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Food Packaging and Shelf Life 24 (2020) 100485

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Food Packaging and Shelf Life


journal homepage: www.elsevier.com/locate/fpsl

Heat sealable soluble soybean polysaccharide/gelatin blend edible films for T


food packaging applications
Chang Liu, Jiao Huang, Xuejing Zheng, Shujie Liu, Kuakua Lu, Keyong Tang, Jie Liu*
School of Materials Science and Engineering, Zhengzhou University, Zhengzhou, Henan 450001, China

ARTICLE INFO ABSTRACT

Keywords: The present study aimed to develop heat sealable soybean polysaccharide (SSPS)/gelatin blend films intended to
Edible film be used as edible food packaging materials. The films were fabricated by solution casting method using SSPS/
Soluble soybean polysaccharide gelatin blends and plasticized by glycerol. The results indicated that the heat sealability, stretchability and
Gelatin resistance to fracture of the films were significantly improved by blending SSPS with gelatin. The incorporation
Heat seal
of gelatin into SSPS films also increased the thermal stability but decreased the water solubility, rigidity and
Food packaging
water vapor permeability of the films. ATR-FTIR spectra and DSC results indicated strong interactions between
SSPS and gelatin. The studies of optical properties, SEM, AFM, and XRD revealed that SSPS and gelatin were
compatible to a certain degree in this blend system. Packaging tests confirmed that the blend films have showing
potential as edible material in food packaging.

1. Introduction coated orange oil emulsions (Nakamura, Furuta, Kato, Maeda, &
Nagamatsu, 2003; Zhao, Wei, Wei, Yuan, & Gao, 2015). Recently, SSPS
A large part of materials currently used for food packaging are non- films cast from aqueous solution were studied with a view to develop
degradable synthetic plastics produced from non-renewable fossil re- suitable candidate for food packaging applications. It was found that
sources. Their increasing production, application, discard and accu- SSPS could be used to produce free-standing films with acceptable
mulation have been regarded as serious threats to our society and the physical properties (Tajik et al., 2013). Further studies have been per-
environment. In an attempt to protect the environment and reduce the formed to address the influence of ZnO, essential oil, nanoclay, nano-
cost of controlling plastic pollution, many countries and districts are TiO2, nano-SiO2 on the structure and properties of SSPS films
starting to gradually reduce the use of single-use plastics in food (Alipoormazandarani, Ghazihoseini, & Nafchi, 2015; Ghazihoseini,
packages. Among the various promising solutions, the production of Alipoormazandarani, & Nafchi, 2015; Salarbashi et al., 2013, 2016;
films from bio-based renewable resources, such as naturally derived Salarbashi et al., 2017; Salarbashi, Tafaghodi, & Bazzaz, 2018; Shaili,
proteins and polysaccharides, provides an important class of eco- Abdorreza, & Fariborz, 2015). On the basis of the highly water solu-
friendly packaging materials to replace non-renewable synthetic plas- bility and excellent film forming property of SSPS, the influence of SSPS
tics (Cazón, Velazquez, Ramírez, & Vázquez, 2017). edible coating on the quality of fruits has been investigated (Dyshlyuk,
Soluble soybean polysaccharide (SSPS), a polysaccharide extracted Babich, Belova, & Prosekov, 2017). The results of these studies strongly
from soy cotyledons, has the potential in producing bio-based films for suggested that SSPS has the property of being a useful film-forming
food packaging applications. The major component of SSPS composed agent for production of food packaging films.
of short-chain homogalacturonan and long-chain rhamnogalacturonan In some practical food packaging applications, edible films are
backbones with a number of branches, including sugar chains of β-1,4- preferred to be processed into soluble pouches, bags, packets or sachets
galactans and α-1,3- or α-1,5-arabinans (Nakamura, Furuta, Maeda, to contain powdered substances, such as seasoning and flavoring ad-
Takao, & Nagamatsu, 2002). SSPS has excellent water solubility, anti- ditives for instant foods, instant coffee, coconut powder, milk powder,
oxidative property, good film-forming ability, emulsifying property, noodles, beverage mixes, edible dyes, tea leaf, and other food additives
and nutritional value. Thus, it has found increased application in the (Das & Chowdhury, 2016). The most prominent advantage of using
past several years mainly in food and beverage industry. For example, such a packaging system is that the edible packages carrying pre-
SSPS has been used to stabilize acid milk dispersions and lactoferrin- weighed quantity of products could be put in use directly without waste


Corresponding author.
E-mail address: liujie@zzu.edu.cn (J. Liu).

https://doi.org/10.1016/j.fpsl.2020.100485
Received 4 November 2019; Received in revised form 3 February 2020; Accepted 10 February 2020
2214-2894/ © 2020 Elsevier Ltd. All rights reserved.
C. Liu, et al. Food Packaging and Shelf Life 24 (2020) 100485

disposal problem. This is similar to the use of capsules as drug delivery with gently stirring. Glycerol was used as a plasticizer to achieve the
vehicles. To achieve this goal, good sealability and sufficient seal concentration of 40 wt.% of total solid. Then, a fixed amount of blend
strength of the films are important to avoid the failure of the pouches or solution was cast onto leveled plastic Petri dishes (diameter =24 cm)
sachets and the release of the packed substances. Heat sealing, which and dried at 50 °C for 12 h. Afterwards, the films were peeled off from
allows for the binding of two films by pressing them between plates or the dishes and stored over silica gel in a desiccator for 7 d before
jaws under heating condition, is widely used in packaging industry to analysis, unless otherwise stated. SSPS/gelatin blend films with weight
produce containers due to its simplicity and cost-effectiveness. Un- ratios of 100/0, 80/20, 60/40, 40/60, 20/80, 0/100 were coded as
fortunately, our preliminary studies have shown that neat SSPS films S100G0, S80G20, S60G40, S40G60, S20G80, and S0G100, respectively.
exhibited poor heat sealability which limits their further applications as The thickness of the films was measured with an electronic digital
packaging materials. Alipoormazandarani et al. (2015) have found that micrometer (model 5130, G-CRAFT, Zhejiang, China).
the seal strength of SSPS film was enhanced through the incorporation
of halloysite nanoclay, and therefore the SSPS/nanoclay films are 2.3. Characterization
considered as heat sealable materials and may have potential applica-
tions in packaging industries. In addition to this report, there have been 2.3.1. Attenuated total reflectance Fourier transform infrared (ATR-FTIR)
very limited studies on the development of heat sealable SSPS-based spectroscopy
edible films. The ATR-FTIR spectra of different films were recorded with a Model
Gelatin is a bio-based protein obtained from animal collagen by a Equinox 55 FTIR spectrometer (Bruker Co., Ettlingen, Germany), using
hydrolysis reaction. There have been many studies aimed at producing a horizontal ATR Trough plate crystal cell (45° ZnSe,
gelatin-based blend films with different properties, and have demon- 80 mm × 10 mm×4 mm) (PIKE Technology Inc., Madison, WI, USA).
strated that gelatin is an excellent film-forming material (Suderman, For each spectrum, 32 scans were continuously collected in the range of
Isa, & Sarbon, 2018). Gelatin could form a physically crosslinked net- 800−4000 cm−1 at a resolution of 4 cm−1.
work in the blend systems which may give strong and flexible films
when plasticized suitably. For instance, gelatin has been blended with 2.3.2. X-ray diffraction (XRD)
chitosan (Hosseini, Rezaei, Zandi, & Ghavi, 2013), starch (Fakhouri, An X-Ray diffractometer (Empyrean, PANalytical, Netherlands) was
Martelli, Caon, Velasco, & Mei, 2015), soy protein isolate (Cao, Fu, & used to obtain XRD patterns of different films. Each sample was scanned
He, 2007), and carboxymethyl cellulose (CMC) (Nur Hazirah, Isa, & over a diffraction angle 2θ from 5 to 60° using Cu Kα radiation (λ
Sarbon, 2016) etc. to achieve improved performance in packaging ap- =1.5418 Å), 40 kV and 30 mA with a scan rate of 0.05°/s.
plications. Additionally, heat sealability of gelatin-based films has been
extensively studied (Nur Hanani, O’Mahony, Roos, Oliveira, & Kerry, 2.3.3. Differential scanning calorimetry (DSC)
2014; Tulamandi et al., 2016). It was found that gelatin generally DSC measurements were conducted on a DSC 204 instrument
presents better heat sealability than those of other common biopoly- (Netzsch, Germany). 3∼5 mg of samples were accurately weighed into
mers due to its inherent chemical structure (Abedinia, Ariffin, Huda, & aluminium crucibles and the analyses were performed under nitrogen
Nafchi, 2018). flow. In order to avoid the potential effect of moisture evaporation on
In order to develop an edible and heat sealable SSPS-based film for glass transition of polymers, the samples were first heated from 20 to
food packaging application, this research aims to evaluate the effects of 130 °C at a heating rate of 10 °C/min, then cooled to 5 °C at 20 °C/min,
different ratios of SSPS/gelatin on the heat sealing, mechanical, and subsequently reheated from 5 to 300 °C at 10 °C/min. DSC data of
thermal, barrier, and optical properties of blend films. The films were each film were collected during the 2nd heat run.
prepared by blending SSPS and gelatin in different weight ratios and
plasticized with glycerol. Additionally, the films were examined by 2.3.4. Scanning electron microscopy (SEM)
attenuated total reflectance Fourier transform infrared (ATR-FTIR) Surface and cross-section morphologies of the films were observed
spectroscopy, X-ray diffraction (XRD), scanning electron microscopy by SEM (Phenom proX, Phenom-World BV, Netherlands). Films were
(SEM), and atomic force microscopy (AFM). We expected that the ad- immersed in liquid nitrogen for about 5 min and then fractured with
dition of gelatin could widen the application of SSPS-based films in food tweezers before SEM analysis. The specimens were mounted on alu-
packaging. minum stub using conductive tape and sputtered with a thin layer of
gold for SEM observation at an acceleration voltage of 20 kV.
2. Material and methods
2.3.5. Atomic force microscopy (AFM)
2.1. Materials The 3D surface topography of representative films was recorded by
atomic force microscopy in tapping-mode using a Keysight’s 5500
SSPS (molecular weight 470∼520 kDa, measured by size exclusion (N9410S, Keysight Technologies Canada Inc., Canada) atomic force
chromatography (SEC)) was kindly provided by JinJing Bio. Co. Ltd. microscope. All images of 256 × 256 pixels were acquired by scanning
(Pingdingshan city, Henan, China). Type A porcine skin gelatin with square areas of 5 μm × 5 μm with a scan speed of 0.3 line/s.
bloom value of approximately 300 g was obtained from Sigma Aldrich
(St. Louis, MO, USA). Glycerol was purchased from Aladdin Reagent Co. 2.3.6. Mechanical properties
Ltd. (Shanghai, China). De-ionized water was produced by a Milli-Q The mechanical properties of films were measured in tensile mode
water purification system (Millipore, Bedford, MA, USA). using a SMSTA.XTPLUS texture analyzer (Stable Micro System, UK).
Films were cut into dumbbell-shaped specimens and then conditioned
2.2. Preparation of the films at 25 ± 1 °C and 50 ± 2 % relative humidity for 7 d in an environ-
mental chamber (BH-TH-50, SH Guangpin (Bogong) Test Equipment
All films with different blending weight ratio of SSPS and gelatin Manufacturing Co. Ltd., Shanghai, China) before testing. The initial grip
were prepared using conventional solvent casting technique. SSPS was separation was set at 30 mm and the specimens were pulled apart at a
stirred into de-ionized water at 85 °C for 30 min to achieve a clear so- crosshead speed of 10 mm/min. Five replicates of each film were tested.
lution. Gelatin solution was obtained by dissolving gelatin powder in
de-ionized water and stirred at 60 °C for 30 min. For the preparation of 2.3.7. Optical properties
blend solution, gelatin solution was slowly added into the SSPS solution The transmittance of the films was recorded with a TU-1901 UV/vis
to make a final solid content of 5.0 % (w/v) and heated at 60 °C for 2 h spectrophotometer (Purkinje General Instrument Co. Ltd., Beijing,

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China). The transparency value was then calculated as follows: 2.3.12. Packaging tests
A series of 3-side sealed pouches were fabricated from the neat SSPS
Transparency value = log T600nm/ L (1)
(S100G0) and S60G40 blend films (100 mm × 50 mm), using the same
where T600nm is the transmittance of film specimens at 600 nm, L is the heat sealing machine and conditions mentioned above. Two kinds of
average thickness of the specimens (mm). The lower the transparency dry powders, instant coffee and coconut powders, were transferred
value, the higher transparency of the films. manually into the 2-side sealed semi-finished pouches and the whole
pouches were heat sealed immediately with each pouch containing
2.3.8. Water vapor permeability (WVP) 3.0 g of powder. Subsequently, the sealed pouches containing powders
WVP of films was evaluated by the modified method of ASTM were stored at 25 ± 1 °C over silica gel for 7 d. In order to test the
standard E96-05 (Yu, Yang, Liu, & Ma, 2009). The films were cut into solubility of the edible pouches in hot water, these pouches were put
circular samples and sealed onto a circular test cups (diameter 45 mm) into hot water (95 ± 2 °C) under gently stirring.
containing 50 mL of de-ionized water, with a distance of 2 cm between
the film and water surface. The test cups were placed into a desiccator 2.3.13. Statistical analysis
over silica gel (0 % RH) at 20 °C. The weight of the cups was recorded at Statistical analysis was performed using a commercial SPSS pro-
intervals of 24 h over a 7-d period. The WVP value of the films was gram (SPSS 13.0, SPSS INC., Chicago, Illinois, USA). The data were
calculated using Eq. (2): expressed as mean ± standard deviation (SD) and p < 0.05 was taken
WVTR × L as the minimal level of significance. One-way analysis of variance
WVP =
(2) (ANOVA) approach was applied and means were compared using
P×A
Duncan’s multiple range tests.
where WVTR represents water vapor transmission rate obtained from
the slope of plot of weight loss vs. time. ΔP is the the water vapor 3. Results and discussion
pressure difference across the film (kPa), and A is the area of the film
(m2). 3.1. Thickness and optical properties

2.3.9. Water solubility All the films produced are flexible, self-supporting, and transparent
The water solubility of the films at 25 °C was assessed according to (Fig. S2), with thickness ranging between 105.2 and 124.8 μm (Table
the method of Kurt, Toker, and Tornuk (2017) with slight modifica- S1). The incorporation of gelatin has no significant effect on the
tions. Films were cut into rectangle pieces (20 mm × 20 mm) and dried thickness of the films (p > 0.05). Similar results were presented for the
at 105 °C to constant weight (Wi). The samples were immersed in 50 mL starch/gelatin film containing different plasticizers (Fakhouri et al.,
of de-ionized water for 15 h. Then, the solution containing the films was 2015).
filtered through stainless steel mesh, and the insoluble matter was dried Since colorless and transparent films are preferred in practical food
at 105 °C for 24 h. The dry residue was weighed (Wr) and the film water packaging applications, measurements of the color and transparency of
solubility was calculated as follows: the SSPS/gelatin films were performed and the results are shown in
Wi Wr Table S1 and 1. In the UV range from 200 to 280 nm, all films show
Water solubility(%) = × 100 good UV barrier properties, which thus help to retard lipid oxidation
Wi (3)
and discoloration in packaged food products. This result has also been
reported for other polysaccharide/gelatin blend films (Soo & Sarbon,
2.3.10. Equilibrium moisture content (EMC) 2018). The transparency value of the SSPS/gelatin films ranged from
The as-prepared films, vacuum dried at 60 °C for 24 h, were placed 0.385 to 1.043, which is similar to the value reported for gelatin/
inside a desiccator maintained at 59 % RH provided by a saturated chitosan blend edible films (Hosseini et al., 2013). With the increase of
solution of NaBr at 20 °C for 7 d. After drying in an oven at 110 °C for gelatin weight fraction from 0 % to 20 %, the transparency value in-
20 h, the dry weight of samples was determined to calculate the EMC creased from 0.663 to 1.043. This may be due to the presence of in-
value according to the following equation: soluble particles in the blend film, or the occurance of micro-phase
Weq Wd separation phenomena (Núñez-Flores et al., 2013). With further in-
EMC (%) = × 100 crease in gelatin weight fraction from 20 % to 100 %, the films became
Wd (4)
more transparent. Cao et al. (2007) reported a similar trend for soy
where Weq is the weight of the sample when reached equilibrium, Wd is protein isolate/gelatin composite films with an increase in the gelatin
the dry weight of the sample. weight fraction. Anyhow, the transparency results confirm that all films
are clear enough for food packaging. The SSPS/gelatin films are more
2.3.11. Heat seal strength transparent than the commonly used commercial synthetic food
Films were cut into strips of 20 mm × 70 mm. Two strips were faced packaging films such as low density polyethylene (LDPE) (transparency
together, and an area of 20 × 10 mm2 near the edge of the strip was value 4.26) and oriented polypropylene (transparency value 1.57)
heat sealed using a heat sealing machine (HST-H6, Labthink (Guerrero, Nur Hanani, Kerry, & de la Caba, 2011; Ramos et al., 2013).
Instruments Co. Ltd., China) at 150 ± 1 °C for 1.50 s of dwell time, and
the heat seal pressure was 300 kPa, as shown in Fig. S1. The width of 3.2. ATR-FTIR spectroscopy
the heat-sealed area was 10 mm. After heat sealing, specimens were
conditioned at 25 ± 1 °C and 50 ± 2 % RH for 48 h before the testing. ATR-FTIR spectra of the SSPS/gelatin films are shown in Fig. 1A.
The peel strength of the heat-sealed samples was determined according The spectrum of neat gelatin film shows several characteristic bands at
to Standard ASTM F-88 with slight modifications (American Society for approximately 3295 cm−1 (amide A, NeH stretching), 1633 cm−1
Testing and Materials (ASTM, 2005), using SMSTA.XTPLUS texture (amide I, C]O stretching), 1542 cm−1 (amide II, NeH bending and
analyzer (Stable Micro System, UK), at 25 ± 1 °C and 50 ± 2 % RH. CeN stretching), and 1235 cm−1 (amide III, in-plane vibration of CeN
Each leg of the sealed film was clamped to the machine and peeled open and NeH groups of bound amide) (Hosseini et al., 2013; Kumar,
at 180° angle (Fig. S1). The initial distance between the clamps (grip Shukla, Baul, Mitra, & Halder, 2018; Staroszczyk, Pielichowska, Sztuka,
length) was 5.0 cm. The crosshead speed was set at 1 mm/s. Seal Stangret, & Kołodziejska, 2012). The spectrum of neat SSPS film shows
strength (N/m) was calculated as follows: seal strength = (the max- broad band at 3305 cm−1 (hydroxyl groups), which are capable of in-
imum load required to cause seal failure/seal width). teracting with hydroxyl and amino groups in protein by creating

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Fig. 1. (A) ATR-FTIR spectra, (B) second-derivative ATR-FTIR spectra, (C) XRD patterns, and (D) DSC thermograms in the range of 5−180 °C of SSPS/gelatin films
with different weight ratios.

hydrogen bonds. The strong peak observed at 1031 cm−1 is related to changes suggest the presence of strong interactions between gelatin and
the CeO stretching vibrations of glycoside structure (Salarbashi et al., SSPS.
2017). Especially, the bands at 1740 cm-1 and 1615 cm−1 are derived
from carbonyl (C]O) stretching vibration, which indicate the presence 3.3. X-ray diffraction
of ester groups in SSPS. Similar bands have also been observed in other
works (Salarbashi et al., 2018). The spectra of blend films generally The XRD characterization of the films was carried out and the re-
retain the characteristic peaks of SSPS and gelatin in proportion to their sults are shown in Fig. 1C. The neat SSPS film exhibits semi-crystalline
weight ratio. However, subtle differences in the position of the char- structure with two neighboring bumps centered at around 2θ = 22.8°
acteristic peaks clearly indicate the bonding of components in the blend and 15.7°, revealing that the film has a short-range order structure. The
films. The absorption bands near 3305 cm−1 become sharper and shift XRD pattern of neat gelatin film shows only one broad diffraction peak,
to lower wavenumbers with increasing weight fraction of gelatin. This confirming it to be an amorphous polymer. Similar results have been
phenomena has been considered to be related to the formation of water- reported in the literature regarding gelatin films prepared by solution
mediated hydrogen bonds (Yakimets et al., 2007). At the same time, the casting process (Nagahama et al., 2009; Sang et al., 2017). However,
peak observed at 1031 cm−1 of neat SSPS shifts to 1036 cm−1 after some studies have reported that a sharp strong peak at about 2θ = 7°,
incorporation of gelatin. The main characteristic bands of gelatin amide corresponding to the triple helix structure, can be observed in the XRD
I, II and III are also shift to higher frequencies after blending with SSPS, patterns of gelatin films (Alexandre, Lourenço, Bittante, Moraes, &
which may be related to the alternations in secondary structure of ge- Sobral, 2016). The absence of such a peak in the present diffractograms
latin polypeptide chains in blend films. could be explained by the low triple helix content as a result of the high
Second-derivative FTIR spectrum can be used to resolve overlapping drying temperature (50 °C in the present study) (Badii, MacNaughtan,
peaks in FTIR spectra. Fig. 1B shows the comparison of second-deri- Mitchell, & Farhat, 2015). This temperature is much higher than the
vative ATR-FTIR spectra of neat SSPS and gelatin films with blend film gelation temperature of gelatin (∼32 °C), thus the biopolymer chains
of S60G40 in the range of 1800−1200 cm−1. The peaks at 1695 cm−1, are difficult to regenerate the helix structure during the drying process.
1660 cm−1 and 1628 cm−1, assigned to carboxyl groups, free-fold α- Additionally, the presence of the diffraction peak observed at about
helix, and imide residues of gelatin, can be observed in the spectrum of 2θ = 15.7° of blend films S80G20, S60G40, S40G60 was likely the re-
blend film (Nakamura et al., 2002; Staroszczyk, Sztuka, Wolska, sult of slight separation phase of the two components. With the increase
Wojtasz-Pająk, & Kołodziejska, 2014). The disappearance of a strong in gelatin weight fraction, this peak gradually weakened, illustrating
peak in the spectrum of blend film at 1549 cm−1, corresponding to that the incorporation of amorphous gelatin suppressed the crystalline
single α-helix peak in the region of amide II band, indicates that the peak of SSPS and resulted into an amorphous matrix of the two com-
interactions between formulation components may affect the helical ponents. This implies an improved compatibility between SSPS and
structure of gelatin (Taravel & Domard, 1995). Overall, the spectra gelatin, which is mainly due to the strong hydrogen bonding interaction

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between SSPS and gelatin molecules (Chen, Wang, Mao, Liao, & Hsieh, groups may provide polymer-water bonding sites within the films. The
2008). A study conducted by Nagahama et al. (2009) reported a similar EMC (at 20 °C and 59 % RH) and WVP data reported here revealed a
reduction of XRD peak intensity ratio when gelatin was added to chit- reduction in hydrophilicity of the SSPS film upon addition of gelatin.
osan membranes. These results were consistent with those observed in the DSC and TG
studies, as discussed above. The WVP value of S80G20 was slightly but
3.4. Thermal properties significantly (p < 0.05) higher than those of neat SSPS and gelatin
films, this result may be related to a micro-phase separation phenom-
DSC has been used as a powerful tool to characterize the thermal enon (Núñez-Flores et al., 2013), which can also be observed in optical
transition of polymers in various forms. Fig. 1D shows the DSC ther- studies. The decrease in WVP values upon addition of more gelatin in
mograms in the range of 5−180 °C of SSPS/gelatin films of different SSPS would be beneficial for improving the stability of packed food
compositions. All films exhibit step-like endothermic transitions cor- products, since efficient barrier ability against water vapor is of quite
responding to the glass transition of the biopolymers. Glass transition importance in controlling moisture content inside food packages.
temperature (Tg) is an important characteristic of amorphous polymeric
materials affecting their properties and potential application fields. 3.6. Microstructure of the films
However, it has been reported that the glass transitions of plasticized
polysaccharides are sometimes difficult to detect by DSC technique The SEM micrographs of surface and cross-section of SSPS, gelatin
(Avérous, Fringant, & Moro, 2001). For neat SSPS film plasticized with and their blend films are shown in Fig. 2. Neat SSPS film exhibits fairly
glycerol, the glass transition appeared with a weak magnitude and the smooth, homogeneous surface and compact cross-section structure
Tg was observed at temperature of 17.8 °C. Similar Tg values have also without distinct pores and cracks, which are comparable with those
been reported by other researchers (Shaili et al., 2015; Tajik et al., observed by Tajik et al. (2013) on glycerol-plasticized SSPS films. In the
2013). For S80G20, S60G40, and S40G60, subtle glass transition events case of neat gelatin film (Fig. 2 F2), the micrograph also shows a con-
were visible and these samples exhibited two Tg values corresponding tinuous, flat and smooth surface, this is associated with the better
to two phases: a SSPS-rich one and a gelatin-rich one. The Tg values of physical properties of gelatin film. On the other hand, some cracks can
gelatin were gradually increased from 49.2 to –54.4 °C with increasing be observed, which is attributed to the brittle nature of gelatin matrix at
gelatin weight fraction in the blend films. At the same time, the melting low temperatures. From the micrographs of blend films, there is only
peak gradually moved to higher temperatures with increasing gelatin slight variation on the microstructure of all formulations of the blend
fraction in blends (see Fig. S4), which indicated that the SSPS/gelatin films. S80G20 and S60G40 films have slightly rough surfaces, and a few
blend films are capable of withstanding higher sealing temperatures micro-sized agglomerates can be seen on the surfaces of these samples.
compared to neat SSPS film. Worthy to note is that, the blend film This may be due to the conformation and association of gelatin chain
G80S20 appeared primarily miscible since only a single Tg (54.0 °C) was within the SSPS matrix, since the protein chains tend to reorganize
observed and the glass transition of SSPS has disappeared. Furthermore, themselves during drying (Acosta, Jiménez, Cháfer, González-Martínez,
the strong interactions between gelatin and SSPS, including hydrogen & Chiralt, 2015). Meanwhile, it should be noted that all the blend films
bonding and electrostatic interaction, may have led to greater steric display relatively continuous and dense cross-section structure, in-
hindrance which notably limited the movements of the macro- dicating compatibility of the SSPS/gelatin blends.
molecules. The strong interaction could minimize the free volume and Topographical imaging was performed by AFM to assess the surface
intermolecular distance in films, thereby increasing the Tg of gelatin roughnesses of three representative films. The representative 3-D
(Mohajer, Rezaei, & Hosseini, 2017; Núñez-Flores et al., 2013). These images, for scanning areas of 5 μm × 5 μm, of the surfaces of neat SSPS,
DSC results agree with the XRD patterns of the blend films, which ex- gelatin and S80G20 films are shown in Fig. 2A3, B3, and F3, respec-
hibited diminished crystalline peak of SSPS. Additionally, the thermal tively. The addition of 20 % gelatin in the SSPS led to obvious increase
degradation behavior of the films was also assessed by thermo- in the roughness of the films, manifested by the increase of average
gravimetry analysis (Supplementary, Fig. S3 & Table S2). surface roughness (Sa) from 0.48 nm (S100G0) to 3.38 nm (S80G20),
and the root mean square roughness (Sq) showed a similar trend. The Sa
3.5. Water solubility, equilibrium moisture content and water vapor value of S0G100 was 1.76 nm. The AFM results revealed that the
permeability morphology of the resulting film was affected by the addition of gelatin,
which induced the formation of small clusters on the surface of the film
Water solubility is an important property of edible films that affects when the weight excess of SSPS was too great. These observations,
their future applications. From Table 2, the water solubility of neat together with the above SEM, optical, DSC and WVP results, demon-
gelatin film is relatively low (31.5 %), that is basically in agreement strating that though there exists compatibility to a certain extent be-
with the value reported by other researchers for bovine hide gelatin tween SSPS and gelatin, slightly phase separation still occurs which
film (∼34.3 %), being inferior to those of fish gelatin films (Gómez- results in a two phase morphology. Similar results have also been re-
Estaca, Montero, Fernández-Martín, & Gómez-Guillén, 2009; Núñez- ported for gelatin/agar and gelatin/pectin blend systems (Farris et al.,
Flores et al., 2013). The neat SSPS and S80G20 films were completely 2011; Mohajer et al., 2017).
soluble in water under the above-mentioned experimental conditions.
However, the addition of 40 % gelatin in the film formulation produced 3.7. Mechanical properties
a remarkable improvement in water resistance. The water solubility of
blended films was continuously reduced with an increase in weight The mechanical strength and flexibility are important character-
fraction of gelatin. Additionally, the decrease of water solubility in istics of films to keep the integrity of food packages. The tensile strength
blend films was accompanied by slightly decreases in equilibrium (TS), elongation at break (EAB) and elastic modulus (EM) of the SSPS/
moisture content and water vapor permeability. This may be explained gelatin films are presented in Table 2. The neat SSPS film showed TS
considering that the incorporation of gelatin may help to establish more and EAB values of 2.57 ± 0.39 MPa and 41.2 ± 8.25 %, respectively,
compact polymeric matrices, thus permitting the free volume to de- being in the same range reported in other studies (Tajik et al., 2013).
crease in the blend film, and produced decrease tendencies in EMC and The TS values for the blend films are between the values of neat SSPS
WVP values. It is generally accepted that there is a relationship between and gelatin films. The blend films with low gelatin fraction (S80G20
free hydroxyl groups and equilibrium moisture content, because these and S60G40) exhibited slightly increase of TS with the increase in the

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C. Liu, et al. Food Packaging and Shelf Life 24 (2020) 100485

Fig. 2. SEM photographs of (A1-F1) surface and (A2-F2) cross-section of (A1, A2) S100G0, (B1, B2) S80G20, (C1, C2) S60G40, (D1, D2) S40G60, (E1, E2) S20G80,
and (F1, F2) S0G100 films; AFM images of (A3) S100G0, (B3) S80G20, and (F3) S0G100 films.

weight fraction of gelatin, while significant increases (p < 0.05) were increase in EAB, while a significant decrease in EM was observed. This
observed in TS when more gelatin was added to SSPS films. This could result is in agreement with Ahmad et al. (2015) who reported that the
be attributed to the increased interaction between the two biopolymers addition of gelatin in rice flour films simultaneously increased TS and
and formation of compact structure of blend films indicated by FTIR, EAB.
SEM, and DSC. According to Sivarooban, Hettiarachchy, and Johnson
(2008)) and Arfat, Benjakul, Prodpran, and Osako (2014), the dis- 3.8. Seal strength
tribution and density of intra- and intermolecular interactions between
biopolymers and plasticizers (including water) play important roles in Sufficient seal strength of packaging material are required in order
determining the mechanical properties of blend films. In the present to prevent the leakage of the products inside the package during sto-
study, the incorporation of more gelatin further increased molecular rage, processing, or handling (Kim & Ustunol, 2006). Poor heat seal
mobility and formed more homogeneous film matrix, led to increased property has long been recognized as a major drawback for edible films
continuity in the film network of blend films. In addition to that, such (Li, Kennedy, Jiang, & Xie, 2006). Preliminary study showed that
an increase in film mechanical properties may be related to the film heating temperature of 150 ± 1 °C, dwell time of 1.5 s, and pressure of
composition. Specifically, gelatin tends to be continuous phase with 300 kPa could provide sufficient melting and fusion for SSPS/gelatin
increasing weight fraction of gelatin. Due to the formation of gelatin films. Seal strength of SSPS, gelatin and their blend films are shown in
physical network containing triple-helix junctions, the blend films ex- Fig. 3. SSPS film shows substantially lower (p < 0.05) seal strength
hibited an improved strength to tolerate external forces. Moreover, it is (50 N/m) when compared with neat gelatin film (590 N/m). This re-
interesting to note that the addition of gelatin caused a significant markable difference is believed to be related to their quite different

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C. Liu, et al. Food Packaging and Shelf Life 24 (2020) 100485

Soponronnarit, 2019), and starch-based films (375 N/m) (Das &


Chowdhury, 2016).

3.9. Packaging tests

Photographs of instant coffee powder and coconut powder packaged


in two different pouches made from neat SSPS and S60G40 films are
shown in Fig. 4A-D. All dry powders packaged in these pouches exhibit
their original colors due to the excellent transparency of the films in the
visible range, as shown by the results listed in Table 1. The in-
corporation of gelatin does not affect the see-through property of the
SSPS film. Fig. 4E and F exhibit the photos captured during the dis-
solution of the SSPS/gelatin pouches containing coconut powder in hot
water. From these photos, it is evident that both of the pouches were
getting dissolved within several seconds (< 30 s) and released the
packaged powder very quickly, which means that the addition of ge-
latin does not affect the rapid hot-water solubility of the SSPS films
Fig. 3. Heat seal strength of SSPS/gelatin films with different weight ratios.
under the current experimental conditions.
Shown results are mean values ± standard deviation (n = 5). NS means no
significant difference and asterisk indicates significant difference (p < 0.05). 4. Conclusions

In order to develop practical edible packages from soluble soybean


chemical composition and aggregation structure (Abedinia et al.,
polysaccharide, it is important to improve the physical properties of its
2018). The seal strength significantly increased (p < 0.05) from 50 to
films, such as the tensile strength, thermal stability and heat seal
150 N/m with increasing weight fraction of gelatin in blend films from
strength. As a solution, gelatin was incorporated into SSPS films to
0 % to 20 %, and dramatically increased to 640 N/m with the addition
prepare blend films by a solution casting method in the present work.
of gelatin up to 60 %. However, further increase in the gelatin fraction
Experimental results suggested that SSPS and gelatin are partially
did not produce significant increase (p > 0.05) in the seal strength.
compatible to form blend films. The addition of gelatin greatly in-
These results suggested that the interaction between the two biopoly-
creased the heat seal strength, tensile strength, thermal stability and
mers might be enhanced after heat pressing (Kim & Ustunol, 2006). The
stretchability of the SSPS films, while reducing their permeability and
SSPS/gelatin blend films developed in this study exhibit comparable
water solubility. The results of optical tests showed high UV barrier
seal strength results to the typical synthetic polymer (> 678 N/m, for
property and good see-through property for all the blend films. The
LDPE), and are much higher than those of carrageenan films
packaging test indicated that SSPS/gelatin edible blend films are po-
(109∼181 N/m) (Farhan & Hani, 2017), chitosan-based films
tential candidates for fabricating quick-dissolving packages for pow-
(110.7 N/m) (Prateepchanachai, Thakhiew, Devahastin, &
dered food and beverage products.

Fig. 4. (A, C) Instant coffee powder and (B, D) coconut powder packaged in heat-sealed edible pouches made from (A, B) S100G0 and (C, D) S60G40 films; photos
captured during the dissolution tests in hot water (95 ± 2 °C): (E) coconut powder in S100G0 pouch; (F) coconut powder in S60G40 pouch.

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C. Liu, et al. Food Packaging and Shelf Life 24 (2020) 100485

Table 1
Light transmittances and transparency values of the SSPS/gelatin films.
Films Light transmittance (%) at different wavelengths Transparency value

200 nm 280 nm 350 nm 400 nm 500 nm 600 nm

S100G0 0.00 9.68 ± 3.95bc 55.04 ± 5.74e 69.22 ± 3.83e 79.18 ± 2.05d 83.4 ± 1.30c 0.663 ± 0.096b
S80G20 0.00 7.26 ± 0.27c 49.00 ± 1.03f 62.30 ± 1.45f 71.82 ± 1.23e 76.68 ± 0.95d 1.043 ± 0.098a
S60G40 0.00 8.08 ± 4.93c 60.88 ± 5.37d 73.86 ± 2.68d 81.32 ± 1.19c 84.40 ± 0.87c 0.579 ± 0.127bc
S40G60 0.00 11.46 ± 1.67abc 71.86 ± 1.40c 80.52 ± 0.74c 85.44 ± 0.36b 87.68 ± 0.33b 0.520 ± 0.046c
S20G80 0.00 13.66 ± 3.74ab 77.90 ± 2.08b 83.34 ± 0.84b 86.48 ± 0.54b 88.08 ± 0.5b 0.554 ± 0.086bc
S0G100 0.00 14.14 ± 1.39a 84.52 ± 0.56a 87.22 ± 0.77a 89.06 ± 0.90a 90.04 ± 0.68a 0.385 ± 0.030d

Results for each film are presented as means ± SD (n = 5). Mean values in the same column with different letters (a, b, c…) are significantly different (p < 0.05).

Table 2
Film water solubility, equilibrium moisture content (EMC), water vapor permeability (WVP), and mechanical properties of SSPS/gelatin films.
Films Water solubility (%) EMC (%) WVP (g mm/m2 kPa h) Tensile strength (TS) (MPa) Elongation at break (EAB) (%) Elastic modulus (EM) (MPa)

S100G0 100a 15.6 ± 0.1a 2.478 ± 0.170ab 2.57 ± 0.39e 41.20 ± 8.25e 11.7 ± 0.7a
S80G20 100a 15.3 ± 3.2a 2.509 ± 0.156a 2.59 ± 0.48e 86.40 ± 20.28d 10.3 ± 0.6a
S60G40 55.2 ± 0.2b 14.9 ± 2.9a 2.386 ± 0.324bc 2.90 ± 0.39de 139.30 ± 14.81c 7.5 ± 0.6b
S40G60 38.1 ± 0.6c 11.2 ± 0.4b 2.034 ± 0.057 cd 4.75 ± 0.99bc 253.20 ± 43.80b 7.5 ± 0.6bc
S20G80 33.8 ± 0.2d 11.8 ± 0.2b 1.926 ± 0.048d 5.20 ± 0.50b 252.70 ± 34.24b 6.9 ± 0.5bc
S0G100 31.5 ± 0.2e 11.2 ± 0.5b 2.278 ± 0.138bc 6.08 ± 1.01a 317.70 ± 58.87a 6.4 ± 0.5 cd

Results for each film are presented as means ± SD (n = 5). Mean values in the same column with different letters (a, b, c…) are significantly different (p < 0.05).

CRediT authorship contribution statement Alipoormazandarani, N., Ghazihoseini, S., & Nafchi, A. M. (2015). Preparation and
characterization of novel bionanocomposite based on soluble soybean polysaccharide
and halloysite nanoclay. Carbohydrate Polymers, 134, 745–751. https://doi.org/10.
Chang Liu: Investigation, Writing - original draft. Jiao Huang: 1016/j.carbpol.2015.08.059.
Investigation, Writing - original draft. Xuejing Zheng: Visualization, American Society for Testing and Materials (ASTM) (2005). Standard test method for seal
Resources. Shujie Liu: Investigation. Kuakua Lu: Investigation. strength of flexible barrier materials. Designation F88. Annual book of ASTM standards.
Philadelphia: American Society for Testing Materials.
Keyong Tang: Validation, Visualization. Jie Liu: Supervision, Arfat, Y. A., Benjakul, S., Prodpran, T., & Osako, K. (2014). Development and char-
Conceptualization, Investigation, Writing - review & editing. acterisation of blend films based on fish protein isolate and fish skin gelatin. Food
Hydrocolloids, 39, 58–67. https://doi.org/10.1016/j.foodhyd.2013.12.028.
Avérous, L., Fringant, C., & Moro, L. (2001). Plasticized starch-cellulose interactions in
Declaration of Competing Interest polysaccharide composites. Polymer, 42(15), 6565–6572. https://doi.org/10.1016/
S0032-3861(01)00125-2.
The author(s) declared no potential conflicts of interest. Badii, F., MacNaughtan, W., Mitchell, J. R., & Farhat, I. A. (2015). The effect of drying
temperature on physical properties of thin gelatin films. Drying Technology, 32(1),
30–38. https://doi.org/10.1080/07373937.2013.808206.
Acknowledgements Cao, N., Fu, Y., & He, J. (2007). Preparation and physical properties of soy protein isolate
and gelatin composite films. Food Hydrocolloids, 21(7), 1153–1162. https://doi.org/
The authors thank to Ms. Fang Wang for heat sealing experiments, 10.1016/j.foodhyd.2006.09.001.
Cazón, P., Velazquez, G., Ramírez, J. A., & Vázquez, M. (2017). Polysaccharide-based
Prof. Xinchang Pang for AFM tests, and Prof. Jie Chen (JiangNan films and coatings for food packaging: A review. Food Hydrocolloids, 68, 136–148.
University) for SEC tests. This work was supported by the Science and https://doi.org/10.1016/j.foodhyd.2016.09.009.
Technology Department of Henan Province, China [grant number Chen, C., Wang, F., Mao, C., Liao, W., & Hsieh, C. (2008). Studies of chitosan: II.
Preparation and characterization of chitosan/poly(vinyl alcohol)/gelatin ternary
172102410022]; the Education Department of Henan Province, China blend films. International Journal of Biological Macromolecules, 43(1), 37–42. https://
[grant number 17HASTIT009], and National Natural Science doi.org/10.1016/j.ijbiomac.2007.09.005.
Foundation of China [grant numbers 51673177, 51473150]. Das, M., & Chowdhury, T. (2016). Heat sealing property of starch based self-supporting
edible films. Food Packaging and Shelf Life, 9, 64–68. https://doi.org/10.1016/j.fpsl.
2016.05.002.
Appendix A. Supplementary data Dyshlyuk, L., Babich, O., Belova, D., & Prosekov, A. (2017). Comparative analysis of
physical and chemical properties of biodegradable edible films of various composi-
tions. Journal of Food Process Engineering, 40(1), e12331. https://doi.org/10.1111/
Supplementary material related to this article can be found, in the
jfpe.12331.
online version, at doi:https://doi.org/10.1016/j.fpsl.2020.100485. Fakhouri, F. M., Martelli, S. M., Caon, T., Velasco, J. I., & Mei, L. H. I. (2015). Edible films
and coatings based on starch/gelatin: Film properties and effect of coatings on quality
of refrigerated Red Crimson grapes. Postharvest Biology and Technology, 109, 57–64.
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