moisture-sensitive products
Predicted shelf life by the GAB model was simulated using the
WVPs of LDPE and OPP films at a standard condition (38 C), which
were 0.2785 and 0.0861g mil d1 m2 mmHg1, respectively.
Predicted shelf life by the GAB model andEp for WVP were simu-
lated using the WVPs of LDPE and OPP films at an actual storage
condition (30 C), which were 0.2288 and 0.0687g mil d1
m2 mmHg1, respectively. The simulated shelf life values of cas-
sava-flour-based baked products in all packages are shown in Table
4. It was found that predicted shelf life by the GAB model and Epfor
WVP yields better shelf life estimation, closer to the actual shelf life
as predicted by the GAB model. The differences between the exper-
imental and the predicted shelf life of the product are minute,
especially in the case of the predicted shelf life by the GAB model
andEpfor WVP, which is based solely on the relationship between
moisture content of the product and the barrier property of the
packaging material, as well as the storage condition. However,
Roca et al. (2006)stated that shelf life of a moisture-sensitive food
product is affected not merely by moisture adsorption but also by
moisture migration in the food product, which is greatly affected
by the complexity of the food structure.
4. Conclusion
The moisture sorption kinetics of cassava-flour-based baked
products was more rapid in the initial stages; a lesser amount of
moisture was adsorbed as the adsorption time increased. GAB, Pe-
leg and Lewicki models were useful to fit moisture sorption iso-
therm data of the products. The product hardness or work
reached the maximum and began to reduce at moisture content
(MC) 6%, when the product texture began to be detected as
becoming slightly soft. The predicted shelf lives estimated by
employing Epfor WVP of LDPE and OPP, and the GAB model were
close to the actual shelf lives. Therefore, the estimation by empir-
ical models and activation energy was found to be applicable for
rapid and accurate shelf life prediction.
Acknowledgments
This work was fully supported by a fund for the promotion of
research at the Center of Advanced Studies for Agriculture and
Food (CASAF), Kasetsart University. The authors express their
thanks and appreciation for this support.
References
Al-Muhtaseb, A.H., McMinn, W.A.M., Magee, T.R.A., 2002. Moisture sorption
isotherm characteristics of food products: a review. Transaction of Institution
of Chemical Engineers 80 (C), 118128.
Araromi, D.O., Olu-Arotiowa, O.A., Olajide, J.O., Afolabi, T.J., 2008. Neuro fuzzy
modeling approach for prediction of equilibrium moisture characteristics and
shelf-life of corn flour. International Journal of Soft Computing 3 (2), 159166.
Azanha, A.B., Faria, J.A.F., 2005. Use of mathematical models for estimating theshelf-life of cornflakes in flexible packaging. Packaging Technology and Science
18 (4), 171178.
Baucour, P., Daudin, J.D., 2000. Development of a new method for fast measurement
of water sorption isotherms in the high humidity range: validation on gelatine
gel. Journal of Food Engineering 44 (2), 97107.
Bell, L.N., Labuza, T.P., 2000. Moisture Sorption: Practical Aspects of Isotherm
Measurement and Use, second ed. American Association of Cereal Chemists,
Inc., St. Paul.
Benczedi,D., 1999. Estimation of thefree volume of starchwaterbarriers. Trendsin
Food Science and Technology 10 (1), 2124.
Berg, C., Bruin, S., 1981. Water activity and its estimation in food systems:
theoretical aspects. In: Rockland, L.B., Steward, G.F. (Eds.), Water Activity:
Influences on Food Quality. Academic Press, New York, pp. 147177.
Brunauer, S., Emmett, P.H., Teller, E., 1938. Adsorption of gases in multimolecular
layers. Journal of the American Chemical Society 60 (2), 309319.
Chang, Y.P., Cilean, P.B., Seow, C.C., 2000. Variations in flexural and compressive
fracture behavior of a brittle cellular food (dried bread) in response to moisture
sorption. Journal of Texture Studies 31 (5), 525540.
Chen, Y., Li, Y., 2003. A new model for predicting moisture uptakeby packaged solidpharmaceuticals. International Journal of Pharmaceutics 255 (12), 217225.Fig. 5. Arrhenius plots of water vapor permeability of LDPE and OPP films.
Table 4
Comparison between experimental shelf life and predicted shelf life of cassava-flour-
based baked product.
Shelf life Days % Difference in
shelf life
LDPE
pouch
OPP
pouch
LDPE
pouch
OPP
pouch
Experimental shelf life 35 119
Predicted shelf life by GAB model 30.47 97.85 12.94 17.77
Predicted shelf life by GAB model
andEp for WVP
36.83 122.77 5.23 3.17
6 R. Kulchan et al. / Journal of Food Engineering xxx (2010) xxxxxx
ARTICLE IN PRESS
Please cite this article in press as: Kulchan, R., et al. Shelf life prediction of packaged cassava-flour-based baked product by using empirical models and
activation energy for water vapor permeability of polyolefin films. Journal of Food Engineering (2010), doi:10.1016/j.jfoodeng.2010.04.031
http://dx.doi.org/10.1016/j.jfoodeng.2010.04.031http://dx.doi.org/10.1016/j.jfoodeng.2010.04.0318/12/2019 Vida Util Harina Yuca Permeabilidad Empaque
7/7
Chirife, J., Iglesias, H.A., 1978. Equations for fitting water sorption isotherms of
foods. Journal of Food Technology 13 (2), 159174.
Del Nobile, M.A., Buonocore, G.G., Limbo, S., Fava, P., 2003. Shelf life prediction of
cereal-based dry foods packed in moisture-sensitive films. Journal of Food
Science 68 (4), 12921300.
Duizer, L.M., Campanella, O.H., Barnes, G.R.G., 1998. Sensory, instrumental and
acoustic characteristics of extruded snack food products. Journal of Texture
Studies 29 (4), 397411.
Geankoplis, C.J., 1993. Transport Process and Unit Operations, third ed. Prentice-
Hall, Inc.
George, J., Bhagawan, S.S., Thomas, S., 1997. Effects of environment on theproperties of low-density polyethylene composites reinforced with pineapple-
leaf fibre. Composites Science and Technology 58 (9), 14711485.
Greenspan, L., 1977. Humidity fixed points of binary saturated aqueous solutions.
Journal of Research of the National Bureau of Standards 81A (1), 89102.
Hecke, E.V., Allaf, K., Bouvier, J.M., 1995. Texture and structure of crispy-puffed food
products I: mechanical properties in bending. Journal of Texture Studies 26 (1),
1125.
Hough, B., Buera, M.P., Chirife, J., Moro, O., 2001. Sensory texture of commercial
biscuits as a function of water activity. Journal of Texture Studies 32 (1),
5774.
Kulchan, R., Suppakul, P., Boonsupthip, W., 2010. Texture of glassy tapioca-flour-
based baked product as a function of moisture content. In: Reid, D.S.,
Sajjaanantakul, T., Lillford, P.J., Charoenrein, S. (Eds.), Water Properties in
Food, Health, Pharmaceutical and Biological Systems: ISOPOW 10. Wiley-
Blackwell, New York.
Labuza, T.P., 1968. Sorption phenomena in foods. Food Technology 23 (1),
1519.
Labuza, T.P., Kaanane, A., Chen, J.Y., 1985. Effect of temperature on the moisture
sorption isotherms and water activity shift of two dehydrated foods. Journal of
Food Science 50 (2), 385389.
Lane, R.H., 1998. Cereal foods. In: AOAC, Official Methods Analysis of AOAC
International, 16th ed. AOAC International, Gaithersburg, pp. 137.
Lewicki, P.P., 1998. A three parameter equation for food moisture sorption
isotherms. Journal of Food Process Engineering 21 (2), 127144.
Li, Y., Kloeppel, M.K., Hsieh, F., 1998. Texture of glassy corn cakes as a function of
moisture content. Journal of Food Science 63 (5), 869872.
Lopez, A.C.B., Pereira, A.J.G., Junqueira, R.G., 2004. Flour mixture of rice flour, corn
and cassava starch in the production of gluten-free white bread. Brazilian
Archives of Biology and Technology 47 (1), 6370.
Martinez-Navarrete, N., Moragu, G., Talens, P., Chiralt, A., 2004. Water sorption and
the plasticization effect in wafers. International Journal of Food Science and
Technology 39 (5), 555562.
Menkov, N.D., 2000. Moisture sorption isotherms of vetch seeds at four
temperatures. Journal of Agricultural Engineering Research 76 (4), 373380.
Mohamed, S., Abdullah, N., Muthu, M.K., 2006. Physical properties of keropok (fried
crisps) in relation to the amylopectin content of the starch flours. Journal of the
Science of Food and Agriculture 49 (3), 369377.
Nicholls, R.J., Appelqvist, I.A.M., Davies, A.P., Ingman, S.J., Lillford, P.J., 1995. Glass
transition and the fracture behavior of gluten and starches within the glassy
state. Journal of Cereal Science 21 (1), 2536.
Oswin, C.R., 1946. The kinetics of package life. III. The isotherm. Journal of the
Society of Chemical Industry 65 (4), 419423.
Peleg, M., 1988. An empirical model for the description of moisture sorption curves.
Journal of Food Science 53 (4). 12161217 and 1219.
Peleg, M., 1993. Assessment of a semi-empirical 4 parameter general model forsigmoid moisture sorption isotherms. Journal of Food Process Engineering 16
(1), 2137.
Roca, E., Guillard, V., Guilbert, S., Gontard, N., 2006. Moisture migration in a cereal
composite food at high water activity: effects of initial porosity and fat content.
Journal of Cereal Science 43 (2), 144151.
Rohm, H., 1990. Consumer awareness of food texture in Austria. Journal of Texture
Studies 21 (3), 363373.
Rohvein, C., Santalla, E., Gely, M.C., 2004. Estimation of sorption isotherm and the
heat of sorption of quinoa (Chenopodium quinoaWild.) seeds. Food Science andTechnology International 10 (6), 409413.
Roos, Y., Roininen, K., Jouppila, K., Tuorila, H., 1998. Glass transition and water
plasticization effects on crispness of a snack food extrudate. International
Journal of Food Properties 1 (2), 163180.
Roudaut, G., Dacremont, C., Le Meste, M., 1998. Influence of water on the crispness
of cereal-based foods: acoustic, mechanical, and sensory studies. Journal of
Texture Studies 29 (2), 199213.
Roudaut, G., Dacremont, C., Valles Pamies, B., Colas, B., Le Meste, M., 2002.
Crispness: a critical review on sensory and material science approaches. Trends
in Food Science and Technology 13 (67), 217227.
Seow, C., Cheah, P.B., Chang, Y.P., 1999. Antiplasticization by water in reduced-
moisture food systems. Journal of Food Science 64 (4), 576581.
Siripatrawan, U., 2009. Shelf-life simulation of packaged rice crackers. Journal of
Food Quality 32 (2), 224239.
Siripatrawan, U., Jantawat, P., 2006. Determination of moisture sorption isotherms
of jasmine rice crackers using BET and GAB models. Food Science and
Technology International 12 (6), 459465.
Toledo, R.T., 1991. Fundamentals of Food Processing Engineering, second ed. Van
Nostrand Reinhold, New York.
Turhan, M., Sayar, S., Gunasekaran, S., 2002. Application of Peleg model to study
water absorption in chickpea during soaking. Journal of Food Engineering 53
(2), 153159.
Xiong, L., 2002. Determination and prediction of shelf life of moisture-sensitive
Post
shredded wheat cereal. School of Packaging, Michigan State University 12,
7794.
R. Kulchan et al. / Journal of Food Engineering xxx (2010) xxxxxx 7
ARTICLE IN PRESS
Please cite this article in press as: Kulchan, R., et al. Shelf life prediction of packaged cassava-flour-based baked product by using empirical models and
activation energy for water vapor permeability of polyolefin films Journal of Food Engineering (2010) doi: 10 1016/j jfoodeng 2010 04 031
http://dx.doi.org/10.1016/j.jfoodeng.2010.04.031http://dx.doi.org/10.1016/j.jfoodeng.2010.04.031