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Biopolymer films synthesis and characterisation

Article in Journal on Processing and Energy in Agriculture · January 2017

DOI: 10.5937/JPEA1701009S

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Biblid: 1821-4487 (2017) 21; 1; p 9-12 Original Scientific Paper
UDK: 664.38 Originalni naučni rad

BIOPOLYMER FILMS SYNTHESIS AND CHARACTERISATION

SINTEZA I KARAKTERIZACIJA BIOPOLIMERNIH FILMOVA
Danijela ŠUPUT, Vera LAZIĆ, Senka POPOVIĆ, Nevena HROMIŠ, Sandra BULUT
Faculty of Technology, University of Novi Sad, 21000 Novi Sad, Bulevar cara Lazara 1, Serbia
e-mail: [email protected]

ABSTRACT
In this study, three biopolymer films were synthesized: zein (protein), gelatin (protein), and starch (polysaccharide) films and
characterized by determining mechanical and physico-chemical properties. Gelatin films proved to be the strongest (tensile strength
84 N/15 mm), while the zein were most flexible (elongation at break 41.6 %). Moisture content was higher in starch films, which is a
result of the hydrophilic nature of the polysaccharide films. Swelling degree was 22.5 % for zein, 90.9 % for gelatin, while the highest
average value was recorded in starch film samples (840.6 %). Starch films had highest value of solubility degree (36.5 %), while zein
film had 27.9 % and gelatin film had 11.85 %.Obtained characterization results are consequences of the different structure of the raw
materials and synthesis routes. All undesirable characteristics could be improved by optimizing the composition of the film, as well as
synthesis of composite/laminated films.
Key words: biopolymer films, zein, gelatin, starch, properties.

REZIME
U ovom radu sintetisana su tri biopolimerna filma različitog porekla, adekvatnim metodama sinteze. Sintetisani su zeinski i
želatinski filmovi (proteinski), kao i skrobni film (polisaharidni). Skrobni i želatinski filmovi su dobijeni iz vodenog filmogenog
rastvora, dok je zeinski film dobijen iz alkoholnog rastvora. Dobijeni filmovi su okarakterisani određivanjem mehaničkih i fizičko-
hemijskih osobina: debljina, zatezna jačina i izduženje pri kidanju, sadržaj vlage, bubrenje i rastvaranje. Želatinski filmovi su se
pokazali kao najčvršći (zatezna jačina 84 N/15mm), dok su zeinski bili najelastičniji (izduženje pri kidanju 41,6%). Izmereni sadržaj
vlage je veći kod uzoraka skrobnih filmova u odnosu na zeinske i želatinske, što je posledica načina sinteze i hidrofilne prirode
polisaharidnih filmova. Vrednost stepena bubrenja filma iznosila je 22,5% kod uzoraka zeinskog filma, a 90,9% kod uzoraka
želatinskog filma, dok su najviše prosečne vrednosti zabeležene kod uzoraka skrobnog filma i iznosile su 840,6%. Skrobni filmovi su
najrastvorljiviji u vodi (stepen rastvorljivosti 36,5%), dok je vrednost stepena rastvorljivosti kod zeinskih iznosila 27,9%, a kod
želatinskih je bila najmanja i iznosila je 11,8%.
Na osnovu dobijenih rezultata konstatuju se različite osobine ispitivanih biopolimernih filmova, koje su posledica različite
strukture polazne sirovine, kao i načina sinteze. Sve karakteristike filmova moguće je unaprediti optimizacijom sastava filma, kao i
sintezom kompozitnih ili laminiranih filmova u zavisnosti od željene primene.
Ključne reči: biopolimerni filmovi, zein, želatin, skrob, osobine.

Hydrocolloids (proteins and polysaccharides) are molecules with

INTRODUCTION expressed film forming characteristics and they are widely used
Great efforts regarding food quality improvement and shelf- to obtain biodegradable films.
life extension concurrently with minimization of packaging Based on the origin, proteins are divided into plant proteins
waste and petroleum derivatives consumption have led to (gluten, zein, soy protein, pea) and animal proteins (casein,
synthesis and application of biopolymer packaging materials whey, collagen, gelatin, keratin). Physical and chemical
(Lazić and Novaković 2010; Tharanathan, 2003). Biopolymers properties of protein films are influenced by amino acid
(IV generation of packaging) are self-destructive biodegradable composition, electrostatic charge, structure changes due to
packaging materials (Lazić and Gvozdenović 2007) and come pressure, heat, irradiation, mechanical damage, chemical and
from renewable sources. Biopolymers are consisted of polymers, enzyme actions etc. (Krochta et al., 2002). Proteins are good
which could be decomposed to eventually obtain water, CO2, film formers exhibiting excellent gas and lipid barrier properties
CH4 and biomass (McKeen, 2012). (Popović et al., 2012). Compared with synthetic films, protein-
Preparation of biopolymer films includes biopolymers based films exhibit poor water resistance and lower mechanical
dissolution or dispersion in different solvents; solution strength, susceptible to cracking due to the strong cohesive
evaporation and, finally, drying. This process (known as casting) energy density of the polymer (Han, 2014). Yet, proteins are still
is based on molecular weight reduction and polymer chains generally superior to polysaccharides in their ability to form
reorganization in the film matrix, and it has been used for the films with greater mechanical and barrier properties (Cuq et al.,
production of polysaccharide and protein biofilms (Embuscado 1998). Protein interconnection by chemical, physical or enzyme
and Huber 2009; Park et al., 2014). In order to be widely treatments improves barrier and mechanical film properties
accepted, biopolymer edible films must have food-grade quality (Senna et al., 2010; Bourtoom, 2009).
in accordance with current legislation. Polysaccharides and their derivatives (starch, cellulose,
Biopolymer films directly extracted from biomass are chitosan, alginates, pectin, carrageenan, etc.) are widely used in
usually classified according to the predominant constituent the production of biodegradable packaging materials.
material (Falguera et al., 2011). Main groups of chemical Polysaccharides are great materials for the film formation, as
compounds that serve as sources for biopolymer films are they show excellent mechanical and structural properties (Šuput
proteins, polysaccharides and lipids (Šuput et al., 2013). et al., 2015; Han, 2014). Due to hydrophilic nature of these

Journal on Processing and Energy in Agriculture 21 (2017) 1 9

 Danijela, Šuput et al./ Biopolymer Films Synthesis and Characterisation

molecules, the application of biopolymers based on grip separation was set at 50 mm, and crosshead speed was set at
polysaccharides is limited because they show poor barrier 50 mm/min. TS and EB measurements for each sample were
properties against water vapor (Falguera et al., 2011). Good repeated eight times.
barrier properties to gases and aromas, good mechanical
properties and ability to carry active components are their major Moisture content is determined as a percentage of weight
potential (Mikkonen et al., 2007). reduction during film drying, expressed on the total weight of
The efficiency of lipid components in the biopolymer film the film:
preparation depends on the nature of lipids: structure,
composition, hydrophobicity and interaction with other film MC (%) = 100 [(m2-m1) – (m3-m1)]/ (m2-m1)
components. Lipids form films which are opaque and relatively
inflexible (Rhim and Shellhammer, 2005). The lipid biofilms are where,
commonly used as coatings to protect food from moisture loss m1- mass of measuring vessel, m2- mass of film samples with
and to increase the gloss. Since lipids have water vapour measuring vessel prior drying,
permeability values, close to those of synthetic plastic films m3- mass of dried film samples with measuring vessel
(Pérez-Gago and Rhim, 2014), they are usually combined with
other biopolymers (hydrocolloids) as emulsion particles or Film solubility
multi-layer coatings in order to increase water vapour resistance Dry film samples, after moisture content determination, were
(Mehyar et al., 2004). Hydrophobic substances used for immersed in deionized water at room temperature for 30 min,
biopolymer film synthesis include natural wax (beeswax, with stirring. After 30 min, excess water was decanted and
carnauba wax, candelilla wax); petroleum-based waxes (paraffin samples were dried in the oven, for 60 min, and weighed (m4).
and polyethylene wax); petroleum, mineral and plant oils; fatty The solubility in water of the examined films was calculated:
acids and resins (shellac and wood rosin) (Pérez-Gago and Rhim
2014; Rhim and Shellhammer, 2005). Films based on waxes Solubility (%) = 100 [(m3–m1) – (m4-m1)]/ (m3–m1)
have the greatest degree of resistance to moisture migration, but
their application is limited because of its thickness, greasy where,
surfaces, and possible taste on fat. m1- mass of measuring vessel, m2- mass of film samples with
In this study, three different biopolymer films - protein and measuring vessel prior drying,
polysaccharide were synthetized and examined. The obtained m3- mass of dried film samples with measuring vessel, m4-
films were characterized by determining the mechanical and mass of dried film samples with measuring vessel after
physico-chemical properties with the aim of comparative immersion and drying
characterization of important properties for their further
application. Film swelling
Film samples (1x2 cm) were weighed (m1), and then dipped
MATERIAL AND METHOD in deionized water at room temperature, for 2 min. Lastly, the
Film synthesis samples were then removed from the water, the excess water
Zein film: Zein was dissolved (10 % w/v in 85 % ethanol) was removed by a filter paper and samples were weighed (m2).
and 0.5 g PEG 400/g zein was added and stirred until complete Swelling degree was calculated:
dissolution. Film forming solution was heated in water bath at 80
°C, poured into Petri dishes (8 g per dish) and dried at room Swelling (%) = 100 (m2 – m1) / m1
temperature. Four films were prepared.
Gelatin film: Aqueous gelatin solution 10 % (w/w) was Where,
prepared and left for 30 minutes at room temperature to undergo m1- mass of film samples prior to dipping in deionized water,
gelation, and then dissolved in a water bath at 50 °C for about 20 m2- mass of film samples after dipping in deionized water
min. Afterwards, 0.1 g glycerol/g gelatin was added and stirred.
Film forming solution was poured into Petri dishes (20 g per Statistical analysis
dish) and dried at room temperature. Four films were prepared. Statistical analysis was carried out using OriginPro 8
Starch film: Aqueous starch solution 1 % (w/w) was (OriginLab Corporation, Northampton, MA, USA). All data
prepared and 130 % of sorbitol (based on the initial weight of the were presented as mean value with their standard deviation
starch) and 0.5 % (based on the initial weight of the starch) of indicated (mean ± SD). Variance analysis (ANOVA) was
guar-xanthan modified mixture were added. Film forming performed, with a confidence interval of 95 % (p < 0.05). Means
solution was heated for 30 min in a water bath at 90 °C, poured were compared by the Tukey test.
into Petri dishes (50 g per dish) and dried at room temperature. RESULTS AND DISCUSSION
Four films were prepared.
Visual examination finds that all the obtained films were
Methods transparent, shiny, odorless and free of cracks or residual air
Film thickness was measured using a micrometer with bubbles (Figure 1). Zein films had the most pronounced dark
sensitivity of 1 µm. Thickness measurements were carried out on yellow color, while starch films were completely transparent,
each film at 8 different positions. without a hint of yellow. The strongest, but also the most non
elastic, were gelatin films. It was confirmed that the casting was
Mechanical properties the simplest way to produce the films in laboratory conditions.
Tensile strength (TS) and elongation to break (EB) were
measured on the Instron Universal Testing Instrument Model No
4301 (Instron Engineering, Canton, Massachusetts, USA),
according to the standard method EN ISO 527-3:1995. Film
samples were cut into rectangular strips (15x80 mm). The initial

10 Journal on Processing and Energy in Agriculture 21 (2017) 1

 Danijela, Šuput et al./ Biopolymer Films Synthesis and Characterisation

Solubility (%)
45
40
35
30
25
20
15
10
5
0
zein gelatin starch

Fig. 1. Visual examination of various biopolymer films: Fig. 2. Solubility of various biopolymer films
1. Zein 2. Gelatin 3. Starch This leads to local dissolution of the hydroxyl group and the
polymer swelling, releasing new groups as active binding sites
The results of mechanical properties examination are shown (Bertuzzi et al, 2007; Ludwiczak and Muha, 2010). The values of
in Table 1. Film thickness varied in the range from 84.1 μm to investigated biopolymer films swelling degree are shown in
172.9 μm, for starch and gelatin film, respectively. Thickness Figure 3.
values were significantly different (p<0.05).

Table 1.Mechanical properties of various biopolymer films Swelling (%)

Film Thickness Tensile strength Elongation at 1000
sample (μm) (N/15mm) break (%) 900
b b a
Zein 131.4 ±39.1 4.4 ±1.5 41.6 ±8.5 800
a a b
Gelatin 172.9 ±27.1 84.0 ±23.4 2.0 ±2.1 700
c b b
Starch 84.1 ±6.9 8.3 ±2.8 1.6 ±0.9 600
500
Basic indicators of mechanical properties of packaging
400
materials are tensile strength (TS) and elongation at break (EB).
The results, of mechanical properties of the tested films are 300
shown in Table 1. Gelatin films had highest tensile strength (84 200
N/15 mm), while zein and starch films were not significantly
different (p>0.05). The most flexible samples were zein films, as 100
evidenced by the elongation at break value (41.6 %), compared 0
to significantly lower values for samples of gelatin and starch zein gelatin starch
films (see Table 1). Compared with many synthetic polymers, Fig. 3. Swelling degree of various biopolymer films
tensile strength and elongation at break values of biopolymer
films are quite low, but enough to make these films find The lowest swelling degree value was measured in the
application in the food industry (Souza et al., 2013, Park et al., samples of zein film and amounted to 22.5 %, while swelling
2014). degree for the gelatin film sample was 90.9 %. The highest
Moisture content was higher in the starch films samples average values were recorded in the sample of starch films and
(17.9 %) in relation to zein (9.1 %) and gelatin (10.2 %), which amounted up to 840.6 %. Such high values of the degree of
may be related to the synthesis route and the hydrophilic nature swelling are the result of highly hydrophobic starch nature.
of the polysaccharide film. Moisture content and the swelling degree were in correlation,
Film solubility and swelling are connected with the water which was in accordance with previous findings (Šuput et al.,
diffusion, the ionization of the carboxyl and amino groups, 2016; Fabra et al., 2010).
dissociation of hydrogen and ionic bonds and with relaxation of The solution of this problem can be the crosslinking or
the polymer in the presence of moisture (Mathew et al., 2006). addition of some other polymer, or some lipid components, in
Solubility values for all examined biopolymer films are less than order to lower the water solubility, as well as the swelling
40%, which is in agreement with earlier studies (Nguyen, 2012). degree. Also, film aging may leads to moisture content reduction
The highest solubility value was recorded in case of starch film and solubility reduction due to increased networking (García et
samples (36.5 %), and the lowest solubility value was recorded al., 2004; Bourtoom and Chinnan, 2009).
in case of gelatin film samples (11.8 %). Swelling is undesirable
characteristic when choosing packaging materials for a specific CONCLUSION
purpose, such as packaging of food with high moisture content.
In contact with water, polar water molecules are attracted to the The purpose of this work was to present the possibility of
hydrophilic surface of the film, and then penetrate into the using different laboratory synthesis techniques for the
matrix, binding to its polar groups (Ganji et al., 2010). production of biopolymer films of various origins. The produced

Journal on Processing and Energy in Agriculture 21 (2017) 1 11

 Danijela, Šuput et al./ Biopolymer Films Synthesis and Characterisation

films showed different characteristics in terms of their Ludwiczak, S.,Mucha, M. (2010). Modeling of water sorption
mechanical and physico-chemical properties. These results are isotherms of chitosan blends, Carbohydrate Polymers, 79 (1),
consequences of different structure of the raw materials and 34-39.
synthesis routes. Based on visual examination it was found that Mathew, S., Brahmakumar, M., Abraham, T. E. (2006).
all the obtained films were transparent, shiny, odorless and free Microstructural imaging and characterization of the
of cracks or residual air bubbles. The strongest films were made mechanical, chemical, thermal, and swelling properties of
of gelatine, while zein films were the most elastic, which starch- chitosan blend films. Biopolymers, 82 (2), 176-187.
correlated well with the results of mechanical properties. The McKeen, L.W. (2012). Introduction to Use of Plastics in Food
highest moisture content and swelling degree, which were in Packaging. In: Ebnesajjad, S.(Ed.): Plastic Films in Food
correlation, were recorded for the starch film samples and lowest Packaging. Elsevier.
for the zein film samples. Solubility values for all examined Mehyar, G.F., Han, J.H. (2004). Physical and mechanical
biopolymer films were less than 40 %. properties of high-amylose rice and pea starch films as affected
The obtained results are the characteristic related to the by relative humidity and plasticizer. Journal of Food Science,
nature of examined biopolymers. As in synthetic polymers, also 69 (9), E449–E454.
biopolymer materials, as monomaterials rarely could Mikkonen, K.S., Rita, H., Helén, H., Talja, R.A., Hyvönen, L.,
demonstrate optimal characteristics. However, all undesirable Tenkanen, M. (2007). Effect of polysaccharide structure on
characteristics could be improved by optimizing the composition mechanical and thermal properties of galactomannan-based
of the film, as well as synthesis of composite/laminated films. films.Biomacromolecules. 8 (10), 3198-3205.
This work has been the basis for further development and Nguyen, M.X.H. (2012). Characterization of allergenic and
improvement of biopolymer materials with great potential for antimicrobial properties of chitin and chitosan and formulation
application in the food industry. of chitosan-based edible film for instant food casing. School of
Applied Sciences.RMIT University, Melbourne, Australia.
ACKNOWLEDGEMENT: This work is part of the project
Park, H.J., Byun, Y.B., Kim, Y.T., Whiteside, W.S., Bae, H.J.
TR-31055, financed by the Ministry of education, science and
(2014). Processes and applications for edible coating and film
technological development, Republic of Serbia.
materials from agropolymers. In: Han J.H. (Ed): Innovations in
REFERENCES Food Packaging. Academic Press, San Diego, CA, USA.
Pérez-Gago, M.B., Rhim, J.W. (2014). Edible coating and film
Bertuzzi, M.A., Vidaurre, E.F.C., Armada, M., Gottifredi, J.C. materials: Lipid Bilayers and Lipid Emulsions. In: Han J.H.
(2007). Water vapor permeability of edible starch based films. (Ed): Innovations in Food Packaging. Academic Press, San
Journal of Food Engineering, 80, 972-978. Diego, CA, USA.
Bourtoom, T. (2009). Protein edible film: Properties Popović, S., Peričin, D., Vaštag, Z., Lazić, V., Popović, Lj.
enhancement. International Food Research Journal, 16 (1), 1-9. (2012). Pumpkin oil cake protein isolate films as potential gas
Bourtoom, T.,Chinnan, M.S. (2009). Improvement of Water barrier coating. Journal of Food Engineering, 110 (3), 374-379.
Barrier Property of Rice Starch-chitosan Composite Film Rhim, J.W., Shellhammer, T.H. (2005). Lipid-based edible films
Incorporated with Lipids. Food Science and Technology and coatings. In: Han J.H. (Ed):Innovations in Food
International,15 (2), 149-158. Packaging, Elsevier, London.
Cuq, B., Gontard, N., Guilbert, S. (1998).Proteins as Senna, M.M., Salmieri, S., El-naggar, A.W., Safrany, A.,
Agricultural Polymers for Packaging Production. Cereal Lacroix, M. (2010). Improving the Compatibility of Zein/Poly
Chemistry, 75 (1), 1–9. (vinyl alcohol) Blends by Gamma Irradiation and Graft
Embuscado, M.E., Huber, K.C. (2009).Edible films and coatings Copolymerization of Acrylic Acid. Journal of Agricultural and
for food applications, Springer Science+Business Media LLC. Food Chemistry, 58 (7), 4470–4476.
Fabra M.J., Talens P., Chiralt A. (2010). Water sorption Souza, A.C., Goto, G.E.O., Mainardi, J.A., Coelho, A.C.V.,
isotherms and phase transitions of sodium caseinate-lipid as Tadini, C.C. (2013). Cassava starch composite films
affected by lipid interactions. Food Hydrocolloids, 24 (4), incorporated with cinnamon essential oil: Antimicrobial
384–391. activity, microstructure, mechanical and barrier properties.
Falguera,V., Quinterob, J.P., Jimenez, A., Munoz, J.A., Ibarz, A. LWT - Food Science and Technology, 54 (2), 346-352.
(2011). Edible films and coatings: Structures, active functions Šuput D., Lazić, V., Pezo, L., Markov, S., Vaštag, Ž., Popović,
and trends in their use. Trends in Food Science & Technology, Lj., Radulović, A., Ostojić, S., Zlatanović, S., Popović, S.
22 (6), 292-303. (2016). Characterization of Starch Edible Films with Different
Ganji, F., Vasheghani-Farahani, S., Vasheghani-Farahani, E. Essential Oils Addition. Polish Journal of Food and Nutrition
(2010). Theoretical Description of Hydrogel Swelling: A Science, 66 (4), 277-285.
Review. Iranian Polymer Journal, 19 (5), 375-398. Šuput D., Lazić, V., Pezo, L., Radulović, A., Popović, S.,
García, M.A., Pinotti, A., Martino, M. N., Zaritzky, N.E. (2004). Hromiš, N., Bulut, S. (2015). Structural changes in starch
Characterization of composite hydrocolloid films. during starch based edible films synthesis. Journal on
Carbohydrate Polymers, 56 (3), 339–345. Processing and Energy in Agriculture, 19 (3), 139-142.
Han, J.H. (2014). Innovations in food packaging.Elsevier, Šuput, D., Lazić, V., Jelić, A., Lević, Lj., Pezo, L., Hromiš, N.,
Academic Press, USA. Popović, S. (2013). The effect of sorbitol content on the
Krochta, J.M. (2002). Proteins as raw materials for films and characteristics of starch based edible film. Journal on
coatings: definitions, current status and opportunities. Processing and Energy in Agriculture, 17 (3), 106-109.
In:GenadiosA. (Ed.): Protein-based films and coatings., CRC Tharanathan, R.N. (2003). Biodegradable films and composite
Press, Boca Raton. coatings: past, present and future. Trends in Food Science
Lazić, V., Gvozdenović, J. (2007).Biopolimeri kao ambalažni Technology, 14 (1), 71-78.
materijali. Prehrambena Industrija, 1-2, 19-22.
Lazić, V., Novaković, D. (2010).Ambalaža i životna sredina,
University of Novi Sad, Novi Sad, Serbia. Received: 02. 02. 2017. Accepted: 31. 03. 2017.

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