Carbohydrate Polymers 250 (2020) 116840

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Carbohydrate Polymers
journal homepage: www.elsevier.com/locate/carbpol

Changes in microstructure and rheological properties of konjac T

glucomannan/zein blend film-forming solution during drying
Chong Lia,b, Fei Xianga,b, Kao Wua,b, Fatang Jianga,b,c, Xuewen Nia,b,*
a
Glyn O. Philips Hydrocolloid Research Centre at HUT, Hubei University of Technology, Wuhan, 430068, China
b
School of Bioengineering and Food Science, Hubei University of Technology, Wuhan, 430068, China
c
Department of Architecture and Built Environment, Faculty of Engineering, University of Nottingham, University Park, Nottingham, NG7 2RD, UK

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

Keywords: During film formation at 60 °C, the microstructure and rheological properties of konjac glucomannan (KGM)
Film-forming process film-forming solution and KGM/zein blend film-forming solution were investigated. The drying process of film-
Microstructure forming solutions was divided into two stages according to the drying curves. Scanning electron microscopy
Rheology showed that KGM chains in the blend solution aggregated into thicker chains and formed a molecular network
Konjac glucomannan
with larger pores. Zein particles grew larger but were homogeneously distributed during drying as observed by
Zein
confocal laser scanning microscopy. The addition of zein improved the thermal stability of the film-forming
solution. As the drying proceeded (up to 8 h), KGM solution exhibited a typical concentrated solution behavior
due to molecular entanglement; whereas the blend solution gradually formed a weak gel after 2 h. Complex
viscosity data for the film-forming solutions were well-fitted by the power-law model. The information obtained
from the study is important for understanding the film-forming mechanism.

1. Introduction assembly, a transition from a rubbery to a vitreous phase, a phase se-

With the increasing concern about global environmental protection
and the rising consumer need for safe and healthy foods, edible or
biodegradable films have received great interest as an alternative to
petroleum-derived plastics on packaging usage. Edible or biodegradable
films perform functions as a barrier against oxygen, moisture and solute
migration within the food itself or between the food and environment
(Bourlieu, Guillard, Vallès-Pamiès, Guilbert, & Gontard, 2009; Hassan,
Chatha, Hussain, Zia, & Akhtar, 2018). Generally, they are prepared
from renewable resources, such as natural polysaccharides, proteins
and lipids (Dehghani, Hosseini, & Regenstein, 2018; Hassan et al.,
2018). In recent times, extensive research works from edible or bio-
degradable films have focused on their composition, structure, thermal,
mechanical and barrier properties (Bourtoom & Chinnan, 2008; Denavi
et al., 2009; Hassan et al., 2018; Łupina et al., 2019; Mohajer, Rezaei, &
Hosseini, 2017; Niu, Shao, Chen, & Sun, 2019; Tong, Xiao, & Lim, 2008;
Wang et al., 2017), while only a few of them studied the film formation
process, e.g. KGM/ethyl cellulose composite films (Xiao et al., 2016).
The film formation process could highly affect the film characteristics,
and involves various complex physical or chemical processes. When the
solvent is removed due to evaporation, various phenomena may occur,
such as solute migration, molecular interaction, polymer chains
paration, and so on. For example, Liu and Han (2005) found that the
film formation of dilute starch solutions included helical formation,
aggregation or gelation, and reorganization of aggregates. The high-
amylose (55 %) starch film showed a heterogeneous structure with both
amylopectin-rich and amylose-rich phases, and there were no visible
boundaries existed due to molecular and supramolecular interaction
between amylopectin and amylose. Subirade, Kelly, Guéguen, and
Pézolet (1998) reported that the conformational changes of glycinin
occurred upon the film-forming process, and intermolecular hydrogen
bonding between segments of the β-sheet may act as junction zones
forming a network. Ghoshal, Mattea, Denner, and Stapf (2010) found
that the spatial heterogeneous distribution of solutes occurred with
evaporation proceeding during gelatin film formation, and the final film
still had structural heterogeneity. Understanding the formation of films
is critical to predict or control their structure and properties.
Konjac glucomannan (KGM) is a natural water-soluble poly-
saccharide derived from the tuber of the Amorphophallus konjac plant C.
Koch. It is mainly composed of β-1, 4-linked D-mannosyl and D-glucosyl
residues in a ratio of approximately 1.6:1 (Kato & Matsuda, 1969), or
1.5:1 (Smith & Srivastava, 1959), actually, the ratio varies with konjac
breeds (Kohyama, Iida, & Nishinari, 1993). KGM has bright application
prospects for edible or biodegradable packaging preparation due to its

⁎
Corresponding author at: Glyn O. Philips Hydrocolloid Research Centre at HUT, Hubei University of Technology, Wuhan, 430068, China.
E-mail address: nixuewen@126.com (X. Ni).

https://doi.org/10.1016/j.carbpol.2020.116840
Received 17 December 2019; Received in revised form 28 July 2020; Accepted 28 July 2020
Available online 15 August 2020
0144-8617/ © 2020 Elsevier Ltd. All rights reserved.
C. Li, et al.
excellent film-forming capability (Jia, Fang, & Yao, 2009). But pure
KGM film does not behave well as moisture barriers because it is highly
hydrophilic in nature. Some researches have been conducted to en-
hance the water barrier properties of KGM film by addition of other
film-forming components (Li et al., 2015; Rhim & Wang, 2013; Wang
et al., 2017; Wei et al., 2015; Wu et al., 2018). Zein is the major storage
protein of corn with abundant sources and low prices. It is insoluble in
pure water due to the high proportion of non-polar amino acid residues,
and it has great potential in film formation (Panchapakesan, Sozer,
Dogan, Huang, & Kokini, 2012; Wang & Padua, 2010). Pure zein film
presents good water vapor barrier properties, however, it lacks elasti-
city and is very brittle (Scramin et al., 2011). Using two or more film-
forming polymers of different categories to prepare composite films by
physically blending is an effective method to improve the properties of
films. According to our previous research (Li et al., 2019; Ni et al.,
2018; Wang et al., 2017), KGM/zein blend films could be formed by
solution casting, which showed better mechanical, thermal, water
vapor and oxygen barrier properties compared to pure KGM film and
zein film. The addition of zein to KGM may change the formation of
KGM molecular network. Further investigation on the KGM/zein film-
forming process could contribute to understandings of film structure
and properties.
The objective of this work was to understand the microstructural
development and the change of rheological properties of KGM/zein
blend film-forming solution during drying at 60 °C. This information is
essential for explaining the film-forming mechanism, as well as pro-
ducing the films with desirable microstructures that determine their
performance.
2. Materials and methods
2.1. Materials
Zein (Mw 2.5 × 104 Da; protein mass fraction was 98 %) was pro-
vided by Beijing J & K Technology Co., Ltd. (Beijing, China). Konjac
glucomannan (KGM) was obtained from Li Cheng Biological
Technology Co., Ltd. (Hubei, China). The KGM sample was character-
ized by a Mw of 1.012 × 106 Da, a molar ratio of mannose:glucose of
1.6:1, and a degree of acetylation of 1.85 %. Ethanol (AR, purity ≧99.5
%) and glycerol (AR, purity ≧99 %) were purchased from Sinopharm
(Chemical Reagent Co., Ltd., Shanghai, China). Rhodamine B (AR,
purity ≧99 %) was purchased from Aladdin Bio-Chem Technology Co.,
Ltd. (Shanghai, China).
2.2. Samples preparation for the film-forming process
Zein (0.1 g) was dissolved in 20 mL of 80 % (v/v) ethanol/water
solvent under stirring for 15 min at 25 °C. KGM (0.9 g) and glycerol (15
% based on the total amount of KGM and zein, w/w) were completely
dissolved in 100 mL water with a continuous stirring electric mixer
(OS20-Pro SCILOGEX Co., Ltd., USA) at 600 rpm for 1.0 h at 60 °C.
Afterward, the zein solution was slowly dropped into the KGM solution
to prepare KGM/zein blend film-forming solution at 60 °C for 30 min at
stirring speed 1000 rpm. Then, the blend film-forming solution was
poured into the glass plates (14.0 cm × 14.0 cm × 1.5 cm), and dried
in an oven (DNG-9031A, Jing Hong Co., Ltd., Shanghai, China) at 60 °C.
During the drying process, the samples were taken out at 0 h, 2 h, 4 h, 6
h, 8 h, and 12 h (completely dried to films), respectively. According to
drying time, the samples were coded as 0 h KZ, 2 h KZ, 4 h KZ, 6 h KZ, 8
h KZ and KZ film, respectively. As the reference sample, pure KGM film
was prepared by drying 100 mL KGM solution (1.0 %, w/v) on glass
plates (14.0 cm × 14.0 cm × 1.5 cm) and the amount of glycerol added
was 15 % (w/w) based on the total solid content.
2
Carbohydrate Polymers 250 (2020) 116840
2.3. Drying curves
The drying curves were obtained by measuring the mass loss during
the drying period. The weight of the samples was recorded accurately
using the electronic balance (JE1002, Puchuang metrology Co., Ltd.,
Shanghai, China) at the designated time intervals until the film formed.
The endpoint of drying was considered to be reached when the moisture
content of the film was 9.0 % (w.b.). The oven was placed in a con-
trolled environment of 25 °C and 68 % relative humidity to maintain
consistent experimental conditions. Three replications of each sample
were performed, and the data given was an average of these results.
2.4. Scanning electron microscopy (SEM)
The microstructures of the samples were observed with a high-re-
solution field emission scanning electron microscope (Su8010, JEOL,
Co., Ltd., Tokyo, Japan). The film-forming solutions at different drying
times were frozen instantaneously with liquid nitrogen and then va-
cuum freeze-dried. Then they were cut into small pieces for surface and
cross-section observation. The cross-section of pure KGM film and
KGM/zein blend film samples were prepared by breaking samples after
freezing in liquid nitrogen. Before testing, all samples were coated with
a thin layer of gold powder. The sputtered time was about 15 s and the
accelerating voltage was 2 kV.
2.5. Confocal laser scanning microscopy (CLSM)
CLSM (TCS SP8, Leica, Co., Ltd., Germany) was used to observe the
morphology and distribution of zein in KGM/zein blend samples.
Protein staining was based on the method of Li et al. (2019). The zein
was stained with rhodamine B. First, 4 mg of rhodamine B was dis-
solved in 1 mL of water to prepare the dye solution. Then 20 μL of the
dye solution was added into 20 mL of zein solution and mixed for 15
min at 150 rpm at 25 °C in the dark to ensure that the solution was
homogeneous, and also to give time for the dye to bind to the protein.
The dyed zein solution was mixed with the KGM solution to prepare the
dyed blend film-forming solution. The upper layer of the blend solution
at different drying times was taken out and placed on the microscope
slide for testing. The samples were excited by a red laser beam at 638
nm.
2.6. Differential scanning calorimetry (DSC)
The thermal properties of the samples were analyzed using a DSC
device (Mettler Toledo, Zurich, Switzerland) referring to the method of
Liu et al. (2020). The upper layer of the sample at different drying times
was taken out, frozen instantaneously with liquid nitrogen, vacuum
freeze-dried, and then placed on a Mettler aluminum pan for testing.
The test conditions were designed under N2 atmosphere, with an empty
pan as a reference. The test temperature was from 20 to 250 °C, and the
heating rate was 10 °C min−1.
2.7. Rheological measurements of film-forming solutions
Dynamical rheological properties of the film-forming solutions dried
at different drying times were measured with a rheometer (RS6000,
Hake Ltd., Germany) equipped with a parallel plate (35 mm diameter).
The gap was set as 1.0 mm and the temperature was set at 60 °C. For
each measurement, the upper layer of the sample was taken out and
placed on the parallel plate instrument. A thin layer of silicon oil was
placed around the sample to prevent the solvent evaporation during the
measurement. The values of the strain amplitude were checked to en-
sure that all measurements were set as 1.0 %, which was within the
linear viscoelastic zone. The frequency sweeps were performed from 0.1
to 10 Hz. The storage modulus (G') and loss modulus (G") were mea-
sured as a function of angular frequency. Complex viscosity (η*, Pa·s)
C. Li, et al.
was calculated as follows Eq. (1).
(G′)2 + (G″)2
η* =
ω (1)
Where ω is the angular frequency.
The relationship between η*and ω was analyzed using a power-law
model Eq. (2).
η* = Kωn (2)
Where K is the consistency index (Pa s ), ω is the angular frequency and
n
n is the power-law index.
2.8. Statistical analysis
All samples were prepared and tested at least in triplicate. Statistical
analysis was conducted using Origin 2017 (originLab corporation,
Northampton MA). Analysis of variance was performed using ANOVA
procedures of the IBM SPSS software (version 20.0, IBM Inc., USA,
2012) by Tukey’s multiple range test at significance level p < 0.05.
3. Results and discussion
3.1. Drying curves
Plots of the solvent evaporation ratio versus drying time are pre-
sented in Fig. 1. Typically, the drying of high moisture materials pre-
sents a constant drying rate period and one or two falling rate periods
(de Moraes, Scheibe, Augusto, Carciofi, & Laurindo, 2015). The drying
curves showed two stages: a first stage with linear solvent loss variation
from 0 to 89 % at a constant rate and a second stage in which the drying
rate decreased. This should be due to that the gradual solidification of
the surface of the film-forming solution prevented evaporation of the
solvent in the second stage. Similar tendencies have been reported
during the drying of soy protein films (Ortiz, de Moraes, Vicente,
Laurindo, & Mauri, 2017) and starch-fiber films (de Moraes et al.,
2015). Using conductive drying, Karapantsios (2006) found that the
falling rate periods of the drying curves of starch films started at below
50 % (w/w) water content for films less than 1 mm, which was inter-
preted by that the evaporation loss was prevented when the starch/
water viscous paste began to transform into a solid-like gel. Throughout
the drying period, the drying rate of KGM/zein blend film-forming so-
lution was greatly higher than that of pure KGM film-forming solution.
The time for KGM/zein blend film-forming solution to reach the
Fig. 1. Drying curves of KGM film-forming solution and KGM/zein blend film-
forming solution at 60 °C.
3
Carbohydrate Polymers 250 (2020) 116840
endpoint of drying was 12 h, which was shorter than that of pure KGM
film-forming solution. This phenomenon was explained by that the in-
teraction between zein and water molecules in the blend solution was
very weak due to the hydrophobic nature of zein, and the interaction
between zein and KGM (Wang et al., 2017) may weaken the interaction
between KGM and water. In addition, the small amount of ethanol in
the blend solution evaporated easier than water.
3.2. Structure and morphology analysis
The SEM micrographs of the solution surface and cross-section
during the formation of KGM film are shown in Fig. 2. KGM exhibited a
random coil conformation with molecular entanglement in water (Jian,
Siu, & Wu, 2015; Ni et al., 2018). At the beginning of drying (0 h), KGM
chains were fully expanded and entangled in water, and the entangled
molecular chains were overlapped in layers. With the increase of KGM
concentration (4 h, 8 h), the density of the molecular chain increased,
and molecular chains crossed and intertwined with each other, forming
more junction zones, and ultimately leading to a strong entanglement
network at higher concentrations. At the end of drying (KGM film),
KGM chains developed into a continuous network structure, and the
movement of the chains was limited, forming a dense solid film. It was
observed from the cross-section that the closer to the solution surface,
the denser the network, the smaller the pore and the thicker the pore
wall. Therefore in the drying mode of heat conduction, the closer to the
solution surface, the faster the water evaporates.
The microstructure change during the formation of KGM/zein blend
film (Fig. 3) indicated a significant difference from KGM film. Zein in
ethanol/water solution (80 %) formed spherical particles due to the
aggregation of molecules (Guo, Liu, An, Li, & Hu, 2005; Kim & Xu,
2008). The KGM/zein blend solution formed a stable homogeneous
system due to the balance between KGM, zein and solvents in the
system (Ni et al., 2018). Zein particles were filled in the KGM molecular
entanglement network during drying, indicating the existence of in-
termolecular interactions between zein and KGM. This was in agree-
ment with previous FTIR spectra result supporting that hydrogen bond
interactions and Maillard reaction occurred between zein and KGM
molecules (Wang et al., 2017). It was found that KGM chains in the
blend solution were thicker than that in the pure KGM solution (0 h KZ
in Fig. 3), and a loose network with a lot of holes was formed. This may
be due to that the hydrophobicity of zein promoted the approach and
overlap of hydrophilic KGM molecules, leading to the aggregation of
KGM chains into thicker chains, and increasing of the distance between
thicker molecular chains, which was conducive to the formation of the
macroporous network. With drying proceeded (4 h, 8 h), the network in
the blend solution was gradually strengthened and became dense. The
network was irregular and had larger pores compared with that in pure
KGM solution. The surface of the final blend film was rough and the
cross-section was not compact compared with pure KGM film. The
molecular network structure of the blend film was different from that of
pure KGM film, which would affect their physical and chemical prop-
erties. Previous reports have also confirmed their significant differences
in performance (Li et al., 2019; Wang et al., 2017).
Further CLSM microstructure observation (Fig. 4) was performed to
visualize zein association states during the drying process of KGM/zein
blend film-forming solution. The zein particles grew to larger sizes and
the particle density increased significantly with the extension of drying
time. The reason was that solvent evaporation led to an increase in zein
concentration, resulting in easy aggregation of zein particles. Zein
particles in all samples were homogeneously distributed in KGM con-
tinuous matrix without phase separation. The high viscosity formed by
KGM water phase could help to prevent large-scale agglomeration of
zein particles. The rough surface of the KGM/zein blend film (Fig. 3)
can be related to zein aggregation. KGM/zein blend films showed better
moisture resistance compared to pure KGM film (Wang et al., 2017),
which was ascribed to that the distribution of zein particles created
C. Li, et al.
Fig. 2. SEM micrographs of surface and cross-section of KGM samples at different drying times.
impermeable obstacles to permeating water vapor molecules and ex-
tended the water diffusion path. The control of the drying process will
also affect the degree of zein aggregation. Li et al. (2019) reported that
different drying temperatures could affect the size of zein aggregation
particles in the film, thus changing the mechanical and barrier prop-
erties of the film.
3.3. Thermal properties
The DSC heating curves of the samples at different drying times are
presented in Fig. 5. It was found that KGM film and KGM/zein blend
4
Carbohydrate Polymers 250 (2020) 116840
film exhibited endothermic peaks at 75.4 °C and 92.7 °C respectively,
corresponding to the respective glass transition temperature (Tg),
consistent with reported results (Li et al., 2019). The higher Tg of the
blend film in comparison to that of KGM film indicated better thermal
stability, which was caused by the interaction and the good compat-
ibility between KGM and zein molecules(Wang et al., 2017). As the
drying progressed, the Tg of 0 h KGM, 4 h KGM, 8 h KGM were 62.1,
65.9 and 71.4 °C, respectively; 0 h KZ, 4 h KZ, 8 h KZ showed Tg at
73.5, 81.1 and 85.0 °C, respectively. The Tg of KGM samples increased
with drying, and the Tg of KZ samples also showed the same trend.
Moreover, under the same drying time, the Tg of the KZ sample was
C. Li, et al. Carbohydrate Polymers 250 (2020) 116840

Fig. 3. SEM micrographs of surface and cross-section of KGM/zein blend samples at different drying times.

5
C. Li, et al. Carbohydrate Polymers 250 (2020) 116840

Fig. 4. CLSM images of KGM/zein blend samples at different drying times. The red area represents zein particles and the black area represents KGM components.

significantly higher than that of the KGM sample. Changes in Tg in-
dicated that the molecular interaction in film-forming solutions was
strengthened during drying, and the addition of zein improved the
thermal stability of film-forming solutions.
3.4. Rheological properties
3.4.1. Dynamic viscoelastic properties
In order to obtain the information of molecular entanglement and
molecular network formation during drying, the dynamic viscoelastic
properties of the film-forming solutions were evaluated. Frequency
dependence of storage modulus G' and loss modulus G" was observed at
different drying times (Figs. 6 & 7 ). Above 8 h drying time, it is difficult
to test and explain the rheological properties because the solid film
begins to form. Therefore, the rheological properties at five drying
times (0 h, 2 h, 4 h, 6 h, 8 h) were investigated.
For KGM film-forming solution dried at 60 °C, both G' and G" of the
samples at different drying times increased with frequency and showed
a crossover (Fig. 6). G" values were higher than G' at lower frequencies
but the G' values became larger than G" at higher frequencies. This is a
typical concentrated solution behavior (Nishinari, 1997). G' is related to
the elastic energy stored in viscoelastic material during deformation,
reflecting the elastic solid-like characteristics of polymers; while G" is
related to the dissipated energy as heat during deformation, reflecting
the viscosity of the material. KGM samples showed more liquid-like
properties at lower frequencies (G" > G') and more elastic solid-like
behavior at higher frequencies (G' > G"). This could be explained by
that the molecular chains had more time to relax and disentangle

Fig. 5. DSC curves of KGM samples and KGM/zein blend samples at different drying times.

6
C. Li, et al.
Fig. 6. Storage modulus (G′) and loss modulus (G″) for KGM samples at different drying times.
during a long period oscillation at low frequencies, and the solution
behaved as a viscous liquid. However, the molecular chains could not
disentangle during a short period oscillation at high frequencies and
formed a temporary three-dimensional network structure, and thus the
solution exhibited an elastic solid-like state (Nishinari, 1997;
Yoshimura, Takaya, & Nishinari, 1998). As drying proceeded, the KGM
concentration increased due to the evaporation of water, and both G'
and G" of the samples were increased. This may be explained as higher
KGM content resulting in an increased chance for macromolecular
chain entanglements, as reflected by the increasing modulus (Wang
et al., 2014). The crossover point moved toward low frequencies. At 0
h, 2 h, 4 h, 6 h and 8 h, the crossover frequency of samples occurred at
1.0 Hz, 0.31 Hz, 0.23 Hz, 0.17 Hz, and 0.13 Hz, respectively. The lower
crossover frequency indicated the stronger effects of entanglement and
hydrogen bonding (Luo, He, & Lin, 2013). It was consistent with the
result of the SEM (Fig. 2) that the entanglement network was
7
Carbohydrate Polymers 250 (2020) 116840
continuously strengthened with drying.
Fig. 7 shows the change in G' and G" as a function of angular fre-
quency for KGM/zein blend film-forming solution. At the initial stage of
drying (0 h), the G' and G" values of the blend solution increased with
frequency. Compared with 0 h KGM solution, G' and G" of the blend
solution were lower and their crossover point shifted to high frequency.
This was due to the low content of KGM in the blend solution, which
reduced the entanglement of molecular chains. Entanglement effects
play an important role in the rheological behavior of flexible linear
polymers, but they do not exist in colloidal suspensions (Tanaka,
Nishikawa, & Koyama, 2005). As drying proceeded (2 h–8 h), the blend
solution showed elastic solid-like behavior (G' > G") and no crossover
was observed over the frequency range. It indicated that the average
chain relaxation time of the blend solution was greater than that of the
0 h blend solution. Furthermore, with the increase of drying time, G'
and G" gradually became parallel, and both moduli showed slight
C. Li, et al.
Fig. 7. Storage modulus (G′) and loss modulus (G") for KGM/zein blend samples at different drying times.
frequency dependence. This might be attributed to the gradual forma-
tion of a weak gel (Nishinari, 1997, 2009). These observations re-
presented that zein particles had a great effect on the entanglement of
KGM molecules, and the blend solution was easier to form a weak gel
than KGM solution. The overlap and entanglement of KGM chains
caused by the addition of zein promoted the transition from solution to
weak gel. Luo et al. (2013) reported that the sodium hydroxide solution
could restrain the expansion of KGM chains and increase the rate of
gelation.
3.4.2. Complex viscosity
The complex viscosity (η*) for film-forming solutions at different
drying times is plotted against the frequency in Fig. 8. As drying pro-
gressed, the η* values at a given frequency were observed to increase
significantly. Moreover, KGM samples and KZ samples revealed shear-
thinning behavior as their η* values decreased gradually with
8
Carbohydrate Polymers 250 (2020) 116840
increasing frequency. In order to quantitatively evaluate the viscoe-
lastic nature of samples at different drying times, a power-law model
had been applied to the complex viscosity and frequency data (Tables 1
and 2), which showed high R2 (all > 0.96). The power-law index (n)
decreased, indicating a more pseudoplastic behavior in samples and the
weak dependence on frequency (Kim & Yoo, 2009). The n value of 2 h
KZ (3.61 % solid content) was almost equal as that of 8 h KGM (6.98 %
solid content), which was obviously smaller than that of 6 h KGM (4.69
% solid content). This may be attributed to the enhanced molecular
entanglement force and improved molecular network with the addition
of zein into KGM solution. Our previous studies (Wang et al., 2017)
showed that KGM/zein blend films had good mechanical properties,
which was related to the enhanced network structure shown in this
study.
C. Li, et al. Carbohydrate Polymers 250 (2020) 116840

Fig. 8. Complex viscosity (η*) of KGM samples (a) and KGM/zein blend samples (b) at different drying times.

Table 1 gel. The η* data for KGM solution and KGM/zein blend solution were
Power-law parameters (K, n) of KGM samples. fitted by the power-law model. As a result, the n value of the blend
Samples Power-law parameters solution became smaller than that of KGM solution with the drying
process, which could be attributed to the enhancement of molecular
K (Pa sn) n R2 entanglement force.
0 h KGM 12.84 ± 1.42a −0.44 ± 0.014a 0.98
2 h KGM 50.18 ± 1.49b −0.48 ± 0.007b 0.98
CRediT authorship contribution statement
4 h KGM 112.47 ± 14.45c −0.53 ± 0.009c 0.98
6 h KGM 153.64 ± 8.80d −0.55 ± 0.012d 0.98 Chong Li: Methodology, Data curation, Software, Writing - original
8 h KGM 225.45 ± 31.74e −0.59 ± 0.008e 0.97 draft. Fei Xiang: Validation, Formal analysis, Visualization. Kao Wu:
Writing - review & editing, Supervision, Data curation. Fatang Jiang:
Different superscript letters (a–e) within the same column indicate significant
Writing - review & editing. Xuewen Ni: Supervision, Funding acquisi-
differences between formulations (p < 0.05).
tion, Conceptualization, Methodology, Visualization, Writing - review &
editing.
Table 2
Power-law parameters (K, n) of KGM/zein blend samples.
Declaration of Competing Interest
Samples Power-law parameters

K (Pa sn) n R2 The authors report no declarations of interest.

0 h KZ 3.138 ± 0.80a
−0.39 ± 0.02a
0.98 Acknowledgements
2 h KZ 36.63 ± 1.79b −0.60 ± 0.007b 0.99
4 h KZ 60.99 ± 2.86c −0.64 ± 0.018c 0.99
6 h KZ 109.58 ± 7.30d −0.73 ± 0.03d 0.99 This work was financially supported by National Natural Science
8 h KZ 353.35 ± 72.60e −0.62 ± 0.25bc 0.97 Foundation of China (Grant No. 31901655) and the technical support
program of Hubei University of Technology (Grant No. CPYF2018004).
Different superscript letters (a–e) within the same column indicate significant
differences between formulations (p < 0.05).
References

4. Conclusions
During film formation, the drying process of KGM solution and
KGM/zein blend solution at 60 °C was divided into two stages: a con-
stant drying rate period and a falling rate period. The gradual solidifi-
cation of the solution surface reduced the rate of solvent evaporation
with drying. The addition of zein affected the entanglement network of
KGM in the blend solution and increased the entanglement force.
Compared with KGM solution, KGM chains in the blend solution were
thicker and formed a molecular network with larger pores. Zein parti-
cles grew to larger sizes due to aggregation but were homogeneously
distributed in KGM continuous matrix without phase separation
throughout the entire drying process. The blend solution showed better
thermal stability than KGM solution. As the drying proceeded (up to 8
h), G' and G" of KGM solution increased with frequency and showed a
crossover. The crossover point moved toward low frequencies with
drying, indicating the stronger effects of entanglement and hydrogen
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