This article was downloaded by: [202.58.85.

58]
On: 10 November 2014, At: 06:35
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House,
37-41 Mortimer Street, London W1T 3JH, UK

Drying Technology: An International Journal

Publication details, including instructions for authors and subscription information:
http://www.tandfonline.com/loi/ldrt20

Influence of Drying Conditions on Physical Properties of

Alginate Films
a

Mariana Altenhofen da Silva , Andra Cristiane Krause Bierhalz & Theo Guenter
Kieckbusch

School of Chemical Engineering, University of Campinas (UNICAMP), Cidade Universitria ,

Zeferino Vaz, Campinas, Brazil
Published online: 02 Nov 2011.

To cite this article: Mariana Altenhofen da Silva , Andra Cristiane Krause Bierhalz & Theo Guenter Kieckbusch (2012)
Influence of Drying Conditions on Physical Properties of Alginate Films, Drying Technology: An International Journal, 30:1,
72-79, DOI: 10.1080/07373937.2011.620727
To link to this article: http://dx.doi.org/10.1080/07373937.2011.620727

PLEASE SCROLL DOWN FOR ARTICLE

Taylor & Francis makes every effort to ensure the accuracy of all the information (the Content) contained
in the publications on our platform. However, Taylor & Francis, our agents, and our licensors make no
representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of the
Content. Any opinions and views expressed in this publication are the opinions and views of the authors, and
are not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied upon and
should be independently verified with primary sources of information. Taylor and Francis shall not be liable for
any losses, actions, claims, proceedings, demands, costs, expenses, damages, and other liabilities whatsoever
or howsoever caused arising directly or indirectly in connection with, in relation to or arising out of the use of
the Content.
This article may be used for research, teaching, and private study purposes. Any substantial or systematic
reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any
form to anyone is expressly forbidden. Terms & Conditions of access and use can be found at http://
www.tandfonline.com/page/terms-and-conditions

Drying Technology, 30: 7279, 2012

Copyright # 2012 Taylor & Francis Group, LLC
ISSN: 0737-3937 print=1532-2300 online
DOI: 10.1080/07373937.2011.620727

Influence of Drying Conditions on Physical Properties of

Alginate Films
Mariana Altenhofen da Silva, Andrea Cristiane Krause Bierhalz, and
Theo Guenter Kieckbusch

Downloaded by [202.58.85.58] at 06:35 10 November 2014

School of Chemical Engineering, University of Campinas (UNICAMP), Cidade Universitaria

Zeferino Vaz, Campinas, Brazil

temperature can vary signicantly. According to the

technical literature, alginate lms are dried using ambient
temperature[3,4] and at 36
C,[5] 40
C,[68] 50
C,[9] 60
C,
and 80
C.[10] The drying time can vary according to the
drying temperature, frame volume, solution concentration,
and relative humidity of the air.
Drying is a simultaneous heat and mass transfer process
and is one of the most challenging steps in the production
of biolms. It is well known that distinct drying methods
and conditions can affect the properties and functionalities
of lms differently.[11,12] During the last few decades a
considerable amount of research has been developed on
biolms and their characterization. However, the inuence
of the drying process is still poorly studied and understood.[13] The drying behaviors of biolms have yet to be
explored, especially for those composed of carbohydrates.
Alcantara et al.[14] stressed that drying conditions are
important in applications where the lms will be used to
cover food materials.
Ashikin et al.[10] veried that the mechanical properties
of alginate lms were greatly affected by the air drying
temperature. Menegalli et al.[15] suggested that gelatin
lm solution must be dried at near room temperature
and relative humidity in order to obtain optimal lm characteristics, including mechanical properties and cohesiveness. In another work, Mayachiew and Devahastin[16]
observed that the mechanical properties and crystallinity
of chitosan lms were affected by different drying methods
(ambient air drying and hot air drying at 40
C, vacuum
drying, and low-pressure superheated steam drying).
Recently, Thakhiew et al.[17] showed that the differences
in the physical properties of chitosan lms prepared by
different drying methods and conditions indeed affected
the release of phenolic compounds incorporated in these
matrices.
The denition of a standard protocol regarding the drying conditions for casting would be of great value to enable
reproducible alginate lm production with suitable functional attributes. The present work evaluated the effect of

The effect of drying conditions of the lm-forming solution on

thickness, moisture content, water vapor permeability, and tensile
properties of alginate lms were investigated. A long period of constant rate was observed in all conditions and the model proposed by
Wang and Singh was able to adjust the drying data. As expected,
there was a clear effect of temperature on drying kinetics; that is,
increasing the drying temperature decreased the drying time. Considerable glycerol losses were observed when alginate gel was oven
dried at temperatures above 40
C. Compared to other drying conditions, lms oven dried at 60
C were thinner, had lower moisture
content, and were less exible.
Keywords Drying; Films; Glycerol; Alginate

INTRODUCTION
In recent years, the use of natural polymers obtained
from renewable sources has greatly increased. Bio-based
lms have been extensively investigated due to their potential use as food packaging, representing an alternative to
nonbiodegradable polymeric lms. Although this kind of
lms is not meant to totally replace traditional synthetic
packaging, they do have the potential to reduce their use,
as well as to function as controlled-release systems of active
substances and to limit moisture, aroma, and lipid
migration between food components.[1] Biopolymer lms
are generally prepared by using biological materials such
as polysaccharides, proteins, and their derivatives.
Alginates are structural polysaccharides extracted from
brown algae. On a molecular basis alginates are composed
of guluronic (G) and mannuronic (M) acid units forming
regions of M-blocks, G-blocks, and blocks of alternating
sequence (MG-blocks), where the relative proportions of
these sequential organizations depend on the source.[2]
Alginate lms, as most biolms, are commonly prepared
by means of a solvent-evaporation technique. The drying
Correspondence: Theo Guenter Kieckbusch, School of
Chemical Engineering, University of Campinas (UNICAMP),
Av. Albert Einstein 500, Cidade Universitaria Zeferino Vaz,
Campinas, SP 13083-852, Brazil; E-mail: theo@feq.unicamp.br

72

73

PHYSICAL PROPERTIES OF ALGINATE FILMS

drying temperatures and conditions on physical properties

of alginate lms.

Downloaded by [202.58.85.58] at 06:35 10 November 2014

MATERIALS AND METHODS

Materials
Medium-viscosity sodium alginate, obtained from
Macrocystis pyrifera seaweed, purchased from Sigma
Aldrich (St. Louis, MO), with an average molecular mass
measured by gel permeation chromatography of
1.61  106 Da, was used as the biopolymer matrix for
lm formation. Calcium chloride dihydrate (Merck,
Darmstadt, Germany) was used as the cross-linking agent,
and glycerol (Synth, Diadema, Brazil) was used as the
plasticizer.
Film Preparation
Alginate lms were made by casting of a prepared polymeric aqueous solution. The manufacturing process
involves a reticulating stage in order to allow for a limited
degree of cross-linking with Ca2 without heterogeneous
local gelling.[8] A lm-forming solution of sodium alginate
(1.5 g=100 mL) was prepared in distilled water already containing 0.6 g glycerol=g alginate at room temperature. The
solution was mechanically stirred at 1,000 rpm (model 713,
Fisatom, Sao Paulo, Brazil) for about 1 h to ensure homogeneity and then heated to 70
C. Then a dilute aqueous
calcium chloride solution was slowly added to the biopolymer solution at a ow rate of 1.0 mL=min delivered by a
peristaltic pump (model 77120-70, Masterex C=L, Vernon
Hills, IL) until a total of 0.04 g CaCl2  2H2O=g alginate
was transferred. A low ow rate and strong agitation were
necessary to avoid local gelation. Aliquots of the solution
(60 g) were poured into square Plexiglas frames (225 cm2)
and dried under six different conditions: oven drying
(OD) in a convection=recirculation oven (420D, Nova
tica, Vargem Grande Paulista, Brazil) at air velocity of
E
0.5 m=s and 30
C (OD 30), 40
C (OD 40), 50
C (OD 50),
and 60
C (OD 60) and also at ambient conditions
(25  2
C and 50% relative humidity [RH]) under natural
convection (NC) and forced air (FC) convection (air velocity
of 0.2 m=s). At the end of the drying process, lms were
detached from the support and conditioned at room temperature and 52% RH for 3 days inside desiccators before
characterization. The lms were weighed before and after
equilibration in the desiccator to determine the moisture gain.
Film Drying Kinetics
Film frames containing the polymeric solution were
weighed at predened time intervals during the drying process (gravimetric control) in order to evaluate the drying
kinetics for each condition (in triplicate). The frames were
dried until a constant weight was reached (equilibrium condition), and different drying times were observed. The nal

moisture content of the lms was determined at the end of

the drying process.
The empirical equation proposed by Wang and Singh[18]
(Eq. (1)), which relates the moisture ratio with drying time,
was adjusted to the experimental data.
X  Xe
kt2 nt 1
Xo  Xe

Dry Matter Loss

The initial dry matter (Mo) was estimated considering
the amounts of alginate, glycerol, and calcium chloride
used in the polymeric solution. The nal dry matter (Mf)
was calculated using Eq. (2):
Mf mfilm  1  xe

where mlm is the lm mass after drying and xe is the equilibrium moisture content on a wet basis (determined using
a vacuum oven at 105
C=24 h or using the Karl Fischer
[KF] oven technique).
The percentage dry matter loss (% loss) was estimated
using Eq. (3):
% loss

Mo  Mf
 100
Mo

Film Characteristics
Film Thickness, d
The lm thickness was controlled by pouring a constant
mass (60 g) of the lm-forming solution over the support.
The thickness of the conditioned lms was measured using
a digital micrometer (MDC-25S, Mitutoyo, Kawasaki,
Japan). Measurements were taken at 10 different positions
of the lm and the mean value is reported.
Moisture Content, x
The moisture content of the lms was gravimetrically
determined in a vacuum oven (Squaroid, Lab-Line,
Melrose Park, IL) at 105
C for 24 h and also by the KF
oven technique in a Metrohm apparatus (758 KFD Titrino
and 768 KF oven, Herisau, Switzerland). In this case, the
sample was initially heated to 110
C. An inert and dry carrier gas (N2) owing through the sample carried the liberated water into a connected titration cell. The moisture
content was determined based on the amount of Karl
Fischer reagent (with its correction factor) required to
titrate the water present in the sample.
Water Vapor Permeability
Water vapor permeability (WVP) coefcients were
determined according to method E96-95.[19] Film samples

74

DA

SILVA ET AL.

were sealed over a circular opening of a Plexiglas

permeation cell containing anhydrous calcium chloride.
These cells were individually kept in hermetically closed
chambers (500 mL) containing a saturated solution of
sodium chloride at 25
C in order to maintain an RH difference of 75%. After the system had reached a constant rate
of weight loss (2 h), the cell was weighed at 12-h intervals
for 3 days using an analytical balance (Analytical Plus,
AP210, Ohaus, Florham Park, NJ). The WVP was calculated using Eq. (4):

Downloaded by [202.58.85.58] at 06:35 10 November 2014

WVP

Gd
A  DRH  Pw

where d is the lm average thickness (mm), G is the permeation rate (g=day) calculated using linear regression of
weight gain versus time, A is the permeation area
(15.21 cm2), DRH is the difference in relative humidity
(0.75), and Pw is the pure water saturation pressure at test
temperature (25
C; 3.167 kPa).
Mechanical Properties
Tensile strength (TS) and percentage tensile elongation
at break (E) of the lms were determined at room temperature using a TA.XT2 (Stable Microsystems SMD,
Gouldming, UK) according to ASTM standard method
D882.[20] Films were cut into strips (10  2.54 cm) and
mounted between the corrugated tensile grips of the instrument. The initial grip spacing and cross-head speed were
set at 50 mm and 0.1 cm=s, respectively. The tensile
strength was expressed as the maximum force at break divided by the initial cross-sectional area of the lm strip and
the elongation at break as a percentage of the original
length.
Crystallinity
In order to observe modications in crystallinity of the
alginate lms induced by different drying conditions,
X-ray diffraction was performed on lm samples with a
Philips Analytical XPert PW 3050 diffractometer (Almelo,
The Netherlands) with Cu-Ka radiation. The X-ray source
was operated at 40 kV and 40 mA. Diffraction intensity
was measured as reection mode at a scanning rate of
0.6
=min for 2h 535
.
Statistical Analysis
The parameters of the proposed model for drying
kinetics data were estimated by nonlinear regression using
Statistica V.1.1.5 (Statsoft, Tulsan, OK).
Analysis of variance and Tukeys test were used to determine statistically signicant differences (p < 0.05) among
averages using Statistica V.1.1.5.

FIG. 1. Drying curves of alginate lms under different drying

conditions.

RESULTS AND DISCUSSION

Drying Kinetics
The drying curves of alginate lms obtained at different
drying conditions for frames initially containing 60 g of
polymeric solution are shown in Fig. 1. As expected, there
was a strong effect of air temperature on the drying
kinetics; that is, as the temperature increased, the drying
time decreased.
A long period with a constant drying rate was predominant in all conditions and practical equilibrium moisture
content was reached at the end of the constant rate period
for all drying runs except for natural convection. The
absence of a falling rate period indicates that no internal
resistance was imposed by the lm=gel structure. The same
trend was observed by Kozempel et al.[21] Tapia-Blacido
et al.[22] Wang et al.[23] Mayachiew and Devahastin,[16]
and Miranda et al.[24] in their studies on the drying kinetics
of calcium caseinate, amaranth our gel, apple pomace,
chitosan lms, and aloe vera gel, respectively.

TABLE 1
Empirical parameters of Wang-Singh model for alginate
lms (60 g) dried under different conditions
Drying
condition
NC
FC
OD
OD
OD
OD

30
40
50
60

k  106
(min2)

n  103
(min1)

R2

0.15
0.75
0.96
5.32
6.37
15.8

0.79
0.75
2.06
4.67
5.54
8.06

0.997
0.995
0.996
0.993
0.992
0.994

75

PHYSICAL PROPERTIES OF ALGINATE FILMS

Downloaded by [202.58.85.58] at 06:35 10 November 2014

FIG. 2. Constant drying rate of alginate lms under different drying

conditions.

The average kinetic parameters k and n estimated by the

tting of the experimental points of all ve drying conditions to the Wang-Singh model are presented in Table 1.
Both parameters increased as the drying temperature
increased. The values of R2 obtained from the Wang-Singh
equation varied from 0.992 to 0.997, conrming that this
model provided a good t to the drying data.
The rate of solvent removal is governed by the surface
evaporation capacity by convection and requires sufcient internal liquid migration from the core in order
for the surface to remain wet, which in turn is partly
dependent on drying air temperature and solution formulation.[25] As expected, the constant drying rate of alginate lms greatly increased by increasing the drying
temperature (Fig. 2).
The drying time and the equilibrium moisture content of
the lms for each drying condition are presented in Table 2.
The drying times varied from 3.4 h for the lm oven
dried at 60
C to 44.8 for lms dried at ambient conditions
under natural convection. The values in Table 2 also indicate that the alginate lms oven dried at temperatures of 50
and 60
C show signicantly lower equilibrium moisture
contents (determined by the conventional 105
C=24 h

oven-drying method) compared to the other drying

conditions. This result reects the lower RH of the drying
air at higher temperatures but might also be an indication
of glycerol losses by evaporation during alginate gel drying,
therefore reducing the lms hygroscopicity. Favetto et al.[26]
have conrmed that a considerable amount of glycerol evaporates from a model intermediate-moisture-content food
when submitted to air drying at temperatures greater than
50
C. These authors recommended that for a selective separation of water from glycarol-containing foodstuffs drying
temperatures below 40
C should be considered.
In all drying conditions, the equilibrium moisture content determined by the KF oven technique was signicantly
lower when compared to the values obtained by the conventional method (105
C=24 h). The high selectivity to
water represents the major advantage of KF titration with
respect to the gravimetric technique: only the water content
is determined, because iodine selectively reacts with water.
In contrast, loss on drying will detect the loss of any volatile substance.[27] So, the differences observed in the values
found for the two methods are probably caused by glycerol
evaporation during moisture determination by the vacuum
oven technique.
A glycerol-free lm, prepared using the same manufacturing conditions as for the OD 30 lm, showed approximately the same equilibrium moisture content by the two
different determination methods of 0.109  0.010 and
0.113  0.004 g H2O=g lm for conventional 105
C=24 h
method and KF oven technique, respectively. These results
conrm the hypothesis that a signicant glycerol loss
occurs during moisture determination by the conventional
method. However, the moisture content of glycerol-free
lm was lower compared to glycerol-containing lms
(OD 30, Table 2). This behavior is expected because
glycerol, which is a plasticizer, tends to increase the hygroscopicity of the matrix.
Considering the moisture contents determined by the
KF method, it can be observed that lms dried under

TABLE 2
Equilibrium moisture content and drying time of alginate lms dried under different conditions
xe (g H2O=g lm)
Drying condition
NC
FC
OD
OD
OD
OD

30
40
50
60

Drying time (h)

44.82
19.80
10.75
6.80
4.17
3.37

Vacuum oven 105
C=24 h

b,A

0.271 (0.013)
0.298 (0.008)a,A
0.319 (0.005)a,A
0.279 (0.020)ab,A
0.197 (0.027)c,A
0.192 (0.015)c,A

Karl Fischer oven technique

0.171 (0.002)a,B
0.166 (0.003)a,B
0.158 (0.003)b,B
0.151 (0.002)b,B
0.155 (0.004)b,B
0.148 (0.005)b,B

Average (standard deviation) of three experimental determinations. Averages with the same lowercase superscript letter in the same
column and with the same capital superscript letter in the same line indicate no signicant difference by Tukeys test (p < 0.05).

76

DA

SILVA ET AL.

TABLE 3
Moisture content and weight gain (after equilibration period at 52% RH) of alginate lms dried
under different conditions
x (g H2O=g lm)
Drying condition
NC
FC
OD
OD
OD
OD

30
40
50
60

Vacuum oven 105
C=24 h

Karl Fischer oven technique

Weight gain (%)

0.271 (0.010)b,A
0.303 (0.005)a,A
0.329 (0.008)a,A
0.291 (0.013)ab,A
0.208 (0.005)c,A
0.213 (0.003)c,A

0.173 (0.005)a,B
0.168 (0.007)a,B
0.167 (0.011)a,B
0.163 (0.008)a,B
0.166 (0.009)a,B
0.164 (0.012)a,B

1.38
ND
2.31
4.20
6.18
12.70

Downloaded by [202.58.85.58] at 06:35 10 November 2014

Average (standard deviation) of three experimental determinations. Averages with the same lowercase superscript letter in the same
column and with the same capital superscript letter in the same line indicate no signicant difference by Tukeys test (p < 0.05). ND: not
detectable.

ambient conditions (NC and FC) still showed higher

equilibrium moisture content compared to other drying
conditions, reinforcing the effect of the higher RH of the
drying environment under these ambient conditions.
Effect of Equilibration Period on Moisture Content of the
Films
Before characterization, all lms were kept inside desiccators under controlled relative humidity (52%) for equilibration. The moisture content and weight gain after this
equilibration period are shown in Table 3. It is interesting
to note that lms dried at ambient conditions showed practically no moisture absorption, whereas lms oven dried at
40 and 50
C absorbed 5% water on average and lms processed at 60
C absorbed about 12%. Despite this greater
moisture absorption, the moisture content (determined by
the conventional loss on drying method) after equilibration
of lms dried at 50 and 60
C was lower than the moisture
content of the other lms. This observation reinforces the
hypothesis that glycerol may have been lost during lm
drying under these conditions. On the other hand, moisture
contents determined by the KF oven method did not
show signicant differences for all drying conditions. As
expected, the conditioning period tends to equilibrate the
moisture content of lms, showing that alginate lms are
highly sensitive to relative humidity changes.
In order to estimate the dry matter losses during the
alginate gel drying, a mass balance considering the values
of moisture content measured by the two methods was
evaluated (Table 4). The percentage dry matter loss calculated by the moisture content determined by the conventional method (105
C=24 h) showed no signicant
differences for all drying conditions. Considering that all
dry matter loss is related to glycerol, the results indicate
that approximately 50% of the initially added plasticizer

is lost during gel drying and moisture determination. Once

only water is quantied by the Karl Fischer method, the
values of dry matter losses estimated by the KF moisture
content, suggest that considerable amount of glycerol is
evaporated when the alginate gel is dried at temperatures
above 40
C.
Film Characteristics
Partially Reticulated Alginate Films
The alginate lms produced were homogeneous, transparent and visually attractive. These partially reticulated
lms were very exible, although the lms oven dried at
60
C were slightly more difcult to handle and remove
from the support. The lms were completely solubilized
in water. Zactiti and Kieckbusch[6] and da Silva et al.[8] also
obtained highly soluble alginate lms when manufactured
without a nal crosslinking contact with calcium ions.
TABLE 4
Dry matter loss during drying of polymeric solution
estimated by different methods
Dry matter loss (%)
Drying
condition

Vacuum oven
105
C=24 h

Karl Fischer
oven technique

NC
FC
OD
OD
OD
OD

19.47 (0.90)a
19.71 (0.75)a
20.09 (1.59)a
21.71 (1.51)a
22.13 (1.45)a
22.32 (1.34)a

2.07 (0.45)c
1.96 (0.67)c
2.20 (0.57)c
10.79 (1.06)b
15.95 (1.52)a
17.47 (1.41)a

30
40
50
60

Average (standard deviation) of three replicates. Averages with

the same superscript letter in the same column indicate no signicant difference by Tukeys test (p < 0.05).

77

Downloaded by [202.58.85.58] at 06:35 10 November 2014

PHYSICAL PROPERTIES OF ALGINATE FILMS

Completely soluble alginate lms were also obtained by

Pavlath et al.[28] by adding up to 0.18 g CaCl2  2H2O=g
alginate in a single stage procedure.
No signicant differences in thickness were observed
among the different drying conditions except for lms oven
dried at 60
C, which were thinner compared to lms produced in all other conditions (Table 5). Kayserilioglu
et al.[29] also reported signicant decreases in thickness of
wheat gluten lms dried at 20, 50, and 80
C. The same
trend was veried by Thakhiew et al.[30] who compared
the effects on chitosan lm properties produced by hot
air drying at 40
C and vacuum and low-pressure superheated steam drying at 90
C, and by Alcantara et al.[14]
who studied whey protein lms dried under ambient conditions and at 95
C. However, when testing the effect of
drying temperatures between 4 and 30
C on whey protein
isolate lms, Kaya and Kaya,[31] detected no differences.
This tendency of decreasing thickness with drying air temperature above 60
C could be related to glycerol losses during drying, because all of the above-mentioned research
used glycerol as the plasticizer.
The data in Table 5 also show that for all drying treatments an increase in lm thickness caused a signicant
increase in the WVP. Nevertheless, no signicant difference
was detected by increasing the drying air temperature in the
temperature range studied. Different trends were found in
the literature with respect to the temperature dependency
of WVP for hydrophilic lms. Chinnan and Park[32]
reported an increase in WVP with an increase in drying
air temperature for cellulose lms. On the other hand, Gennadios et al.[33] and Jangchud and Chinnan[34] observed a
decrease in WVP with an increase in drying air temperature
for wheat gluten and soy protein isolate lms and for peanut protein lms in the drying temperature range of 535
C
and 7090
C, respectively. In the case of protein lms,
Jangchud and Chinnan[34] hypothesized that the increase
in WVP with drying air temperature was related to the formation of a tighter and more compact protein network due

to thermal cross-linking. This experimental observation,

however, can also be related to the thinner lm thicknesses,
higher tensile strength, and lower elongation observed for
protein lms dried at higher air temperatures.
The values of the mechanical properties of alginate lms
prepared under different drying conditions are also given in
Table 5. The mechanical properties of biolms can be
affected by drying conditions.[13,31] TS accounts for the lm
mechanical resistance due to the cohesion between the
chains, and the elongation at break (E) measures its plasticity, which is a quantitative measure of the lms ability
to extend before breaking. The effect of drying temperature
on the tensile strength of alginate lms did not show a clear
tendency. For oven-dried lms, there was a decrease in TS
with an increase in lm thickness. According to Cuq
et al.[35] this behavior is expected for lms manufactured
with the same formulation. Values of tensile strength ranged from 13.0 to 19.8 MPa. Alginate lms submitted to a
more intense cross-linking level with calcium ions in order
to produce an insoluble matrix have a much higher resistance, on the order of 100160 MPa.[7,8] Calcium reticulated
lms, however, show considerable lower lm elongation
(26%), resulting in a major disadvantage in most of the
lms applications.
The elongation at break of alginate lms varied from
20.4 to 34.8%. The plasticity of lms oven dried at 60
C
was signicantly lower compared to other drying conditions (Table 5). These results corroborate the hypothesis
of glycerol loss during drying at higher temperatures. Glycerol, as a plasticizer, penetrates through the polymer
matrix, decreasing intermolecular forces and therefore
increasing polymer mobility and decreasing glass transition
temperature. As already stated by da Silva et al.[8] a comparison between the experimental data in Table 5 conrms
that variations in the plasticizer concentration exert an
appreciable effect on lm elongation but only a moderate
effect on tensile strength. Ashikin et al.[10] and Thakhiew
et al.[30] identied the same trend when comparing alginate

TABLE 5
Thickness (d), water vapor permeability coefcient (WVP), tensile strength (TS), and elongation at break (E) of alginate
lms dried under different conditions
Drying condition

da (mm)

WVPb (g  mm=m2  d  kPa)

TSa (MPa)

Ea (%)

NC
FC
OD
OD
OD
OD

52 (2.2)a
52 (3.3)a
51 (3.2)a
54 (1.4)a
52 (1.7)a
46 (1.5)b

13.26 (0.35)a
11.43 (0.89)ab
11.54 (0.81)ab
10.07 (0.93)b
10.95 (0.36)b
10.85 (0.53)b

19.14 (3.42)a
16.55 (1.12)ab
16.43 (1.22)ab
17.15 (1.53)ab
13.81 (2.07)b
14.16 (0.91)b

29.47 (1.40)a
30.62 (1.93)a
32.74 (2.06)a
34.82 (0.98)a
30.42 (2.78)a
22.20 (2.75)b

30
40
50
60

Average (standard deviation) of 10 experimental determinations.

Average (standard deviation) of three experimental determinations.
Averages with the same superscript letter in the same column indicate no signicant difference by Tukeys test (p < 0.05).
b

78

DA

SILVA ET AL.

the conventional 105
C=24 h method. A mass balance

showed that considerable glycerol losses were observed
when alginate gel was oven dried at temperatures above
40
C. Compared to other drying conditions, lms oven
dried at 60
C were signicantly thinner, had lower moisture content, and were less exible. The information gathered in the present study suggests that an oven drying
process at 30
C would be an appropriate method for solvent evaporation in the manufacture of alginate lms.

Downloaded by [202.58.85.58] at 06:35 10 November 2014

FIG. 3. X-ray diffractograms of alginate lms obtained under different

drying conditions.

lms dried at 40 and 60
C and chitosan lms dried at 40

and 90
C, respectively.
The X-ray diffraction patterns of alginate lms prepared
under different drying conditions are shown in Fig. 3. The
diffractogram of the lm dried under ambient conditions
under NC revealed two characteristic crystalline peaks at
2h 14 and 16
, whereas lms produced under other conditions appeared to have a more amorphous morphology.
This behavior is probably due to the slower evaporation
rate of the gellm matrix allowing more time for
molecules to arrange themselves into a more organized
structure. Despite these changes in lattice structure, the
properties and functionality of the lms were apparently
not affected.
Similar results were found by other investigators. Comparing chitosan lms properties dried under ambient
conditions and vacuum oven dried at 70, 80, and 90
C,
Mayachiew and Devahastin[16] found that lms dried in
the vacuum oven had lower crystallinity (7.5%) than lms
dried under ambient conditions (15.3%). Higher levels of
amorphousness were also observed by Ashikin et al.[10]
for alginate lms dried at higher temperatures.
CONCLUSIONS
The drying conditions of alginate lms were varied to
establish an initial understanding of how the air drying
temperature, under natural and forced convection, could
affect the lm thickness, moisture content, WVP, and
mechanical properties. The drying rates were air temperature dependent and, for all ve conditions tested, the drying curves showed a long period of constant drying rate.
The Wang-Singh model was adequate to adjust the drying
data of alginate lms. The KF oven technique proved to be
a more adequate method for moisture determination of
lms, because glycerol evaporation skews the results of

NOMENCLATURE
A
Permeation area (cm2)
G
Permeation rate (g  day1)
k
Wang-Singh parameter (min1)
M
Dry matter (g)
m
Mass (g)
n
Wang-Singh parameter
P
Pure water saturation pressure at 25
C (kPa)
RH Relative humidity (%)
t
Time (min)
X
Moisture content (dry basis) (g water  g1)
Greek Letters
d
Thickness (mm)
x
Moisture content (wet basis) (g water  g1)
Subscripts
e
Equilibrium
f
Final
o
Initial
w
Water

ACKNOWLEDGMENT
The authors acknowledge the State of Sao Paulo
Research Foundation (FAPESP) for nancial support
(Proc. 2008=52830-9).
REFERENCES
1. Krochta, J.M.; De Mulder-Johnston, C. Edible and biodegradable
polymer lms: Challenges and opportunities. Food Technology 1997,
51(2), 6174.
2. Ertesvag, H.; Valla, S. Biosynthesis and applications of alginates.
Polymer Degradation and Stability 1998, 59(13), 8591.
3. Rhim, J.W. Physical and mechanical properties of water resistant
sodium alginate lms. Lebensmittel-Wissenchaft und Technologie
2004, 37(3), 323330.
4. Russo, R.; Malinconico, M.; Santagata, G. Effect of cross-linking
with calcium ions on the physical properties of alginate lms.
Biomacromolecules 2007, 8(10), 31933197.
5. Olivas, G.I.; Barbosa-Canovas, G.V. Alginate-calcium lms: Water
vapor permeability and mechanical properties as affected by plasticizer and relative humidity. Lebensmittel-Wissenchaft und Technologie
2008, 41(2), 359366.
6. Zactiti, E.M.; Kieckbusch, T.G. Potassium sorbate permeability in
biodegradable alginate lms: Effect of the antimicrobial agent concentration and crosslinking degree. Journal of Food Engineering 2006,
77(3), 462467.

Downloaded by [202.58.85.58] at 06:35 10 November 2014

PHYSICAL PROPERTIES OF ALGINATE FILMS

7. Zactiti, E.M.; Kieckbusch, T.G. Release of potassium sorbate from
active lms of sodium alginate crosslinked with calcium chloride.
Packaging Technology and Science 2009, 22(6), 349358.
8. da Silva, M.A.; Bierhalz, A.C.K.; Kieckbusch, T.G. Alginate and pectin composite lms crosslinked with Ca2 ions: Effect of plasticizer
concentration. Carbohydrate Polymers 2009, 77(4), 736742.
9. Sriamornsak, P.; Kennedy, R.A. Swelling and diffusion studies of calcium polysaccharide gels intended for lms coating. International
Journal of Pharmaceutics 2008, 358(12), 205213.
10. Ashikin, W.H.N.S.; Wong, T.W.; Santagata, G. Plasticity of hot air
dried mannuronate- and guluronate-rich alginate lms. Carbohydrate
Polymers 2010, 81(1), 104113.
11. Donhowe, I.G.; Fennema, O. The effects of solution composition and
drying temperature on crystallinity, permeability and mechanical
properties of methylcellulose lm. Journal of Food Processing and
Preservation 1993, 17(4), 231246.
12. Debeaufort, F.; Volley, A. Effect of surfactants and drying rate on
barrier properties of emulsied edible lms. International Journal Food
Science and Technology 1995, 30(2), 183190.
13. Denavi, G.; Tapia-Blacido, D.R.; Anon, M.C.; Sobral, P.J.A.; Mauri,
A.N.; Menegalli, F.C. Effects of drying conditions on some physical
properties of soy protein lms. Journal of Food Engineering 2009,
90(3), 341349.
14. Alcantara, C.R.; Rumsey, T.R.; Krochta, J.M. Drying rate effect on
the properties of whey protein lms. Journal Food Processing and
Preservation 1998, 21(5), 387405.
15. Menegalli, F.C.; Sobral, P.J.; Roques, M.A.; Laurent, S. Characteristics of gelatin biolms in relation to drying process conditions near
melting. Drying Technology 1999, 17(78), 16971706.
16. Mayachiew, P.; Devahastin, S. Comparative evaluation of physical
properties of edible chitosan lms prepared by different drying methods. Drying Technology 2008, 26(2), 176185.
17. Thakhiew, W.; Waisayawan, P.; Devahastin, S. Comparative evaluation of mathematical models for release of antioxidant from chitosan
lms prepared by different drying methods. Drying Technology 2011,
29(12), 13961403.
18. Wang, C.Y.; Singh, R.P. Use of variable equilibrium moisture content
in modeling rice drying. Transactions of American Society of Agricultural Engineers 1978, 11, 668672.
19. American Society for Testing and Materials. Standard Test Methods
of Water Vapor Transmission of Material, E96-95; American Society
for Testing and Materials: Philadelphia, 1995.
20. American Society for Testing and Materials. Standard Test Method
for Tensile Properties of Thin Plastic Sheeting, D882-02; American
Society for Testing and Materials: Philadelphia, 1995.

79

21. Kozempel, M.; McAloon, A.J.; Tomasula, P.M. Drying kinetics of

calcium caseinate. Journal of Agricultural and Food Chemistry 2003,
51(3), 773778.
22. Tapia-Blacido, D.; Sobral, P.J.; Menegalli, F.C. Development and
characterization of biolms based on Amaranth our (Amaranthus
caudatus). Journal of Food Engineering 2005, 67(12), 215223.
23. Wang, Z.; Junhong, S.; Liao, X.; Chen, F.; Guanghua, Z.; Wu, J.; Hu,
X. Mathematical modeling on hot air drying of thin layer apple pomace. Food Research International 2007, 40(1), 3946.
24. Miranda, M.; Maueira, H.; Rodrguez, K.; Veja-Galvez, A. Inuence
of temperature on the drying kinetics, physicochemical properties, and
antioxidant capacity of aloe vera (Aloe barbadensis Miller) gel. Journal
of Food Engineering 2009, 91(2), 297304.
25. Wong, T.W. Use of microwave in processing of drug delivery systems.
Current Drug Delivery 2008, 5(2), 7784.
26. Favetto, G.; Chirife, J.; Bartholomai, G. Determination of moisture
content in glycerol-containing intermediate moisture foods. Journal
of Food Science 1979, 44(4), 12581259.
27. De Caro, C.A.; Aichert, A.; Walter, C.M. Efcient, precise and fast
water determination by the Karl Fischer titration. Food Control
2001, 12(7), 431436.
28. Pavlath, A.E.; Gosset, C.; Camirand, W.; Robertson, G.H. Ionomeric
lms of alginic acid. Journal of Food Science 1999, 64(1), 6163.
29. Kayserilioglu, B.S .; Bakir, U.; Yilmaz, L.; Akkas, N. Drying temperature and relative humidity effects on wheat gluten lm properties.
Journal of Agricultural and Food Chemistry 2003, 51(4), 964968.
30. Thakhiew, W.; Devahastin, S.; Soponronnarit, S. Effects of drying
methods and plasticizer concentration on some physical and mechanical properties of edible chitosan lms. Journal of Food Engineering
2010, 99(2), 216224.
31. Kaya, S.; Kaya, A. Microwave drying effects on properties of whey
protein isolate edible lms. Journal of Food Engineering 2000, 43(2),
9196.
32. Chinnan, M.S.; Park, H.J. Effect of plasticizer level and temperature
on water vapor transmission of cellulose-based edible lms. Journal of
Food Process Engineering 1995, 18(4), 417429.
33. Gennadios, A.; Brandenburg, A.H.; Park, J.W.; Weller, C.L.; Testin,
R.F. Water vapor permeability of wheat gluten and soy protein isolate
lms. Industrial Crops and Products 1994, 2(3), 189195.
34. Jangchud, A.; Chinnan, M.S. Peanut protein lm as affected by drying temperature and pH of lm forming solution. Journal of Food
Science 1999, 64(1), 153157.
35. Cuq, B.; Gontard, N.; Cuq, J.L.; Guilbert, S. Functional properties of
myobrillar protein-based biopackaging as affected by lm thickness.
Journal of Food Science 1996, 61(3), 580584.