Food Hydrocolloids 87 (2019) 173–179

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Food Hydrocolloids
journal homepage: www.elsevier.com/locate/foodhyd

Effects of acid hydrolysis on the physicochemical properties of pea starch T

and its film forming capacity
Hui Zhanga, Hanxue Houa,∗, Pengfei Liub,∗∗, Wentao Wanga, Haizhou Donga
a
Department of Food Science and Engineering, Shandong Agricultural University, Engineering and Technology Center for Grain Processing of Shandong Province, Tai'an,
PR China
b
State Key Laboratory of Biobased Material and Green Papermaking, School of Food Science and Engineering, Qilu University of Technology, Shandong Academy of
Sciences, Ji'nan, PR China

A R T I C LE I N FO A B S T R A C T

Keywords: The effects of acid hydrolysis treatment on the properties of pea starch (PS) and PS-based films by solution
Pea starch casting were investigated. Native pea starch granules were partially hydrolyzed with 2% hydrochloric acid for
Film 0.5, 1.0, 1.5, 2.0, and 2.5 h. Acid hydrolysis treatment lowered the molecular weight of amylopectin from
Acid hydrolysis 27.94 × 107 g/mol for native PS to 9.16 × 107 g/mol for the sample of 2.5 h hydrolysis, but had no obvious
Molecular weight distribution
effect on the molecular weight of amylose. Micrographs of the hydrolysis starch granules exhibited surface
Mechanical properties
erosion and fragmentation. The relative crystallinity slightly increased, whereas the peak, trough, final and
setback viscosities decreased during acid hydrolysis. After acid hydrolysis treatment, the tensile strength of the
pea starch film significantly increased and reached a maximum of 21.21 MPa with 2.0 h of acid hydrolysis.

1. Introduction
Starch is regarded as one of the most promising raw material for the
production of edible and biodegradable films as it is a renewable,
biodegradable, abundant, and widely available biopolymer (Jiménez,
Fabra, Talens, & Chiralt, 2009). However, the poor mechanical prop-
erties and moisture barrier properties of the films made from native
starch limit their extensive application in many fields (Mali, Debiagi,
Grossmann, & Yamashita, 2010). The modification of starches by phy-
sical (Deep, Bawa, Riar, & Saxena, 2009; Zavareze et al., 2012) and
chemical (Lopez, Garcia, & Zaritzky, 2008) processes has been an ef-
fective way to improve the performance of starch films.
The molecular weight, chain length distribution and crystallinity are
important factors that influence the properties of polymer films (Cheng,
Abd Karim, & Seow, 2007; Chung & Lai, 2007; Fonseca et al., 2015;
Lazaridou, Biliaderis, & Kontogiorgos, 2003; Sothornvit and Krochta,
2000a, 2000b). Although the main industrial applications of acid-
modified starches are found in the fields of paper, textile and gum
candy fields, their use in edible and biodegradable films is increasing
due to their good film-forming capacities (Lopez et al., 2008; Luchese,
Frick, Patzer, Spada, & Tessaro, 2015). Acid-modified starches are
particularly suited for applications utilizing the film-forming properties
of starch (Wurzburg, 1986, pp. 17–40). Acid modification could in-
crease water solubility, degree of crystallinity, and gel strength of
starch. Meanwhile, it could decrease molecular weight and viscosity of
starch (Hoover, 2000; Luchese et al., 2015). These properties are de-
sired for the ease of handling of the dispersion, pasting, casting and
drying processes in the preparation of starch films.
Chung and Lai (2007) reported the effects of modification with
0.36% HCl in methanol at 25 °C and 45 °C on the properties of corn
starch and its films. The results showed that acid modification increased
the homogeneity of the corresponding films and decreased the moisture
absorption rate and maximum moisture content. Acid modification with
0.25, 0.5 and 1.0 mol/L hydrochloric acid for 2 h increased the punc-
ture and tensile strength of water chestnut starch films (Deep et al.,
2009). Luchese et al. (2015) reported that hydrolysis by a specific
concentration of hydrochloric acid could increase the homogeneity and
water vapor permeability of a pinhao starch film. Up to now, the re-
lationships between the physicochemical properties of acid-modified
starches and the performance of the corresponding films are still not
been clear. Furthermore, the effects of the acid hydrolysis time on the
properties of pea starch-based films have not yet been reported.
In this study, pea starch (PS) was chosen as the film-forming ma-
terial because of its high amylose content, which favors film production

∗
Corresponding author. Department of Food Science and Engineering, Shandong Agricultural University, Tai'an City, Shandong Province, 271018, PR China.
∗∗
Corresponding author. Qilu University of Technology (Shandong Academy of Sciences), Daxue Road, Changqing District, Ji'nan City, Shandong Province,
250353, PR China.
E-mail addresses: hhx@sdau.edu.cn (H. Hou), zxliupf@163.com (P. Liu).

https://doi.org/10.1016/j.foodhyd.2018.08.009
Received 8 May 2018; Received in revised form 5 August 2018; Accepted 5 August 2018
Available online 06 August 2018
0268-005X/ © 2018 Elsevier Ltd. All rights reserved.
H. Zhang et al.
(Li et al., 2011; Muscat, Adhikari, Adhikari, & Chaudhary, 2012). Pea
starch hydrolysates were prepared by hydrochloric acid treatment. The
properties of the hydrolysis pea starch and its films were studied. The
aim of this study was to investigate the effects of acid hydrolysis
treatment on the properties of pea starch and its film forming capacity
and to obtain the appropriate hydrolyzation extent of pea starch for
film preparation.
2. Materials and methods
2.1. Materials
Pea starch was provided by the Yingfei Food Co. Ltd. (ZhaoYuan,
China). Standard P-82 pullulans were purchased from Showa (Denko
KK, Tokyo, Japan). Sodium azide was analytical grade and obtained
from Bodi Chemical Reagent Co. Ltd. (Tianjin, China). Sorbitol was of
food grade standard and purchased from Jinquan Chemical Reagent Co.
Ltd. (Jinan, China). All other chemicals were of at least analytical grade
standard.
2.2. Methods
2.2.1. Acid hydrolysis of pea starch
Pea starch (172.46 g, dry base) was suspended in 350 mL HCl so-
lution (2% by weight) in a 500-mL flask. The suspension was magne-
tically stirred at 45 °C for 0.5, 1.0, 1.5, 2.0 and 2.5 h, followed by
filtering through What-man No. 1 filter paper. Then, samples were
washed with 1M NaOH until the washings became neutral. After that,
the acid-modified starches were washed four times with distilled water.
The filter cake was dried at 50 °C for 24 h in an air oven. Finally, the
dried samples were ground and passed through a 100 mesh sieve. The
starches were sealed within separate airtight containers for at least
48 h. The samples were coded as PS for native pea starch and PS-0.5 h,
PS-1.0 h, PS-1.5 h, PS-2.0 h and PS-2.5 h for samples treated with 2%
HCl for 0.5, 1.0, 1.5, 2.0 and 2.5 h, respectively.
2.2.2. X-ray diffraction of the starches
At room temperature, a certain amount of starch prepared in section
2.2.1 was packed tightly into a sample cell compacted by a glass slide,
the crystallinity of starch was determined by X-ray diffraction (XRD) on
the sample table. X-ray diffractograms were recorded over an angular
range (2θ) of 5°–30° at 0.02 intervals by a D8 Advance diffractometer
(Bruker AXS GmbH, Karlsruhe, Germany) at 40 kV and 40 mA. From the
scattering spectrum, the percentage of efficacious crystallinity was
calculated as the ratio of the integrated crystalline intensity (sharp
peaks) to the total intensity (both amorphous background and crystal-
line peaks) (Flores, Fama, Rojas, Goyanes, & Gerschenson, 2007; Liu,
Wang, Kang, Cui, & Yu, 2018).
2.2.3. Starch granule morphology
A scanning electron microscope (QUANTA-FEG250, FEI, U.S.) was
used to study the starch granule morphology. Starch samples were
mounted on a circular aluminum stub, coated with gold, and then ex-
amined at an acceleration potential of 10 kV, with images being re-
corded.
2.2.4. Molecular weight distribution of the starches
The molecular weight distribution of the acid-modified starches was
determined with high performance size exclusion chromatography
(HPSEC). Methods for dissolution of samples and determination of
molecular weight all referred to the method of Lin, Lee, and Chang
(2003). Each sample solution was filtered through a 5.0-μm syringe
filter, 100 μL of filtrate was injected into an HPSEC system.
The HPSEC system consisted of a refractive index (RI) detector
(Optilab rEX, Wyatt Tech., USA), and a multiangle laser lightscattering
(MALLS) detector (DAWN HELEOS, Wyatt Tech., USA), with a helium-
174
Food Hydrocolloids 87 (2019) 173–179
neon laser light source (λ = 658 nm). The chromatography columns
were two TSK gel columns (7.8 mm ID × 30 cm per column) in series
(G4000 PWXL, G5000 PWXL; Tosohaas, Japan) combined with a PWXL-
guard column (Tosohaas, Japan). A 0.1 M sodium nitrate solution
containing 0.02% sodium azide was used as the mobile phase. Elution
was performed at 60 °C at a flow rate of 0.5 mL/min. The refractive
index of mobile phase was 1.331, the refractive index increment of
starch molecules in solution was set to dn/dc = 0.146. The electronic
outputs of the MALLS and RI detectors were collected by ASTRA soft-
ware (ver. 5.3.4.20, Wyatt Tech., USA). The MALLS and RI signals were
used to determine the molecule weight of amylopectin (the first frac-
tion). Because of the reduced sensitivity of MALLS for small molecular
weight species, the molecular weight of the second fraction (amylose
and degraded amylopectin fragments) of starches was calculated by the
RI signal using a calibration curve constructed from a series of pullulan
standards with molecular weight of 78.8 × 104, 40.4 × 104,
21.2 × 104, 11.2 × 104, 4.73 × 104, 2.28 × 104, 1.18 × 104and
0.59 × 104 Da.
2.2.5. Pasting properties of the starches
The pasting properties of the starches were analyzed by a Rapid
Visco Analyser (RVA) Super 3 (Newport Scientific Pty Ltd.,
Warriewood, Australia). The AACC Approved Method 76–21 (American
Association of Cereal Chemists, 2000) standard 2 profile for the com-
puter was used. Starch (2.5 g, 14% moisture basis, m.b.) was mixed
with 25 mL distilled water in the RVA sample canister. The peak visc-
osity (PV), trough viscosity (TV), final viscosity (FV), pasting tem-
perature (PT), setback viscosity (SV) and breakdown viscosity (BV)
were established.
2.2.6. Film preparation
Native and acid-treated starch films were prepared by solution
casting. The amount of sorbitol was weighed and dissolved into distilled
water and then starch was added to obtain a film-forming suspension.
The starch concentration in the suspension was 4% (w/w) of overall
water content independent of sorbitol concentration. Starch: sorbitol
ratio was 100:40 (w/w). Film forming suspension was heated with
continuous mixing at 90 °C for 30 min. Then, the suspension was cooled
down to 50 °C to obtain the film forming solution. The air bubbles that
formed during mixing were removed by placing the film forming so-
lution into a desiccator under a vacuum until no bubbles were ob-
served. Film forming solution was poured on teflon-coated plate.
Starch-based films were obtained by evaporating water in an oven at
50 °C. All of the tested film samples were equilibrated at 23 ± 2 °C and
53% relative humidity in the constant temperature humidity chamber
for at least 48 h prior to testing.
2.2.7. Mechanical properties
The mechanical properties of the films were determined by a TA-
XT2i texture analyser (Stable Micro System, UK) according to ASTM
D882-02 (ASTM. D882-02, 2002) with some modifications. Film strips
(15 mm × 80 mm) were stretched at 1 mm/s with an initial distance
between grips of 50 mm. The tensile strength (TS, MPa) and elongation
at break (E, %) were calculated with the following equations (Tang,
Alavi, & Herald, 2008):
Lp
TS = × 10−6 MPa
a (1)
where Lp is the peak load (N) and a is the cross-sectional area of samples
(m2);
ΔL
E= × 100
L (2)
where ΔL is the increase in length at the breaking point (mm) and L is
the original length (mm).
H. Zhang et al.
2.2.8. Water vapor permeability
The water vapor permeability (WVP) values of the films were ana-
lyzed with a PERME™ W3/030 Automatic WVP Tester (Languang Co.,
Ltd., China) according to the methodology described by Yan, Hou, Guo,
and Dong (2012). The test films were cut into round shapes
(33.00 cm2). The film thickness was measured with a digital micro-
meter caliper (0 mm–25 mm, 0.001 mm, Guanglu Digital Measurement
and Control Co., Ltd., China). The relative humidity and temperature
used in the test were 90% and 38 °C, respectively.
2.2.9. Statistical analysis
The data were subjected to analysis of variance (ANOVA) using
SPSS 18.0 Windows Software. Duncan's multiple range test (p < 0.05)
was adopted to detect differences among the mean values of the sample
properties.
3. Results and discussion
3.1. X-ray diffraction (XRD)
The effects of acid hydrolysis on the crystalline structure of PS were
investigated. Fig. 1 shows the XRD patterns and relative crystallinity of
the native and hydrolysis PS samples. The native PS granules exhibited
a typical A-type crystalline structure with the main strong diffraction
peaks at approximately 15°, and 23° (2θ), and a weak doublet with
peaks at 17° and 18°, in accordance with other reports (Wang, Blazek,
Gilbert, & Copeland, 2012). Acid hydrolysis treatment did not alter the
crystalline structure of PS granules, but slightly increased the relative
crystallinity of PS granules. With the increase of acid hydrolysis time,
the relative crystallinity values of the starch gradually increased. The
relative crystallinity of native PS and PS-2.5h sample were 40.0% and
43.6%, respectively. This can be attributed to the preferential hydro-
lysis of the amorphous regions by acid. In addition, this behavior may
be ascribed to better orientation of the crystallites for the hydrolysis
starch. This result corroborated the previous findings (Beninca et al.,
2013; Utrilla-Coello, R.G et al., 2014) that mild acid hydrolysis for a
short time predominantly affected the amorphous regions of starch,
thereby rendering a more refined crystallinity for residual starch. Ac-
cording to Salgado Guerra, Andrade and Oliveira (2005), the pre-
servation of the crystallinity indicated stronger internal connections of
Diffraction Intensity
5 10 15
Fig. 1. X-ray diffraction curves of native and acid-treated pea starches.
Food Hydrocolloids 87 (2019) 173–179
the starch molecules and higher degree of association between the
starch chains.
3.2. Granule morphology
The micrographs of starch granules were obtained by scanning
electron microscopy. Overviews of the granules of native PS and hy-
drolysis PS with a magnification of 3000 are shown in Fig. 2. The
average diameter of the native PS granules ranged from 5 to 20 μm.
Native PS granules exhibited regular oval- or sphere-like shapes with
smooth granule surfaces (Fig. 2a). For the 0.5 h-1.5 h of acid hydrolysis
treatment, there was no obvious configuration change in starch gran-
ules, such as swelling or deformation. However, surface erosion and
roughness, which implied an acid attack, were quite obvious on the
surfaces of the starch granules. As was previously stated, the results of
the evaluation of the crystallinity (Fig. 1) showed that acid attack
predominantly affected the amorphous regions under limited hydrolysis
conditions. It was suggested that the amorphous regions on the per-
iphery of the granule were preferentially attacked by acid during the
acid hydrolysis treatment process. Similar observations had been re-
ported by Deep et al. (2009) working with partially acid-hydrolyzed
water chestnut starch. Micrographs for PS-2.0h and PS-2.5h samples
showed more severe acid erosion, which was indicated by the amount,
size and depth of erosion of the granule surfaces, and starch granules
with smaller sizes appeared with evidence of fragmentation and de-
formation.
3.3. Molecular weight distribution
The molecular weight properties of the starches are shown in Fig. 3
and Table 1. In Fig. 3, the first fraction (P1) was corresponded to
amylopectin, and the second fraction (P2) was attributed to amylose
and low molecular weight molecules. Native PS had a higher percen-
tage of P1 and a lower percentage of P2 (Table 1). With the increase of
acidolysis time, the percentage of the P1 fraction decreased and the
percentage of the P2 fraction increased. The amylopectin molecular
weight of PS decreased from 27.94 × 107 g/mol for native PS to
9.16 × 107 g/mol for the sample with 2.5 h hydrolysis. It was suggested
that acidolysis caused amylopectin to disintegrate and transform into
low molecular weight molecules (amylose or smaller branching starch
Relative
crystallinity (%)
PS-2.5h 43.6
PS-2.0h 42.1
PS-1.5h 41.7
PS-1.0h 41.6
PS-0.5h 40.9
PS 40.0
20 25 30 35
2 °
175
H. Zhang et al.
Fig. 2. Scanning electron micrographs of native and acid-treated pea starch granules.
molecules). According to a review by Hoover (2000), possible struc-
tures for acid-treated starches include linear chains, singly branched
chains, or a multiple branched chain. Lin et al. (2003) and Chang, Lin,
and Chang (2006) investigated the molecular structure of maize and
potato starches treated with acid–alcohol, and it was found that starch
hydrolysates consist of amylose, long chains and short chains of amy-
lopectin. Miao, Jiang, Zhang, and Jin (2011) studied the effect of mild
acid hydrolysis on waxy maize starch, similar result had been obtained.
Polydispersity index I offered a definition describing the molecular
weight distribution: I is equal to 1 in a monodisperse system (Chanda &
Roy, 2006). A higher value of I indicates more spread in the molecular
weight distribution of the starch. Table 1 shows that the molecular
weight distribution of amylopectin decreased progressively with the
increase of acidolysis time, but the distribution of amylose did not
176
Food Hydrocolloids 87 (2019) 173–179
change obviously. The molecular weight distribution of amylopectin
was more concentrated by acidolysis than that of amylose. The result
was in agreement with the studies made by Carvalho, Zambon, A.da
Silva, and Gandini (2005) and Miao et al. (2011), who suggested that
the longer or more branched starch molecules were more sensitive to
scission from acid attack.
From the results of granular micrographs (Fig. 2) and molecular
weight properties (Table 1), starches subjected to acid-hydrolysis for a
shorter time exhibited less molecular degradation and granular struc-
ture alteration compared to native starch. PS-2.5h sample showed the
highest degradation and greatest alteration in the molecular and
granular structure. According to Chang et al. (2006), the reduction of
the molecular mass of the starch was related to the alteration of the
granular internal structure. It could be speculated that the degradation
H. Zhang et al. Food Hydrocolloids 87 (2019) 173–179

Fig. 3. HPSEC chromatograms of native and acid-treated pea starches.

Table 1 shift toward amylose and low molecular weight starch molecules
Molecular size of native and acid-treated pea starches. (Table 1), which was suggested to cause the decreasing pasting visc-
P1 P2 osities. This result was similar to those observed by Deep et al. (2009)
and Utrilla-Coello et al. (2014). The low SV values of the acid-hydro-
Mw Mn I % Mw Mn I % lyzed samples might be due to the insufficient time for the starch mo-
(107 g/ (107 g/ (105 g/ (105 g/ lecules to align themselves during this measurement (Lin et al., 2003).
mol) mol) mol) mol)
Acid-hydrolyzed PS samples showed higher PT than PS. The PT in-
PS 27.94 14.32 1.96 71.41 0.37 0.15 2.42 28.59 creased from 74.3 °C (PS) to 77.9 °C (PS-2.5h). Nevertheless, no sig-
PS-0.5h 18.69 11.79 1.59 71.40 0.44 0.19 2.32 28.60 nificant changes were observed for the PT values of acid-hydrolyzed
PS-1.0h 17.31 10.85 1.58 70.03 0.43 0.18 2.37 29.97 samples with different acid hydrolysis times. The increase in the crys-
PS-1.5h 14.83 10.17 1.46 69.15 0.41 0.17 2.40 30.85
tallinity for acid-hydrolyzed PS samples might bring about the re-
PS-2.0h 11.94 8.4 1.42 67.44 0.34 0.15 2.24 32.56
PS-2.5h 9.16 6.7 1.37 66.35 0.38 0.16 2.31 33.65 sistance of the granules to swelling, which may be caused by the
strengthening of the intragranular binding force (Deep et al., 2009).
Mw = apparent weight-average molecular weight; Mn = apparent number This change might explain the increase in the PT and the decrease in the
average molecular weight; I (apparent polydispersity) = Mw/Mn; Weight (%) BV in acid-hydrolyzed starches.
= (Area of peak)/(total area) × 100%.

3.5. Mechanical properties

of starch molecules could bring about an increase in the alteration of
the internal structure in starch granules, thereby increasing the mobi-
lity of molecules and their crystallinity.
3.4. Pasting properties
The pasting parameters of native and hydrolysis PS samples are
presented in Table 2. The results indicated that the pasting properties of
hydrolysis PS samples differed significantly from those of native PS. The
TV, PV, FV, BV and SV values of acid-treated PS samples were sig-
nificantly lower than those of native PS, and these viscosities gradually
decreased as the extent of acid hydrolysis increased. The TV, PV, FV, BV
and SB of PS and PS-2.5h were 2852 and 343 mPa s, 1572 and
188 mPa s, 2996 and 348 mPa s, 1280 and 155 mPa s, and 1424 and
160 mPa s, respectively (Table 2). A longer period of acid hydrolysis
elicits a lower peak viscosity for the starch. The PV decreased from
2852 mPa s (PS) to 1435 mPa s (PS-0.5h), 710 mPa s (PS-1.5h) and
343 mPa s (PS-2.5h). The acid modification induced the amylopectin to
Fig. 4 presents the mechanical properties of the films prepared by
native PS and acid-modified PS. The hydrolysis time had an obvious
effect on the tensile properties of the PS-based films. The TS (tensile
strength) values of the films increased significantly (P < 0.05) as the
hydrolysis time increased. An opposite trend was observed in the E
(elongation at break) values. Such trends were similar to the results
described in the literature obtained by Cheng et al. (2007) and Abd El-
Kader, Abdel Hamied, Mansour, ElLawindy, & El-Tantaway, 2002, who
studied the effect of molecular weight on the properties of konjac
glucomannan-based films and poly (vinyl alcohol)-based films. To ex-
plain the results, a few factors should be considered, e.g., the chain
length, chain mobility, chain flexibility, degree of entanglement, and
available segmental motion (Yoshimura & Nishinari, 1999), as all of
these did play an important role in modifying the mechanical properties
of the films. The acid hydrolysis transformed amylopectin molecules
into amylose and low molecular weight starch molecules. These smaller
starch molecules could function as a slippage area between large

177
H. Zhang et al. Food Hydrocolloids 87 (2019) 173–179

Table 2
RVA parameters of native and acid-treated pea starches.
PV (mPa s) TV (mPa s) FV (mPa s) BV (mPa s) SV (mPa s) PT (°C)

PS 2852 ± 15a 1572 ± 17a 2996 ± 17a 1280 ± 15a 1424 ± 13a 74.3 ± 0.29b
PS-0.5h 1435 ± 14b 1024 ± 14b 1486 ± 15b 411 ± 16b 462 ± 13b 77.4 ± 0.34a
PS-1.0h 1102 ± 16c 680 ± 12c 1086 ± 14c 422 ± 13b 406 ± 12b 77.2 ± 0.63a
PS-1.5h 710 ± 12d 408 ± 15d 676 ± 13d 302 ± 15c 268 ± 14c 77.4 ± 0.31a
PS-2.0h 454 ± 10e 236 ± 13e 425 ± 16e 218 ± 14d 189 ± 15d 77.1 ± 0.42a
PS-2.5h 343 ± 11f 188 ± 14f 348 ± 14f 155 ± 12e 160 ± 13e 77.9 ± 0.38a

a) Data are the means of three determinations ± standard deviation, and values within the same column followed by different letters are significantly different at
P < 0.05.
b) PV, peak viscosity; TV, trough viscosity; BV, breakdown viscosity; FV, final viscosity; SV, Setback viscosity; PT, pasting temperature.

amylopectin molecules to confer a viscous flow in the film-forming

solution, which might bring more chain alignment by hydrogen 6 a
bonding during the drying process. These changes led to an obvious
enhancement in the reinforcement of the polymer matrix during the
film-making process. This explanation was consistent with the results of

g cm cm s Pa )
-1
5
the evaluation of the crystallinity (Fig. 1). In addition, anti-plasticiza-

-1
-2
tion, where the free volume between starch chains in the amorphous b
regions could be filled with small molecular weight chains, could also
4 c
cause the film to become denser and stiffer (Cheng et al., 2007). All of c

-1 2
c

WVP (10
these factors may account for the increase in the TS and decrease in the d
E. On the other hand, a slow rise in the TS and a rise in the E occurred as
3
the acid hydrolysis time was increased to more than 2.0 h. As the acid
hydrolysis time was prolonged, the starch molecules became too small
to form entanglements between the chains, which facilitated segmental
mobility and restrained chain alignments. Therefore, compared with 2
0 0.5 1 1.5 2 2.5
film PS-2.0h, PS-2.5h-based film had a similar TS value but a higher E
value. The results indicate that, under the present acid hydrolysis Acidolysis Time (h)
conditions, an acid hydrolysis time of 2.0 h was found to be effective in Fig. 5. Water vapor permeabilities of native and acid-treated pea starch films.
improving the mechanical properties of the PS-based films. Data are the means of three determinations ± standard deviation, and values
within the same column followed by different letters are significantly different
at P < 0.05.
3.6. Water vapor permeability
based films. The values of WVP ranged from 3.47 × 10−12 to
The water vapor permeability of the acid hydrolysis treated and 5.74 × 10−12 (g cm cm−2 s−1 Pa−1) for the acid-hydrolyzed PS-based
native PS-based films are shown in Fig. 5. It can be seen from Fig. 5 that films compared with 3.16 × 10−12 (g cm cm−2 s−1 Pa−1) for the
the acid hydrolysis significantly increased the WVP values of the PS-

22 80
a e e

21 d
70

20
60
TS
c
TS(MPa)

19 E
E(%)

b 50
18
b c 40
cd
17
de
e
a
30
16

15 20
0 0.5 1 1.5 2 2.5

Acidolysis Time(h)
Fig. 4. Tensile strength and elongation at break of native and acid-treated pea starch films. Data were means of three determinations ± standard deviation. The
values within the same index followed by different letters are significantly different at P < 0.05.

178
H. Zhang et al.
native PS-based film. The WVP values of the films slowly and gradually
increased when the hydrolysis time ranged from 0 to 1.5 h. When the
hydrolysis time exceeded 1.5 h, the WVP values rapidly increased. As
Cheng, Abd Karim, Norziah, and Seow (2002) suggested, the WVP value
of a polymer film depended on the number of polar (eOH) groups in the
polymer matrix. More polar chain ends would have been generated
during the acid hydrolysis treatment, and this behavior would promote
water molecules penetration into the external surface of the acid-hy-
drolyzed PS-based films. In addition, the polymer chains, which con-
nected the junction zone areas would become shorter with reduced
molecular weight values (Yoshimura & Nishinari, 1999). Thus, water
molecules could penetrate more easily into the polymer film matrix
which was formed by less molecular weight PS. These results were
consistent with those obtained by Cheng et al. (2007), in which films
prepared from the hydrolysis of konjac glucomannan exhibited higher
WVP values than the films without hydrolysis treatment.
4. Conclusions
This study showed that acid hydrolysis treatment allows some of the
specific properties of starch and its films to be elicited. PS exhibited
different physicochemical properties after acid hydrolysis. Specifically,
the molecular weight of the amylopectin decreased and the crystallinity
increased as the acid hydrolysis time increased. It was indicated that
the breakage of starch chains had occurred mainly in the amorphous
regions. The PV, TV, BV, FV, and SB values of acid-treated PS were
lower than those of the native PS. After acid hydrolysis, the tensile
strength and WVP values of the films were significantly increased.
These properties of the films could be regulated by controlling the ex-
tent of acid hydrolysis and the molecular weights of the starch mole-
cules. It was demonstrated that acid hydrolysis is an effective method to
improve the mechanical properties of starch films. The moisture re-
sistance of the films treated by acid hydrolysis should be further studied
to improve the performance of starch-based films.
Acknowledgements
The authors appreciate the financial support of the Natural Science
Foundation of Shandong Province (ZR2014CL037), Key Research and
Development Plan of Shandong Province (2015GNC113008,
2018GNC113004) and Science and Technology Plan of Tai'an
(201540700).
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