pubs.acs.

org/journal/ascecg Research Article

Synergistic Effect of Sodium Alginate and Lignin on the Properties

of Biodegradable Poly(vinyl alcohol) Mulch Films
Weiyi Su, Zhiwei Yang, Haoyang Wang, Jing Fang,* Chunli Li, Gaojin Lyu, and Hao Li*
Cite This: ACS Sustainable Chem. Eng. 2022, 10, 11800−11814 Read Online

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ABSTRACT: Replacing petrochemical polymers with biomaterials

for biodegradable mulch applications has attracted widespread
attention. However, improving film performance and reducing costs
remain an issue. In this work, we found that the synergistic effect of
Downloaded via SOGANG UNIV on November 23, 2023 at 02:40:08 (UTC).

sodium alginate and quaternary lignin significantly improved the

performance and reduced the cost of poly(vinyl alcohol) films. The
water retention, ultraviolet (UV) resistance, heat collection, light
transmission, mechanical properties, soil consolidation, and the
degradation rates of the composite films were systematically studied.
We found that the addition of lignin enabled the film to achieve
complete UV resistance, while the sodium alginate synergistically
improved the mechanical and water-holding properties of the film.
The film improved soil slumping, and the water vapor permeability
of the film was 109.2 g·m−2·day−1. The degradation of the film was facilitated by the self-degradation properties of sodium alginate
and lignin, which degraded 55% after 50 days.
KEYWORDS: degradable, mulch film, lignin, sodium alginate, poly(vinyl alcohol)

■ INTRODUCTION
Arid regions cover ∼45% of the Earth’s land surface, which
treatment and control means.15 Mechanizing the recycling of
plastic films is difficult, resulting in high economic costs that
comprises integral parts of agricultural systems.1 Water hinder the rational recycling of films.16 Therefore, biodegrad-
resources in agriculture are significant constraints for crop able films have to be produced to solve “white pollution” while
production; therefore, water-holding technology using natural offering the same performance as traditional petroleum-based
coverings such as mulch and synthetic mulch films has been films.17
Green biodegradable mulch films have been widely studied
used.2 Synthetic agricultural mulches are typically used in the
in recent years. The biodegradable material is one that can
form of monopoly furrows, flat sheets, and drip irrigation,
itself be completely broken down into carbon dioxide and
which are then used to cover the soil surface of crops.3 The
water by microorganisms such as bacteria, fungi, and
main role of agricultural mulch is to hold water, though it also
actinomycetes.18 Biodegradable mulch should possess charac-
provides other functions such as weeding,4 pest prevention,5
teristics such as temperature increase, water retention, and
drought and flood prevention,6 salt suppression,7 soil improve-
production promotion.5 Therefore, it can replace polyethylene
ment,8 dustproof and sand fixation,9 and keeping the
film in solving the problem of “white pollution.” Biodegradable
agricultural products clean.10 Thus, agricultural films serve
raw materials are commonly used as chemical synthesis
the purpose of promoting crop growth, increasing yields, and
materials, for example, poly(vinyl alcohol) (PVA), etc. PVA
improving agricultural efficiency.
offers better mechanical properties as a crystalline polymer.19
Currently, the raw materials used in traditional agricultural
PVA exhibits strong hydrophilic, water-soluble, and adhesive
land films mainly include petroleum-based polymers such as
physical properties, and it can also biodegrade into CO2 and
polyethylene.11 However, the “white pollution” caused by
H2O.20 Therefore, PVA has been widely used in the
these materials has been shown to be very harmful to the soil.12
Traditional petroleum-based films are extremely difficult to
degrade in the soil, resulting in residue buildup that can reduce Received: April 17, 2022
soil permeability. This can hinder water uptake and the root Revised: August 19, 2022
development of crops.13 With time, this residue can result in Published: August 31, 2022
the accumulation of harmful substances in the crops, which can
be transmitted to humans.14 Traditional film recycling and the
development of green biodegradable films are the two current

© 2022 American Chemical Society https://doi.org/10.1021/acssuschemeng.2c02290

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Scheme 1. Principle of Quaternary Amination of the Lignin (a) and Preparation Process of the Plastic Film (b)
preparation of biodegradable films.21 The raw materials of
natural polymers mainly include starch, chitosan, and sodium
alginate (SA). Starch films have been extensively studied due
to the easy reaction of the hydroxyl groups.22 However, starch
exhibits no thermoplasticity or fluidity.23 Chitosan exhibits
certain crystalline and improved mechanical properties.
However, the film-coating efficiency of chitosan is low.24 SA
has mild film-forming conditions while exhibiting polyionic
behavior in aqueous solutions.25 Films prepared by mixing SA
and other polymers have shown important breakthroughs for
certain applications such as food packaging and medicine.26
When mulch films are composed of several of the above
biomolecular materials, it can lead to defects in the mechanical
properties and poor water resistance. PVA offers better
mechanical properties; however, it has low water resistance
after being produced into a film, as well as poor water holding
and low plasticity properties. Therefore, PVA often has to be
modified and blended with other materials to achieve
enhanced utility.27
For PVA film preparation, cross-linking with glutaralde-
hyde16 and citric acid28 or addition of xylan, eggshell powder,29
liquefied chitin,30 starch,31 chitosan,32 or cellulose33 natural
polymers has shown to significantly improve tensile strength.
However, the addition of chitosan and cellulose will reduce the
elongation at break of the material, and the addition of citric
acid-modified xylan34 and SA35 will reduce the tensile strength.
However, the elongation at break will be enhanced
accordingly. In addition, SA exhibits antibacterial and
corrosion resistance properties. The addition of glutaraldehyde
cross-linking, clay,36 and chitosan can be used to improve
water resistance, while the addition of clay, cellulose, xylan, and
other substances can reduce the water vapor permeability,
making the material suitable for use in food packaging. The
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addition of lignin37 can also improve the UV resistance of the
film. In summary, combining PVA with other degradable
materials offers a low-cost material with water holding, water
permeability, and good mechanical properties as well as
corrosion resistance, antifouling potential, and film-forming
abilities.38
Lignin is the only aromatic ring polymer in nature and has a
unique structure and a large number of phenolic hydroxyl
groups.39 The phenolic hydroxyl groups in lignin exhibit some
antioxidant and antibacterial abilities.40 Lignin also has
biocompatibility and degradability.41 Thus, lignin has been
used to prepare films such as PVA and PLA. For example,
when lignin was added, the oxidation resistance and
mechanical strength of PLA films improved.42 When lignin
was mixed with chitosan@PVA alcohol to prepare a film, the
oxidation resistance and the mechanical strength of the film
containing lignin significantly improved.43 In lignin@chitosan
blend films, the antioxidant and UV resistance of the lignin-
containing films improved, and the visible light transmission
reached 30−50%.44 The elongation at break of the lignin@
starch blend film also increased, while the tensile strength was
slightly reduced.45 Overall, the addition of lignin has been
shown to improve the oxidation resistance, UV resistance,
mechanical properties, and water retention of films.
This work explored the influence of SA and quaternized
lignin (MAL) on the performance of PVA when used as an
agricultural film. The addition effects of SA and MAL were
explored on water resistance, mechanical properties, light
transmittance, heat collection, UV resistance, water-holding
performance, soil fixation, and degradability of the blend film.
Moreover, the addition effect of poly(ethylene glycol) on the
mechanical properties, water retention, and degradability of the
blended film was evaluated. The mechanism of performance
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enhancement of the PVA film was studied by Fourier
transformation infrared spectroscopy (FTIR), scanning elec-
tron microscope (SME), and X-ray diffraction analysis (XRD).
■ MATERIALS AND METHODS
Materials. PVA (degree of polymerization: 1700, 88% hydrolyzed)
and SA (purity 98%, molecular weight Mn: 398.31) were purchased
from Shanghai Aladdin Technology Co., Ltd. Glutaraldehyde (GA, 25
wt %), poly(ethylene glycol) 300 (PEG 300), sodium hydroxide
(NaOH), and trihydroxypropyl dimethylammonium chloride (60 wt
%) were purchased from Tianjin Kemiou Chemical Reagent Co., Ltd.
Alkali lignin (AL, molecular weight Mn: 1500) was purchased from
Shandong Shengquan Co., Ltd. All commercially available chemicals
and reagents were used as received without further purification.
Film Fabrication. MAL (quaternary ammonium lignin) was
prepared by reacting AL with tris(hydroxypropyl) dimethylammo-
nium chloride with a mass ratio of 1:1 at a temperature of 85 °C for 4
h under alkaline conditions. The principle is shown in Scheme 1a. A
schematic showing the fabrication of the films is presented in Scheme
1b. The PVA was dissolved in a constant temperature water bath at 90
°C, and the resulting 10 g PVA (10 wt %) solution was cooled and set
aside. Afterward, the prepared MAL was added to the beaker
dissolved, and then SA was added. The mixture was magnetically
stirred at 900 rpm for 2 h to obtain the 10 g MAL + SA mixed
solution. Then, the mixed solution was mixed with an equal mass of
PVA (10 wt %) solution and poured into a 250 mL round-bottom
flask. Afterward, the GA (1 wt %) cross-linking agent was reacted at
80 °C for 4 h, cooled to room temperature, and then prepared for use.
Then, 8 milliliters of the film casting solution was poured into a
poly(tetrafluorethylene) (PTFE) mold, dried at room temperature for
24 h, and placed in a 60% relative humidity (RH) environment. The
film thickness was ∼80 μm. The SA/PVA/MAL composite mulch
films (Table 1) were produced by the following method.
Table 1. Composition in Weight Percent of the SA/PVA/
MAL Composite Mulch Films
coded values of formulations SA (wt %) PVA (wt %) MAL (wt %)
0%SA/PVA 0 100 0 Water Retention Test of the Covered Soil. A container with an
5%SA/PVA 5 100 0
10%SA/PVA 10 100 0
15%SA/PVA 15 100 0 Changes in the pot weight were recorded every 24 h until the total
0%MAL/SA/PVA 5 100 0 weight did not change by more than 5%.
5%MAL/SA/PVA 5 100 5 Degradation Assessment. The membrane samples were buried
10%MAL/SA/PVA 5 100 10
15%MAL/SA/PVA 5 100 15
20%MAL/SA/PVA 5 100 20
Preparation of the PEG films was consistent with the above
methods. The films were prepared with PEG to 5%SA + 15%MAL/
PVA cast film volume ratios of 0.04/8, 0.08/8, 0.12/8, 0.16/8, and
0.2/8 (mL), which were denoted as 5%SA + 15%MAL/PVA/
0.5%,1.0%, 1.5%, 2.0%, and 2.5%PEG.
Characterization. The liquid to be tested was slowly poured into
the viscosity tester, and the mean was measured at least three times
for each sample (viscometer NDJ-5s, China). The different membrane
samples in the 1000−4000 cm−1 range were analyzed using Fourier
transformation infrared spectroscopy (ATR-FTIR, TENSOR 27,
Bruker, Germany). The surface and profile characteristics of the
membrane samples were analyzed using field-emitting electron
microscopes (FEI, Nova NanoSEM 450, The Netherlands). Different
membrane samples were also analyzed by XRD (XRD, ESCALAB
250Xi), where the measurement angle was 5−60° and the scanning
speed was 6°/min.
Mechanical Properties. The mechanical properties of the film
samples were tested by an electronic single yarn strength tester
(HD021NS). The membrane samples were cropped to a size of 100
mm in length and 10 mm in width, and the universal puller had a
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spacing of 90 mm and a tensile rate of 100 mm/min. The tensile
strength was obtained by
F = f /(L × ) (2.1)
where F is the tensile strength (MPa), f is the pull size (N), L is the
sample width (m), and μ is the sample thickness (m).
Water Permeability and Water Content. Using the proposed
cup method, 10 g of anhydrous calcium chloride was added to an 80
mL glass vial. The membrane samples were fixed at the mouths of the
bottles, and then the glass bottles were placed in a high humidity
environment (65% RH) at room temperature. Changes in bottle
weight were recorded every 24 h until the total weight did not change
by more than 5%. The blank control for water vapor permeability
consisted of a bottle mouth without film. This was used to test the
water vapor transmission rate, which was calculated according to
Pwater = m/(S × d) (2.2)
−2 −1
where Pwater is the amount of water vapor through (g·m ·day ), S is
membrane area (m2), and d denotes the time in days.
The initial weights of the membrane samples were recorded as m1.
Subsequently, membrane samples were dried in an oven at 100 °C for
24 h and then weighed and recorded as m2. The water content μ was
calculated by
= (m1 m2)/m1 (2.3)
Light Transmittance and Heat Collection. The membrane
samples were fixed on a UV−Visible spectrophotometer (Cary 100
UV−Vis spectrometer, Agilent, China), and the film transmittance
was measured at wavelengths near UV light at 380 nm and visible
light at 650 nm.
The membrane samples were fixed on the soil surface, and a solar
simulator (PL-X500) was used to illuminate the samples for 1 h under
a light intensity of 1 kW/m2. Then, an infrared thermometer (Testo
865) was used to measure the temperature changes on the film and
soil surfaces. At least five different positions, 2 cm apart, were used to
measure the temperature of each sample, and the average value was
obtained.
open area of 30 cm2 was prepared, and the container was filled with
soil containing 20 g of water. The film casting solution was drenched
on the soil surface, and the container was left at room temperature.
10 cm deep below the soil surface, and the soil moisture was
maintained by spraying quantitative amounts of water at 5-day
intervals.46 The simulated soil degradation experiments47 were carried
out at room temperature. After 50 days, the film surfaces were rinsed
with water and dried in an oven for 24 h before, and they were
weighed and assessed according to
F = (m3 m4)/m3 × 100% (2.4)
where m3 is the mass of the sample before it was buried and m4 is the
mass of the sample after it was buried.
■ RESULTS AND DISCUSSION
Characterization of the Blend Membranes. FTIR. The
FTIR spectra of the PVA, PVA + GA, and 5%SA/PVA films
are shown in Figure 1. After cross-linking agents GA and SA
were added, the intermolecular hydrogen bonds of the film
moved from 3288 cm−1 in the low band to 3313 cm−1 in the
high band. Thus, the addition of GA and SA weakened the
intermolecular hydrogen bonds of the PVA molecular chains.
Also, a new peak appeared in the 5% SA/PVA film at a
wavelength of 1612 cm−1 (C�O), which was attributed to the
stretching vibrations of the carboxylic acid group in SA. The
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Figure 1. FTIR spectra of the pure PVA, PVA + GA, 5%SA/PVA
films.
new peak at 1021 cm−1 (C−O−C) was due to the reaction
between GA and −OH, forming a new chemical bond.
The FTIR spectra of the 5%SA/PVA films with different
MAL contents are shown in Figure 2. The increase in MAL
addition shifted the characteristic peak of −OH at 3302 cm−1
to the lower band at 3294 cm−1, and MAL enhanced the
intermolecular hydrogen bonding in the PVA (Figure 2a). The
−OH peak area of the film with 10%MAL content significantly
increased. This was due to the formation of a spatially
reticulated cross-linked gel structure with increased water
molecules between the films, as MAL consisted of quaternary
ammonium salt with no obvious peak position. However, the
effect of MAL on the intermolecular forces of the membrane
could be determined by observing the C�O peak in the
carboxylic acid group. An increase in MAL addition shifted the
COO-antisymmetric stretching vibration peak at 1616 cm−1 to
the lower frequency band at 1586 cm−1 (Figure 2b). This was
attributed to the gradual increase in electrostatic interactions
between the positively charged quaternary ammonium group
Figure 2. FTIR spectra of the 5%SA/PVA films with different MAL contents: (a) 700−4000 cm−1 and (b) 1500−1650 cm−1.
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of MAL and carboxylic acid on SA. Meanwhile, the peak area
of 1600 cm−1 (C�O) gradually increased, and the peak shape
was gradually sharpened. Thus, the increase in free carboxylic
acid groups was confirmed. The characteristic peaks of the
−OH and COO− vibrations in the films with different MAL
contents are shown in Table 2. In summary, the hydrogen
Table 2. Characteristic Peaks of the −OH and COO−
Vibrations in the Films with Different MAL Contents
−OH wavenumber COO− wavenumber
content (cm−1) Δ (cm−1) Δ
0% 3302 0.0 1616 0.0
5% 3311 +9.0 1610 −6.0
10% 3303 +1.0 1609 −7.0
15% 3299 −3.0 1587 −29.0
20% 3294 −8.0 1586 −30.0
bonding due to surface hydroxyl groups of PVA and SA were
enhanced by MAL in the composite film. The electrostatic
forces of the seasonal ammonium salt were enhanced by the
carboxylic acid group. In this study, the degradable film was
fully characterized by XRD analysis, as shown in Figure S1. It
was confirmed that the electrostatic interaction between MAL
and SA could improve the regularity of SA and PVA molecules.
The FTIR spectra of the PEG plasticized 5%SA + 15%
MAL/PVA films are shown in Figure 3. The characteristic peak
(−OH) of the film at 3299 cm−1 shifted to 3348 cm−1, and its
peak shape gradually became wider, and the peak area
gradually decreased. This showed that the addition of PEG
weakened the intermolecular hydrogen bonds of the film. It
also reduced the number of intermolecular hydrogen bonds
(Figure 3a). The C−H stretching vibration peak shifted from
2931 to 2873 cm−1 in the lower band, while the peak area
gradually strengthened. This was because PEG contained a
large amount of ethyl groups, which allowed the PVA
molecular chains to play a role in softening and spacing. As
a result, this led to a weakening of the intermolecular hydrogen
bonds of PVA. The peak at 1021 cm−1 almost disappeared
(C−O−C), which confirmed that the effective response of GA
in the composite film was reduced. The addition of PEG
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Figure 3. FTIR spectra of the PEG plasticized 5%SA + 15%MAL/PVA films at (a) 700−4000 cm−1 and (b) 1450−1700 cm−1.

shifted the peak of the film at 1587 cm−1 (COO−) to the the above results confirmed that the addition of PEG hindered
lower 1569 cm−1 band. The peak area of the film containing the reaction between PVA and GA. However, the electrostatic
2.5% EPG at this wavelength was drastically reduced (Figure effect between MAL and SA gradually increased. The
3b). The characteristic peaks for the −OH and C−H vibration appearance of the C−N characteristic peak in the film at a
in the different PEG sample films are shown in Table 3. All of wavelength of 1650 cm−1 confirmed that excessive PEG
addition could significantly increase the agglomeration of
Table 3. Characteristic Peaks of the −OH and C−H MAL. Therefore, this showed that the compatibility of MAL
Vibrations for the Different PEG Sample Films with PVA could be reduced.
−OH wavenumbers C−H wavenumbers Surface Morphology. SEM analysis of the film cross
content (cm−1) Δ (cm−1) Δ sections was carried out to observe the compatibility of MAL
0% 3299 0 2931 0 with the films, as shown in Figure 4. When a small amount of
0.5% 3297 −2 2927 −4 MAL was added to the PVA/SA film (5% MAL), it existed
1.0% 3301 +2 2925 −6 mostly in the form of single molecules, and almost no
1.5% 3299 0 2923 −8 aggregates were seen in the cross sections due to the
2.0% 3340 +41 2875 −56 entanglement of MAL and SA. The particle size of the MAL
2.5% 3353 +54 2873 −58 aggregates gradually increased (0.5−2 μm) with increasing
MAL addition. The MAL aggregates started to appear in the
cross sections of 10% MAL film, and the maximum number of

Figure 4. SEM images showing the profiles of 5%SA/PVA films with different MAL contents.

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Figure 5. Dispersion behavior of the different concentrations of MAL in the films.
MAL aggregates reached 2 μm in the 20% MAL film. Excessive
MAL aggregation affected the compatibility with PVA, which
in turn reduced the performance of the film. Thus, 15% MAL/
2% PEG had smaller intersectional MAL aggregates compared
to the 15% MAL film. Thus, we confirmed that PEG promoted
the dispersion of MAL in PVA, and the 15% MAL/2% PEG
films had good mechanical properties compared to the pure
PVA films. According to the above results, we concluded that
the dispersibility and compatibility of MAL were crucial to the
performance of the film.
The dispersion mechanism of MAL in the film is shown in
Figure 5. When the MAL concentration was low, it resulted in
a double cross-linked network of PVA and SA. MAL was
electrostatically wound in the two ends of the SA chain, which
weakened the original SA and PVA and the hydrogen bonding
between PVA. However, with increasing concentration of MAL
(whose particle size also progressively increased), the SA
chains formed a core−shell structure with SA on the outside
and MAL on the inside through electrostatic effects. The SA
wrapped around the surface of MAL, while GA cross-linked the
PVA with the SA/MAL complex. Therefore, different MAL
concentrations affected the other properties of the film, such as
the mechanical properties and water retention.
Material Selection and Exploration. The water resist-
ance of films is a fundamental part of their applications. In this
study, when PVA was used as the main film material, a
preliminary exploration experiment was carried out on the
water resistance of the films. We found that adding MAL
improved the water resistance of the PVA film (Figure 6a),
where the colors of the films in the images were due to the
addition of indicators (methyl orange and basic magenta).
Figure 6. (a) Water resistance of MAL among different films and (b)
dispersibility of MAL in the films ((A) PVA film; (B) SA/PVA film;
(C) MAL/PVA film; (D) SA/MAL/PVA film).
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However, the direct blending of MAL and PVA resulted in a
problem of maldistribution lignin dispersion (Figure 6b).
Macroscopic observations revealed that the addition of
polyelectrolyte anionic SA improved the dispersion of MAL
in the PVA film. The compatibility of MAL with PVA was
improved, and the water resistance of the film was also
significantly improved. As shown in Figure 6, the PVA/SA/
MAL films had the best water resistance and dispersibility.
Therefore, investigation experiments of SA and MAL on the
PVA film were conducted.
Effect of SA Concentration on PVA Film. Mulch film
will be influenced by its viscosity and mechanical properties
derived from its preparation and application. Viscosity can
affect the spraying and flow of liquid mulch film. The water
retention properties of the mulch film served as an important
indicator for application. The viscosity, mechanical properties,
and water vapor permeability of the PVA films after SA
addition are shown in Figure 7. For the GA cross-linked PVA
film, as SA addition increased, the viscosity of the casting
solution significantly increased. This is due to the higher
molecular weight and higher viscosity of SA. Meanwhile, water
vapor permeability increased, and the mechanical properties
gradually declined, and were lower than those of the PVA
films. Because SA contained more hydroxyl and hydrophilic
properties than PVA, the water vapor permeability increased.
However, the decline in mechanical performance was because
the reaction activity of SA with GA was greater than PVA. As a
result, the reaction between GA and SA with polyhydroxyl
groups occurred more easily. In comparison, the reaction of SA
with PVA was difficult. The above discussion was explained by
FTIR analysis. The purpose of SA addition was to adjust the
dispersion of the added MAL without affecting the mechanical
properties and water vapor permeability of the PVA cross-
linked film. Therefore, SA addition was more beneficial at a
content level of 5% in the film (SA to PVA mass ratio of 5%) in
terms of its mechanical properties and water vapor
permeability.
Effect of MAL on PVA/SA Films. The viscosity,
mechanical properties, and water vapor permeability of the
PVA/SA films after the MAL addition are shown in Figure 8.
The viscosity of the MAL cast film solution was significantly
reduced with a small addition amount. Because MAL acted as a
cation surfactant, it reduced the viscosity. However, the
viscosity of the casting solution increased as MAL and SA
underwent mutual entanglement resulting from electrostatic
interactions when the MAL addition amount was high.
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Figure 7. Influence of cross-linking agent and SA on the PVA film: (a) viscosity of the casting liquid, (b) water vapor permeability, and (c)
mechanical properties.
Therefore, the addition of MAL caused the tensile strength of
the film to decrease from 110 to 87 MPa. However, an increase
in MAL addition caused the pull-up strength of the film to
initially increase and then decrease, and the 5%SA + 15%
MAL/PVA film had the largest tensile strength of 112 MPa.
This was because the particle size of MAL gradually increased
as the concentration of MAL in the solution increased. When
the concentration was low, MAL was in the form of small
single molecules. At a high concentration, however, MAL
entangled with SA and aggregated. When the aggregate particle
size is too large, the chemical bond and linkage between MAL
and PVA film become weak, and holes appear between
molecules. Therefore, the tensile strength decreased. The
barrier performance of the film to water vapor initially
increased and then decreased as a result of the 15%MAL
film (5%SA + 15%MAL/PVA). Compared to the film without
MAL, the barrier performance decreased when the MAL
addition amount was too low (5%MAL/PVA) or too high
(20%MAL/PVA). The pore size and free volume of the film
were higher, and the water vapor permeability increased.
Therefore, the water vapor permeability of the 15%MAL film
was 109.2 g·m−2·day−1.
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Light Transmission and Heat Collectivity of the Film.
The mulch film was exposed to sunlight for a long period, as
UV light can cause photoaging of mulch films. In addition, the
temperature of the mulch film and soil were increased, as
suitable temperatures are conducive to the growth of crops.
Thus, the UV resistance and heat preservation abilities of the
mulch were studied. The light transmission of different films at
380 and 650 nm is shown in Figure 9a. When the PVA film
was compared to the 5%SA/PVA films, the addition of SA to
the film showed almost no effect on the transmittance at UV
wavelengths of 380 and 650 nm. The transmittance of the film
containing MAL was almost zero at a UV wavelength of 380
nm due to the UV absorption properties of lignin. The
addition of MAL to the film gradually decreased the visible
light transmittance at 650 nm. Because lignin was brown, the
color of the film gradually deepened as the addition amount
increased. Thus, the light barrier performance of the film was
gradually enhanced. In addition, full-wavelength measurements
of UV light were performed on the films, as shown in Figure
S2, and it was again confirmed that the film has UV resistance
in the UV range (200−400 nm). The different heat collection
and insulation properties of the films as a result of the color are
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Figure 8. Effects of different MAL additions on 5%SA/PVA films: (a) casting film viscosity, (b) water vapor permeability, and (c) mechanical
properties.
also shown in Figure 9b (relative temperature changes). When
the MAL content in the film increased, the surface temperature
of the film gradually increased. The maximum temperature
increased by 15% compared to the original film; however, the
soil temperature after film coverage gradually decreased. The
lowest temperature was 13% lower than the original film, and
the addition of MAL reduced the transmittance of the film.
Thus, the film exhibited heat collection and light barrier
properties. These properties could also inhibit the growth of
weeds to a certain extent,48 as the light blocking properties of
the film could prevent weeds from performing photosynthesis.
As a result, weed growth would be inhibited, and the weeds
would gradually wither, while the heat collection properties of
the film could promote crop growth to a certain extent.49
Currently, the evaluation system of the types of biodegradable
mulch and the effects on crops during growth is not well
developed, for example, application matching the properties of
different biodegradable mulches (water vapor permeability,
mechanical properties, temperature increase, degradability, and
other aspects) to different plants.50
Effects of PEG Addition. Figure 10 shows the viscosity,
mechanical properties, and water content characteristics of the
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film, which were investigated after PEG addition.51 As the
addition of PEG in the film increased, the film’s viscosity
gradually increased. This was because PEG itself exhibited
viscosity, and the reaction between PEG and PVA was more
than SA and MAL, which were competitive. We found that the
addition of PEG in small amounts resulted in a significant
decrease in the tensile strength of the film. However, there
were no significant increases in elongation at break. This also
indicated that when PEG was added in small amounts, the
mechanical properties of the films were significantly reduced.
The viscosity also reflected the fact that the cross-linking of the
film decreased after a small amount of PEG addition.
Increasing the addition of PEG to the film caused the tensile
strength to gradually decrease, and the elongation at break
initially increased and then decreased. The elongation at break
of the PEG films with a mass ratio of 2% also reached 162%, as
with excessive addition of PEG, the intermolecular forces of
PVA were reduced. At the same time, PEG would compete
with PVA, SA, and MAL, forming a reaction. The reaction of
more GA with PEG reduced the mechanical properties of the
film. We found that the degree of plasticization of PEG was
related to the water content of the film. Although PEG was a
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ACS Sustainable Chemistry & Engineering
Figure 9. 5%SA/PVA films with different MAL contents: (a) transmittance at 380 and 650 nm UV wavelengths and (b) temperature variation of
film surface based on 0%SA/PVA, warming variation of soil based on 20%SA/PVA.
significant plasticizer, the high water content of the film would
affect the practical usability of the film. Thus, the relative
stability and plasticization of PEG had a softening effect on the
film.
The tensile strength of the biodegradable agricultural land
film was greater than 2.75 MPa, while the elongation at break
was more than 150%, and the water vapor transmission was
less than 800 g·m−2·day−1. These values were in line with the
Chinese National Standard (GB/T35795-2017). Thus, the
tensile strength (117 MPa) and water vapor barrier perform-
ance (109.2 g·m−2·day−1) of the 5%SA + 15%MAL/PVA film
were significantly improved, while the addition of PEG
increased the fracture elongation of the film (162.24%). This
film studied has the best mechanical properties and UV
resistance compared with the literature.9,48 This confirmed that
the addition of MAL enhanced the water vapor barrier,
mechanical properties, and UV resistance performance of the
film.
Water Retention and Solid Soil of the Film. Soil water
retention experiments with different films are shown in Figure
11a,b, indicating that the rate of water evaporation (910 g·m−2·
day−1) in the soil covered by the PVA film was slightly lower
than the soil water not covered with film (1200 g·m−2·day−1).
The retention period for water was extended from 6 to 7 days.
When the 5%SA/PVA cast film fluid was sprayed on the soil
surface to form the film, the water-holding performance further
improved. The evaporation rate of water in the soil decreased
to 700 g·m−2·day−1, while the water retention time increased to
11 days. The water retention of the 5%SA + 15%MAL/PVA
film was the best for soil (water evaporation rate of 500 g·m−2·
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pubs.acs.org/journal/ascecg Research Article
day−1); however, the water retention properties of 5%SA +
20% MAL/PVA film were reduced. Furthermore, cracking of
the soil surface after water loss with or without the mulch film
was observed, as shown in Figure 11c. The soil surface integrity
of the soil covered with mulch film was better than the blank
(pure soil). For a clearer view, Figure 11d−f shows the three
viewpoints of the soil solidification of the mulch film. A
comparison of the mulch film formed by pouring pure PVA
and MAL cast film solutions indicated that the former caused
severe soil consolidation with a slab layer of ∼2 cm. This
caused the formation of the mulch film to be incomplete and
prone to cracking, which was detrimental to plant growth but
improved the water retention properties of the soil. This was
due to the low viscosity of the film casting fluid, which made
connections between the molecules difficult; therefore, a large
amount of the solution penetrated below the soil surface. The
mulch film containing MAL held ∼3 mm of the soil surface
layer, making it esthetically complete, and it did not form slabs,
as the added MAL was linked to the SA molecules, which
increased the intermolecular forces between the cast film
liquids. This prevented the overflowing liquid from penetrating
the soil in large quantities.
To further study the PEG plasticizer effect on the films, a
similar study was conducted, as shown in Figure 12. The
addition of PEG reduced the water evaporation rate from 910
to 676.7 g·m−2·day−1 in the film-covered soil compared to the
PVA film. PEG addition increased the film’s water-holding
performance, as PEG had a certain degree of moisture
absorption and water-holding performance. We also found
that the film formed by the cast film solution without MAL
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ACS Sustainable Chemistry & Engineering
Figure 10. Properties of the PEG plasticized 5%SA + 15%MAL/PVA film: (a) viscosity, (b) water content, and (c) mechanical properties.
addition caused soil slumping. However, the addition of MAL
improved soil consolidation and the water-holding properties
of the PEG film, which also improved the soil slumping
problem.
Weight Loss Evaluation. Figure 13 shows the degradation
rates of different films buried deep in the soil at 10 cm. The
degradation range of biodegradable agricultural land film has
been shown to be ∼20.7 to 60% after 50 days of soil burial.52
The degradation of the 5%SA/PVA films increased from 35 to
39% compared to the degradation of the PVA film. As a
polysaccharide polymer, SA was compatible and highly reactive
with PVA. Therefore, the addition of SA did not significantly
change the film degradability; however, MAL significantly
improved the degradability of the films. The degradability of
the films gradually increased with increasing MAL addition.
Thus, the degradability of 5%SA + 20%MAL/PVA film was as
high as 57.5%. This is because the new chemical bond (C−O−
C) formed by the hydroxyaldol condensation reaction of GA
and −OH is replaced by van der Waals forces and hydrogen
bonds formed between MAL, SA, and PVA, while MAL was
easily degraded. The addition of 2% PEG to the film further
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pubs.acs.org/journal/ascecg Research Article
improved the degradability to 66%, which, compared to the 5%
SA + 15% MAL/PVA film (55%), was an improvement of
13.3%. This was due to the addition of PEG, which weakened
the intermolecular forces and also weakened the binding
interactions between PVA, SA, and MAL.
■ CONCLUSIONS
To improve the water vapor barrier performance of PVA films,
PVA/SA/MAL ternary blends of biodegradable mulch films
were prepared. SA improved the dispersion and addition of
MAL in PVA. Lignin improved the water resistance, water
holding, heat collection, degradation, soil consolidation, and
thermal stability properties of the PVA/SA films, thus
preserving the mechanical properties of PVA films. Relying
on the synergistic effect of SA and MAL, SA was entangled on
the lignin surface in the blended films, which increased the
bonding between lignin and PVA, and the performance of the
film in all aspects improved. With an optimal addition amount,
the water vapor permeability of the film was 109.2 g·m−2·day−1,
the water evaporation rate after the mulch film covered the soil
was 500 g·m−2·day−1, and degradability reached 55% after 50
https://doi.org/10.1021/acssuschemeng.2c02290
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ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Research Article

Figure 11. Actual water evaporation rates of the soil covered with 5%SA/PVA films with different MAL contents: (a) dynamics, (b) linear fit, and
(c) shapes of the soil surfaces after the 5%SA/PVA films with different MAL contents were cast with the film fluids. The actual soil surface was
sprayed to form the films, which were sprayed with 5%SA/PVA films with different MAL contents: mulch film map (d) front, (e) back, and (f)
cross.

11810 https://doi.org/10.1021/acssuschemeng.2c02290
ACS Sustainable Chem. Eng. 2022, 10, 11800−11814
ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Research Article

Figure 12. Actual water evaporation rates that formed the films after PEG was added: (a) dynamics, (b) linear fit, and (c) the formation of mulch
film on the soil surface.

days. Moreover, the visible light transmission rate was only

20%, achieving complete absorption of UV light. The 2% (vol/
wt) PEG films were optimally tough, and their elongation at
break was 160%. Therefore, the PVA/SA/MAL ternary blend
of the biodegradable mulch film may offer promising
applications in agriculture and horticulture.

■
*
ASSOCIATED CONTENT
sı Supporting Information

The Supporting Information is available free of charge at

https://pubs.acs.org/doi/10.1021/acssuschemeng.2c02290.
In this study, the degradable film was fully characterized
by XRD (Figure S1. XRD pattern of different films: (a)
5%SA/PVA films with different MAL contents, (b)
different PEG plasticized 5%SA + 15%MAL/PVA film,
Figure 13. Degradation of the 5%SA/PVA films with different MAL
and (c) SA, MAL, and PEG effects on PVA films); full-
contents after 50 days of burial.
wavelength measurements of UV light were performed
on the films (Figure S2. UV transmittance of 5% SA/
PVA films with different MAL contents) (PDF)

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ACS Sustainable Chemistry & Engineering
■ AUTHOR INFORMATION
Corresponding Authors
Jing Fang − National-Local Joint Engineering Laboratory for
Energy Conservation in Chemical Process Integration and
Resources Utilization, School of Chemical Engineering and
Technology, Hebei University of Technology, Tianjin 300401,
China; orcid.org/0000-0003-3071-5771; Email: ctstfj@
hebut.edu.cn
Hao Li − National-Local Joint Engineering Laboratory for
Energy Conservation in Chemical Process Integration and
Resources Utilization, School of Chemical Engineering and
Technology, Hebei University of Technology, Tianjin 300401,
China; Key Laboratory of Pulp and Paper Science &
Technology of Ministry of Education, Qilu University of
Technology (Shandong Academy of Sciences), Jinan 250353,
China; State Key Laboratory of Pulp and Paper Engineering,
South China University of Technology, Guangzhou 510640,
China; orcid.org/0000-0002-7842-5362;
Email: ctstlihao@hebut.edu.cn
Authors
Weiyi Su − National-Local Joint Engineering Laboratory for
Energy Conservation in Chemical Process Integration and
Resources Utilization, School of Chemical Engineering and
Technology, Hebei University of Technology, Tianjin 300401,
China
Zhiwei Yang − National-Local Joint Engineering Laboratory
for Energy Conservation in Chemical Process Integration and
Resources Utilization, School of Chemical Engineering and
Technology, Hebei University of Technology, Tianjin 300401,
China
Haoyang Wang − National-Local Joint Engineering
Laboratory for Energy Conservation in Chemical Process
Integration and Resources Utilization, School of Chemical
Engineering and Technology, Hebei University of Technology,
Tianjin 300401, China
Chunli Li − National-Local Joint Engineering Laboratory for
Energy Conservation in Chemical Process Integration and
Resources Utilization, School of Chemical Engineering and
Technology, Hebei University of Technology, Tianjin 300401,
China
Gaojin Lyu − Key Laboratory of Pulp and Paper Science &
Technology of Ministry of Education, Qilu University of
Technology (Shandong Academy of Sciences), Jinan 250353,
China; orcid.org/0000-0002-8427-6391
Complete contact information is available at:
https://pubs.acs.org/10.1021/acssuschemeng.2c02290
Author Contributions
W.S.: conceptualization, writing�original draft preparation,
data curation, and investigation. Z.Y.: performing experiments,
data curation, and investigation. H.W.: performing experi-
ments, data curation, and visualization. J.F.: methodology,
supervision, and fund support. C.L.: supervision. G.L.:
provided experiments. H.L.: reviewing and editing, method-
ology, conceptualization, and fund support.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
The work was supported by the National Natural Science
Foundation of China (21808047), Tianjin Technical Innova-
11812
pubs.acs.org/journal/ascecg Research Article
tion Guidance Special Project (20YDTPJC00630), State Key
Laboratory of Pulp and Paper Engineering (202216), Key
Laboratory of Pulp and Paper Science & Technology of
Ministry of Education of China (KF202006), and The
National Science Foundation of HeBei Province
(B2020202015).
■ REFERENCES
(1) Yang, N.; Sun, Z.-X.; Feng, L.-S.; Zheng, M.-Z.; Chi, D.-C.;
Meng, W.-Z.; Hou, Z.-Y.; Bai, W.; Li, K.-Y. Plastic Film Mulching for
Water-Efficient Agricultural Applications and Degradable Films
Materials Development Research. Mater. Manuf. Processes 2015, 30,
143−154.
(2) Yin, W.; Chai, Q.; Guo, Y.; Fan, H.; Fan, Z.; Hu, F.; Zhao, C.;
Yu, A. The physiological and ecological traits of strip management
with straw and plastic film to increase grain yield of intercropping
wheat and maize in arid conditions. Field Crops Res. 2021, 271,
No. 108242.
(3) Jia, H.; Wang, Z.; Zhang, J.; Li, W.; Ren, Z.; Jia, Z.; Wang, Q.
Effects of biodegradable mulch on soil water and heat conditions,
yield and quality of processing tomatoes by drip irrigation. J. Arid
Land 2020, 12, 819−836.
(4) Giaccone, M.; Cirillo, C.; Scognamiglio, P.; Teobaldelli, M.;
Mataffo, A.; Stinca, A.; Pannico, A.; Immirzi, B.; Santagata, G.;
Malinconico, M.; Basile, B. Biodegradable mulching spray for weed
control in the cultivation of containerized ornamental shrubs. Chem.
Biol. Technol. Agric. 2018, 5, 21.
(5) Tofanelli, M. B. D.; Wortman, S. E. Benchmarking the
Agronomic Performance of Biodegradable Mulches against Poly-
ethylene Mulch Film: A Meta-Analysis. Agronomy 2020, 10, 1618.
(6) Li, Y.; Hu, Y.; Song, D.; Liang, S.; Qin, X.; Siddique, K. H. M.
The effects of straw incorporation with plastic film mulch on soil
properties and bacterial community structure on the loess plateau.
Eur. J. Soil Sci. 2021, 72, 979−994.
(7) Ma, Q.-J.; Li, X. G.; Song, W.-Y.; Jia, B.; Zhang, Q.; Lin, L.; Li,
F.-M. Plastic-film mulch and fertilization rate affect the fate of urea-
15N in maize production. Nutr. Cycl. Agroecosyst. 2018, 112, 403−
416.
(8) Chen, N.; Li, X.; Š imůnek, J.; Shi, H.; Hu, Q.; Zhang, Y.
Evaluating the effects of biodegradable and plastic film mulching on
soil temperature in a drip-irrigated field. Soil Till. Res. 2021, 213,
No. 106116.
(9) Liang, J.; Ning, R.; Sun, Z.; Liu, X.; Sun, W.; Zhou, X.
Preparation and characterization of an eco-friendly dust suppression
and sand-fixation liquid mulching film. Carbohydr. Polym. 2021, 256,
No. 117429.
(10) Wang, J.; Du, G.; Tian, J.; Jiang, C.; Zhang, Y.; Zhang, W.
Mulched drip irrigation increases cotton yield and water use efficiency
via improving fine root plasticity. Agric. Water Manage. 2021, 255,
No. 106992.
(11) Hou, L.; Xi, J.; Chen, X.; Li, X.; Ma, W.; Lu, J.; Xu, J.; Lin, Y. B.
Biodegradability and ecological impacts of polyethylene-based
mulching film at agricultural environment. J. Hazard. Mater. 2019,
378, No. 120774.
(12) Wang, X.; Fan, J.; Xing, Y.; Xu, G.; Wang, H.; Deng, J.; Wang,
Y.; Zhang, F.; Li, P.; Li, Z. The Effects of Mulch and Nitrogen
Fertilizer on the Soil Environment of Crop Plants. Adv. Agron. 2019,
153, 121−173.
(13) Ruimin, Q.; Jones, D. L.; Zhen, L.; Qin, L.; Changrong, Y.
Behavior of microplastics and plastic film residues in the soil
environment: A critical review. Sci. Total Environ. 2019, 703,
No. 134722.
(14) Iqbal, S.; Xu, J.; Allen, S. D.; Khan, S.; Nadir, S.; Arif, M. S.;
Yasmeen, T. Unraveling consequences of soil micro- and nano-plastic
pollution for soil-plant system with implications for nitrogen (N)
cycling and soil microbial activity. Chemosphere 2020, 260,
No. 127278.
https://doi.org/10.1021/acssuschemeng.2c02290
ACS Sustainable Chem. Eng. 2022, 10, 11800−11814
ACS Sustainable Chemistry & Engineering
(15) Steinmetz, Z.; Wollmann, C.; Schaefer, M.; Buchmann, C.;
David, J.; Troger, J.; Munoz, K.; Fror, O.; Schaumann, G. E. Plastic
mulching in agriculture. Trading short-term agronomic benefits for
long-term soil degradation? Sci. Total Environ. 2016, 550, 690−705.
(16) Zhang, Z.; Liu, Y.; Lin, S.; Wang, Q. Preparation and properties
of glutaraldehyde crosslinked poly(vinyl alcohol) membrane with
gradient structure. J. Polym. Res. 2020, 27, 1−7.
(17) Zhou, S.-J.; Wang, H.-M.; Xiong, S.-J.; Sun, J.-M.; Wang, Y.-Y.;
Yu, S.; Sun, Z.; Wen, J.-L.; Yuan, T.-Q. Technical Lignin Valorization
in Biodegradable Polyester-Based Plastics (BPPs). ACS Sustainable
Chem. Eng. 2021, 9, 12017−12042.
(18) Kawai, F.; Hu, X. Biochemistry of microbial polyvinyl alcohol
degradation. Appl. Microbiol. Biotechnol. 2009, 84, 227−237.
(19) E, S.; Ning, D.; Wang, Y.; Huang, J.; Jin, Z.; Ma, Q.; Yang, K.;
Lu, Z. Ternary Synergistic Strengthening and Toughening of Bio-
Inspired TEMPO-Oxidized Cellulose Nanofibers/Borax/Polyvinyl
Alcohol Composite Film with High Transparency. ACS Sustainable
Chem. Eng. 2020, 8, 15661−15669.
(20) Li, Y.; Li, S.; Sun, J. Degradable Poly(vinyl alcohol)-Based
Supramolecular Plastics with High Mechanical Strength in a Watery
Environment. Adv. Mater. 2021, 33, No. 2007371.
(21) Bian, H.; Wei, L.; Lin, C.; Ma, Q.; Dai, H.; Zhu, J. Y. Lignin-
Containing Cellulose Nanofibril-Reinforced Polyvinyl Alcohol Hydro-
gels. ACS Sustainable Chem. Eng. 2018, 6, 4821−4828.
(22) Merino, D.; Gutiérrez, T. J.; Mansilla, A. Y.; Casalongué, C. A.;
Alvarez, V. A. Critical Evaluation of Starch-Based Antibacterial
Nanocomposites as Agricultural Mulch Films: Study on Their
Interactions with Water and Light. ACS Sustainable Chem. Eng.
2018, 6, 15662−15672.
(23) Sarkar, A.; Biswas, D. R.; Datta, S. C.; Dwivedi, B. S.;
Bhattacharyya, R.; Kumar, R.; Bandyopadhyay, K. K.; Saha, M.;
Chawla, G.; Saha, J. K.; Patra, A. K. Preparation of novel
biodegradable starch/poly(vinyl alcohol)/bentonite grafted polymeric
films for fertilizer encapsulation. Carbohydr. Polym. 2021, 259,
No. 117679.
(24) Shi, S.; Liu, X.; Li, W.; Li, Z.; Tu, G.; Deng, B.; Liu, C. Tuning
the Biodegradability of Chitosan Membranes: Characterization and
Conceptual Design. ACS Sustainable Chem. Eng. 2020, 8, 14484−
14492.
(25) Li, J.; Ma, J.; Chen, S.; He, J.; Huang, Y. Characterization of
calcium alginate/deacetylated konjac glucomannan blend films
prepared by Ca2+ crosslinking and deacetylation. Food Hydrocolloids
2018, 82, 363−369.
(26) Ahmad, A.; Mubarak, N. M.; Jannat, F. T.; Ashfaq, T.; Santulli,
C.; Rizwan, M.; Najda, A.; Bin-Jumah, M.; Abdel-Daim, M. M.;
Hussain, S.; Ali, S. A Critical Review on the Synthesis of Natural
Sodium Alginate Based Composite Materials: An Innovative Bio-
logical Polymer for Biomedical Delivery Applications. Processes 2021,
9, 137.
(27) Tian, H.; Yuan, L.; Wang, J.; Wu, H.; Wang, H.; Xiang, A.;
Ashok, B.; Rajulu, A. V. Electrospinning of polyvinyl alcohol into
crosslinked nanofibers: An approach to fabricate functional adsorbent
for heavy metals. J. Hazard. Mater. 2019, 378, No. 120751.
(28) Wen, L.; Liang, Y.; Lin, Z.; Xie, D.; Zheng, Z.; Xu, C.; Lin, B.
Design of multifunctional food packaging films based on carbox-
ymethyl chitosan/polyvinyl alcohol crosslinked network by using
citric acid as crosslinker. Polymer 2021, 230, No. 124048.
(29) Wu, H.; Xiao, D.; Lu, J.; Li, T.; Jiao, C.; Li, S.; Lu, P.; Zhang, Z.
Preparation and Properties of Biocomposite Films Based on
Poly(vinyl alcohol) Incorporated with Eggshell Powder as a Biological
Filler. J. Polym. Environ. 2020, 28, 2020−2028.
(30) Zhang, J.; Xu, W. R.; Zhang, Y.; Li, W.; Hu, J.; Zheng, F.; Wu,
Y. Liquefied chitin/polyvinyl alcohol based blend membranes:
Preparation and characterization and antibacterial activity. Carbohydr.
Polym. 2018, 180, 175−181.
(31) Wang, W.; Zhang, H.; Jia, R.; Dai, Y.; Dong, H.; Hou, H.; Guo,
Q. High performance extrusion blown starch/polyvinyl alcohol/clay
nanocomposite films. Food Hydrocolloids 2018, 79, 534−543.
11813
pubs.acs.org/journal/ascecg Research Article
(32) Liu, L.; Liang, H.; Zhang, J.; Zhang, P.; Xu, Q.; Lu, Q.; Zhang,
C. Poly(vinyl alcohol)/Chitosan composites: Physically transient
materials for sustainable and transient bioelectronics. J. Cleaner Prod.
2018, 195, 786−795.
(33) Haque, A. N. M. A.; Naebe, M. Flexible water-resistant semi-
transparent cotton gin trash/poly (vinyl alcohol) bio-plastic for
packaging application: Effect of plasticisers on physicochemical
properties. J. Cleaner Prod. 2021, 303, No. 126983.
(34) Wang, Y.; Guo, X.; Li, J.; Jia, W.; Qian, F.; Wang, H.; Lv, Y.
Synergistic effects of (3-mercaptopropyl)trimethoxysilane and citric
acid on the improvement of water vapor barrier performance of
polyvinyl alcohol/xylan packaging films. Ind. Crops Prod. 2021, 171,
No. 113822.
(35) Hu, O.; Lu, J.; Chen, G.; Chen, K.; Gu, J.; Weng, S.; Hou, L.;
Zhang, X.; Jiang, X. An Antifreezing, Tough, Rehydratable, and
Thermoplastic Poly(vinyl alcohol)/Sodium Alginate/Poly(ethylene
glycol) Organohydrogel Electrolyte for Flexible Supercapacitors. ACS
Sustainable Chem. Eng. 2021, 9, 9833−9845.
(36) Lim, M.; Kim, D.; Han, H.; Khan, S. B.; Seo, J. Water sorption
and water-resistance properties of poly(vinyl alcohol)/clay nano-
composite films: Effects of chemical structure and morphology. Polym.
Compos. 2015, 36, 660−667.
(37) Sadeghifar, H.; Ragauskas, A. Lignin as a UV Light Blocker-A
Review. Polymers 2020, 12, 1134.
(38) Kabir, E.; Kaur, R.; Lee, J.; Kim, K.-H.; Kwon, E. E. Prospects
of biopolymer technology as an alternative option for non-degradable
plastics and sustainable management of plastic wastes. J. Cleaner Prod.
2020, 258, No. 120536.
(39) Wang, J.; Qian, Y.; Zhou, Y.; Yang, D.; Qiu, X. Atomic Force
Microscopy Measurement in the Lignosulfonate/Inorganic Silica
System: From Dispersion Mechanism Study to Product Design.
Engineering 2021, 7, 1140−1148.
(40) Zheng, T.; Zheng, D.; Li, X.; Cai, C.; Lou, H.; Liu, W.; Qiu, X.
Synthesis of Quaternized Lignin and Its Clay-Tolerance Properties in
Montmorillonite-Containing Cement Paste. ACS Sustainable Chem.
Eng. 2017, 5, 7743−7750.
(41) Hambardzumyan, A.; Foulon, L.; Chabbert, B.; Aguie-Beghin,
V. Natural organic UV-absorbent coatings based on cellulose and
lignin: designed effects on spectroscopic properties. Biomacromolecules
2012, 13, 4081−4088.
(42) He, X.; Luzi, F.; Hao, X.; Yang, W.; Torre, L.; Xiao, Z.; Xie, Y.;
Puglia, D. Thermal, antioxidant and swelling behaviour of transparent
polyvinyl (alcohol) films in presence of hydrophobic citric acid-
modified lignin nanoparticles. Int. J. Biol. Macromol. 2019, 127, 665−
676.
(43) Yang, W.; Owczarek, J. S.; Fortunati, E.; Kozanecki, M.;
Mazzaglia, A.; Balestra, G. M.; Kenny, J. M.; Torre, L.; Puglia, D.
Antioxidant and antibacterial lignin nanoparticles in polyvinyl
alcohol/chitosan films for active packaging. Ind. Crops Prod. 2016,
94, 800−811.
(44) Izaguirre, N.; Gordobil, O.; Robles, E.; Labidi, J. Enhancement
of UV absorbance and mechanical properties of chitosan films by the
incorporation of solvolytically fractionated lignins. Int. J. Biol.
Macromol. 2020, 155, 447−455.
(45) Acosta, J. L. E.; Torres Chávez, P. I.; Ramírez-Wong, B.; Bello-
Pérez, L. A.; Vega Ríos, A.; Carvajal Millán, E.; Plascencia Jatomea,
M.; Ledesma Osuna, A. I. Mechanical, thermal, and antioxidant
properties of composite films prepared from durum wheat starch and
lignin. Starch − Stärke 2015, 67, 502−511.
(46) Wang, H.; Wei, D.; Zheng, A.; Xiao, H. Soil burial
biodegradation of antimicrobial biodegradable PBAT films. Polym.
Degrad. Stab. 2015, 116, 14−22.
(47) Chen, L.; Qiang, T.; Chen, X.; Ren, W.; Zhang, H. J.
Fabrication and evaluation of biodegradable multi-cross-linked mulch
film based on waste gelatin. Chem. Eng. J. 2021, 419, No. 129639.
(48) Adhikari, R.; Bristow, K. L.; Casey, P. S.; Freischmidt, G.;
Hornbuckle, J. W.; Adhikari, B. Preformed and sprayable polymeric
mulch film to improve agricultural water use efficiency. Agric. Water
Manage. 2016, 169, 1−13.
https://doi.org/10.1021/acssuschemeng.2c02290
ACS Sustainable Chem. Eng. 2022, 10, 11800−11814
ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Research Article

(49) Wang, K.; Wang, C.; Chen, M.; Misselbrook, T.; Kuzyakov, Y.;
Soromotin, A.; Dong, Q.; Feng, H.; Jiang, R. Effects of plastic film
mulch biodegradability on nitrogen in the plant-soil system. Sci. Total
Environ. 2022, 833, No. 155220.
(50) Briassoulis, D.; Giannoulis, A. Evaluation of the functionality of
bio-based plastic mulching films. Polym. Test. 2018, 67, 99−109.
(51) Sofla, M. S. K.; Mortazavi, S.; Seyfi, J. Preparation and
characterization of polyvinyl alcohol/chitosan blends plasticized and
compatibilized by glycerol/polyethylene glycol. Carbohydr. Polym.
2020, 232, No. 115784.
(52) Kasirajan, S.; Ngouajio, M. Polyethylene and biodegradable
mulches for agricultural applications: a review. Agron. Sustainable Dev.
2012, 32, 501−529.

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11814 https://doi.org/10.1021/acssuschemeng.2c02290
ACS Sustainable Chem. Eng. 2022, 10, 11800−11814