basiak ewlina et al 2014
basiak ewlina et al 2014
basiak ewlina et al 2014
Original article
Characterisation of composite edible films based on wheat starch
and whey-protein isolate
Summary Composite films prepared by casting wheat starch and whey-protein isolate at proportions of 100–0%, 75–
25%, 50–50%, 25–75% and 0–100% were characterised. Combination of both substances gave continuous
and homogeneous films. The more the starch is in a film, the more dull is the appearance. The highest water
adsorption was observed for pure whey-protein films and the lowest for pure wheat starch films with the
final water content of 0.264 and 0.324 g water g d.m.1, respectively. An exponential equation well fitted
the experimental data of water vapour kinetics (R2 ≥ 0.99). The highest values of thickness and elongation
at break were observed for films obtained by blending of wheat starch and whey protein. With the increas-
ing content of whey-protein isolate, the values of the swelling index and tensile strength increased from
34.31% to 71.01% and from 2.29 to 8.90 MPa, respectively. The values of water vapour permeability
depended on humidity conditions and decreased slightly with the increasing content of whey-protein isolate.
Keywords Edible films, mechanical properties, microstructure, moisture, wheat starch, whey protein.
doi:10.1111/ijfs.12628
© 2014 Institute of Food Science and Technology
2 Wheat starch/whey protein composite films E. Basiak et al.
the polymer chains (Oses et al., 2009; Murillo-Martınez Films were dried at 25 °C and 40% of relative humid-
et al., 2011; Jimenez et al., 2012). There are several ways ity (RH) for 24 h. Thus, the films were peeled off and
to obtain coatings and films from starch and whey pro- conditioned at 53 1% RH and 25 1 °C for 7 days
teins. They include casting, injection, extrusion, thermo prior to testing. The time of 48 h widely used for edi-
moulding, blowing and sheeting. During the manufac- ble films was not sufficient to obtain the films with
ture of coatings and films, the main aim is to obtain desired state (Galus & Lenart, 2013).
homogeneous material, thin and strong (Fu et al.,
2011). Films made from one type of film-forming sub-
Water content
stance often have limited properties. To improve the
process, several mixtures of biopolymers are used. That Water content was measured by determination of the
is because films which consist of 2–3 types of substances weight loss of the film after 24 h of drying at 105 °C.
have better properties than those made from a single Measurements were repeated three times (Araujo-Far-
type (Kurek et al., 2014). ro et al., 2010).
The aim of the study was to investigate physical
properties of composite edible films based on wheat
Thickness
starch and whey-protein isolate, including thickness,
swelling index, water solubility, colour, tensile strength, Film thickness was measured with an electronic gauge
elongation at break, water vapour permeability, sorp- (METRISON, Poland). Precision of the measurement
tion properties and microstructure of composite films. was 1 lm. Prior to film thickness measurements, the
electronic gauge was calibrated at 74 and 139 lm
using standards. Thickness of each film was measured
Materials and methods
in five places, one in the centre part of the film and
four around its perimeter, and a mean value was used
Materials
in the calculations (Galus & Lenart, 2013).
The native wheat starch containing 26% of amylose
and 84% of amylopectin (WS, min. 97% of starch,
Swelling index
0.3% protein, 0.2% ash, 13% moisture, pH 6.0) was
supplied by Hortimex (Konin, Poland). The whey-pro- The samples were prepared from five different films of
tein isolate (WPI, 97.7% protein, 0.2% fat, 2.0% ash, the same kind. They were cut into 2 9 2 cm pieces
4.9% moisture, pH 6.9) BiPRO was obtained from and weighed. They were then immersed in distilled
Davisco Foods International Inc. (Le Sueur, MN, water (25 °C) for 2 min. Wet samples were wiped with
USA). Anhydrous glycerol and silica gel were pur- filter paper to remove excess liquid and weighed. The
chased from POCH S.A. (Gliwice, Poland). Saturated amount of adsorbed water was calculated in percent-
salt solution of sodium chloride (POCH, Gliwice, ages. The measurement was repeated for each type of
Poland) was used to investigate water vapour perme- film three times, and the arithmetic mean was taken as
ability and water vapour sorption kinetics at relative the final result.
humidity 75.3% and temperature 25 °C.
Water solubility
Film preparation
Films were cut into 2 9 2 cm pieces and dried at
Film-forming aqueous solutions were prepared by 105 °C for 24 h. After drying, films were weighed
casting wheat starch and whey-protein isolate in the exactly to 0.0001 g, which makes up their dry mat-
following proportions: 100–0%, 75–25%, 50–50%, 25– ter. Films were individually placed in 50 mL beakers
75% and 0–100%. Glycerol was used as a plasticiser filled with 20 mL of distilled water, capped and stored
at 50% (% w/w of materials) to obtain the films not at 25 1 °C for 24 h. Film pieces were then taken
brittle, broke or cracked. Wheat starch film-forming out and dried at 105 °C for 24 h to determine the final
solutions were prepared by dissolving whey starch weight of dry matter. These steps were repeated three
powder in distilled water (5%). Whey-protein film- times. Loss of total soluble matter was calculated from
forming solutions were also prepared by dissolving the initial and final dry weight of films (Gontard et al.,
WPI in distilled water (5%). The solutions were sepa- 1994).
rately heated in a water bath with shaker under a
700 g at 85 °C for 30 min to fully gelatinise the starch
Colour
and to denature the whey protein, and then, they were
cooled down (Chen et al., 2007). Volume of each film- Colour of films was determined with a colorimeter (Mi-
forming solution poured onto a plate was controlled nolta, Model CR-300, Japan) using the CIELAB col-
and always the same to obtain the final film thickness. our parameters: L*, from black (0) to white (100); a*,
International Journal of Food Science and Technology 2014 © 2014 Institute of Food Science and Technology
Wheat starch/whey protein composite films E. Basiak et al. 3
from green () to red (+); and b*, from blue () to yel- Texture Analyser (Stable Microsystems, Godalming,
low (+) (Gennadios et al., 1996). Colour of films was Surrey, UK) according to the ASTM D882-95 method
expressed as the total colour difference (ΔE) according (ASTM, 1995). Self-tightening roller grips were used
to the following equation (Sobral et al., 2005): to perform tensile tests. The initial distance between
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi the grips and the initial velocity were adjusted to
DE ¼ ðDL Þ2 þ ðDa Þ2 þ ðDb Þ2 ð1Þ 50 mm and 1 mm s1. Mechanical properties were
calculated using the arithmetic mean of thickness of
where ΔL*, Δa* and Δb* – the differentials between each film sample.
the colour parameter of a standard used as the film
background (L* = 96.74, a* = 0.09, b* = 2.20) and the
sample colour parameter. Microstructure
Film microstructure was observed under a scanning
Water vapour sorption kinetics electron microscope (Quanta 200, FEI, Brno, Czech
Republic). A 0.5 9 0.5 cm film was fixed on the sup-
Measurement of water vapour sorption kinetics was port using silver paste, at an angle of 90° to the sur-
conducted in at least three repetitions for each type of face, which allowed observation of the cross-section of
film under conditions of constant temperature of 25 °C the film. Films were observed at a magnification of
and relative humidity of 75.3%. The samples 5009 (view) and 15009 (cross-section).
(2 9 2 cm) were removed from the dessicator and
weighed periodically for 158 h (until the samples
reached a constant mass). The experimental absorbed Statistical analysis
moisture content values were averaged and fitted by an Statistical analysis was performed with the program
exponential equation (Kowalska et al., 2006) as follows: Statgraphics Plus, version 5.0 (Manugistics Corp.,
u ¼ a þ bð1 expðcsÞ Þ ð2Þ Rockville, MD, USA). The analysis of variance (ANO-
1 VA) and Fisher’s LSD multiple comparisons were per-
where u – water content (g water g d.m. ), a, b and c formed to detect significant differences in properties of
– constant parameters of equation, s – time (h). films. The significance level used was 0.001.
The adequacy of the fitted exponential equation was
Water vapour permeability evaluated by the determination coefficient (R2) and
mean relative error (MRE) using the following equa-
Water vapour permeability of films was measured tions:
gravimetrically according to Debeaufort et al. (1993). Pn
Film samples were placed between two rubber-based ðup ue Þ2
rings on the top of three glass cells containing the fol- R ¼ Pi¼1
2
ð4Þ
n
i¼1 ðue ue Þ2
lowing: silica gel (the first one), sodium chloride (the
second one) and distilled water (the third one). By 100 X ue up
such means, the internal relative humanity (RH) of MRE ¼ u ð5Þ
n e
permeation cells at 75% and 100% was obtained. In
addition, these permeation cells were placed in a venti- where n – number of observations; up – predicted
lated chamber with maintained RH of 30% and tem- water content (g water g d.m.1); ue – average water
perature of 25 °C. Water vapour permeability was content (g water g d.m.1); ue – experimental water
calculated using the following equation: content (g water g d.m.1).
Dm e
WVP ¼ ð3Þ
A Dt Dp Results and discussion
where Dm/Dt – weight of moisture loss per unit of time First of all, during the production of composite films,
(g s1), A – film area exposed to moisture transfer some limitations related to the film formulation had to
(8.04 9 104 m2), e – film thickness (m) and Dp – be taken into account. The preparation of films based
water vapour pressure difference between two sides of on two different materials such as starch and protein
the film (Pa). Measurements were performed at least is difficult due to the isolubilisation of one of the poly-
three times. mers or to the formation of insoluble complexes
between them, especially when these two materials
have not the same pH value (6.0 for wheat starch and
Mechanical properties
6.9 for whey protein). The formation of film structure
Tensile strength and elongation at break of the films depends on the starch – protein interaction and its
(10 9 2.5 cm) were measured ten times using a TA-XT2i miscibility.
© 2014 Institute of Food Science and Technology International Journal of Food Science and Technology 2014
4 Wheat starch/whey protein composite films E. Basiak et al.
International Journal of Food Science and Technology 2014 © 2014 Institute of Food Science and Technology
Wheat starch/whey protein composite films E. Basiak et al. 5
et al. (2013) analysed the films based on cassava starch films in a ratio of 1:1 and pure protein isolate films.
and stearic acid and they noted that water solubility Analogically, samples containing 75% starch and 25%
increased with the higher concentration of stearic acid. protein isolate and 25% starch and 75% protein iso-
Lower values for water solubility could be the result late are of much higher values than the pure ones
of greater interaction between components of these (pure starch films and pure protein isolate films) and
structures. the one with a ratio of 1:1 (50S-50WP). Galus & Len-
art (2013) obtained values of ΔE of alginate/pectin
films between 1.90 and 5.49 and noted that ΔE
Colour
increased significantly with the higher content of
One of the most important parameters of food prod- pectin.
ucts, crucial for consumer’s choice, is colour. Table 2
shows colour parameters for investigated films.
Water sorption kinetics
According to the obtained results of lightness, three
homogeneous groups were observed. The first group Figure 1 shows water sorption kinetics of whey-protein
constitutes starch films (100S-0WP), starch-protein isolate/wheat starch films at relative humidity of
isolate films 1:1 (50S-50WP) and protein isolate films 75.3%. The highest water adsorption was observed for
(0S-100WP). Their values are of a similar level, and pure whey-protein films and the lowest for pure wheat
their amounts are 95.62, 95.41 and 95.39. The value starch films. Final water content was 0.264 and
for the standard (white plate) is 96.74. This means that 0.324 g water g d.m.1, in pure wheat starch and pure
samples which are in the first homogeneous group are whey-protein films, respectively. Because of the hydro-
of high lightness. The second homogeneous group philic nature of whey protein and wheat starch, high
constitutes a sample with 75% wheat starch and 25% water vapour adsorption was observed for all investi-
whey-protein isolate. Its value is 94.23. The last homo- gated films. All of the analysed films reached their
geneous group consists of a sample with 25% wheat state of equilibrium within the 24-h timeframe set for
starch and 75% whey-protein isolate. Also in this case, the tests. Water vapour sorption kinetic curves had a
the value is quite similar (94.78), which means that this similar course for investigated films. Sorption is depen-
kind of film is transparent, too. dent on relative humidity of the environment. The
Parameter a has minus values for four types of higher the relative humidity of the environment the
films. These are samples which contain starch. Their samples were stored in, the greater their ability to
values are between 0.10 and 0.81. This means that absorb water (Ciurzy nska et al., 2013). The highest
the colour of films changes to green. Parameter a for changes of dry mass for all films were observed during
whey-protein samples indicates a change of colour to the first 24 h.
red. Similar observations were obtained for other hydro-
Coefficient b values for samples of pure starch films, colloid films. Galus & Lenart (2013) observed an equi-
50% starch and 50% whey-protein films and pure librium state after 10 h of the kinetic process for pure
whey-protein films are of a similar level, and their pectin, pure alginate and composite pectin/alginate
amounts are 2.90, 3.62 and 3.92. Starch and protein films. Mali et al. (2005) also observed more rapid
isolate samples with a ratio of 3:1 (75S-25WP) and 1:3 moisture adsorption for cassava starch films at the ini-
(25S-75WP) have much higher values than the previ- tial stages of the storage at all relative humidity condi-
ous ones (pure starch films, films in a ratio of 1:1 and tions (32%, 58%, 90%). Moisture equilibrium time
pure protein isolate films). influenced by storage conditions was presented for soy
Values of total colour difference (ΔE) range from protein films as well (Cho & Rhee, 2002).
0.81 to 13.27. Similar to coefficient b, ΔE values show Measured water sorption curve data were fitted to
nearly the same trend for samples of pure starch films, an exponential equation. The constants a, b and c,
a–d
Values with different superscripts within columns are significantly different (P < 0.001).
© 2014 Institute of Food Science and Technology International Journal of Food Science and Technology 2014
6 Wheat starch/whey protein composite films E. Basiak et al.
0.3 25% wheat starch + 75% whey protein; E: 100% whey protein)
International Journal of Food Science and Technology 2014 © 2014 Institute of Food Science and Technology
Wheat starch/whey protein composite films E. Basiak et al. 7
Table 5 Tensile strength and elongation at break of composite edi- protein films plasticised with glycerol (tensile strength
ble films based o wheat starch/whey-protein isolate; (A: 100% wheat ~6.3 MPa). In all formulations, starch significantly
starch; B: 75% wheat starch + 25% whey protein; C: 50% wheat reduced the TS. Cao et al. (2007) also reported that
starch + 50% whey protein; D: 25% wheat starch + 75% whey pro-
the tensile strength of soy protein and fish gelatin com-
tein; E: 100% whey protein)
posite films increased when the content of gelatin was
Film Tensile strength (MPa) Elongation at break (%) higher. Dong et al. (2007) made composite films of
alginate and gelatin. The authors reported that TS
A 2.29 0.33a
10.22 0.81a increased when protein content increased. Also, Cham-
B 3.90 0.56b 16.17 1.11a bi & Grosso (2006) found a dependence between two
C 4.67 0.19b 76.26 8.92b
film components. The higher the gelatin content, the
D 5.10 0.89b 51.35 4.83c
E 8.90 1.01c 13.12 1.42a
higher was TS. The value of TS increased when the
amount of protein increased in mixed films.
a–c
Values with different superscripts within columns are significantly
different (P < 0.001).
Microstructure
The structure of the film depends on chemical interac-
Tensile strength values range from 2.29 (pure starch tions of film hydrocolloids and on the drying method
films 100S-0WP) to 8.90 MPa (pure protein isolate of film-forming solutions. Micrographs provide infor-
films 0S-100WP). Values for starch-protein isolate mation about how the film’s components are located
samples are between the lowest and the highest results. and how they are arranged in a film matrix (Fabra
The lowest value was for pure starch films. When et al., 2009).
more protein isolate was added, values were higher. Photographs taken with scanning electron micros-
More protein isolate caused a higher value of tensile copy (SEM) give a better insight into the homogeneity
strength. The elongation at break values for pure and the films’ microscopic structure. In Fig. 2a–j,
starch films, 75% starch and 25% protein isolate films scanning electron micrographs are presented (Fig. 2a,
and pure protein isolate films varied from 10.22 to c,e,g,i – surface and Fig. 2b,d,f,h,j – cross-section).
16.17%, whereas the values for films of starch and Starch samples (pure starch films 100S-0WP) are
protein isolate in a ratio of 1:1 and films of 25% dull, while those with protein isolate (pure whey-
starch and 75% protein isolate were a few times protein isolate films 0S-100WP) are shiny on the side
higher. Pure starch films are stiffer and more fragile facing the casting plate with the film but dull on its
than films with addition of protein isolate. Whey-pro- reverse side (Fig. 2a,j). Samples, which contain 75%
tein isolate films combined with wheat starch showed starch and 25% protein isolate are dull, while samples
greater flexibility than pure films. Rhim et al. (1998) in a ratio of 1:1 are slightly shiny on the facing side of
reported similar results of tensile properties for soy the plate, whereas samples 25% starch and 75%
Figure 2 Scanning electron micrographs of view (a,c,e,g,i; magnification 5009) and cross-section (b,d,f,h,j; magnification 15009) of wheat
starch/whey protein isolate films - a: 100% wheat starch; b: 75% wheat starch + 25% whey protein; c: 50% wheat starch + 50% whey protein;
d: 25% wheat starch + 75% whey protein; e: 100% whey protein.
© 2014 Institute of Food Science and Technology International Journal of Food Science and Technology 2014
8 Wheat starch/whey protein composite films E. Basiak et al.
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