polymers

Article
Biodegradable Mulching Films Based on Polycaprolactone and
Its Porous Structure Construction
Ning Yang 1,2 , Li Ying 1,2 , Kaiyu Li 1,2 , Feng Chen 1,2 , Fengyan Zhao 1,2 , Zhanxiang Sun 1,2 , Liangshan Feng 1,2, *
and Jialei Liu 3,4,5, *

1 Liaoning Academy of Agricultural Sciences, Shenyang 110161, China

2 Key Laboratory of Water-Saving Agriculture of Northeast, Ministry of Agriculture and Rural Affairs,
Shenyang 110161, China
3 Institute of Environment and Sustainable Development in Agriculture,
Chinese Academy of Agricultural Sciences, Beijing100081, China
4 Key Laboratory of Prevention and Control of Residual Pollution in Agricultural Film,
Ministry of Agriculture and Rural Affairs, Beijing 100081, China
5 Western Agricultural Research Center, Chinese Academy of Agricultural Sciences, Changji 831100, China
* Correspondence: [email protected] (L.F.); [email protected] (J.L.)

Abstract: Polycaprolactone (PCL) is one of the promising linear aliphatic polyesters which can be used
as mulching film. Although it has suitable glass transition temperature and good biodegradability,
further practical applications are restricted by the limited temperature-increasing and moisturizing
properties. The rational design of the PCL structure is a good strategy to enhance the related
properties. In this study, thermally-induced phase separation (TIPS) was introduced to fabricate a
PCL nanoporous thin film. The introduction of a nanoporous structure on the PCL surface (np-PCL)
exhibited enhanced temperature-increasing and moisturizing properties when used as mulch film.
In detail, the average soil temperature of np-PCL was increased to 17.81 ◦ C, when compared with
common PCL of 17.42 ◦ C and PBAT of 17.50 ◦ C, and approaches to PE of 18.02 ◦ C. In terms of
water vapor transmission rate, the value for np-PCL is 637 gm−2 day−1 , which was much less than
Citation: Yang, N.; Ying, L.; Li, K.;
the common PCL of 786 and PBAT of 890 gm−2 day−1 . As a result, the weed biomass under the
Chen, F.; Zhao, F.; Sun, Z.; Feng, L.;
np-PCL was suppressed to be 0.35 kg m−2 , almost half of the common PCL and PBAT. In addition,
Liu, J. Biodegradable Mulching Films
Based on Polycaprolactone and Its
the np-PCL shows good thermal stability with an onset decomposition temperature of 295 ◦ C. The
Porous Structure Construction. degradation mechanism and rate of the np-PCL in different pH environments were also studied to
Polymers 2022, 14, 5340. https:// explore the influence of nanoporous structure. This work highlights the importance of the nanoporous
doi.org/10.3390/polym14245340 structure in PCL to enhance the temperature-increasing and moisturizing properties of PCL-based
biodegradable mulching film.
Academic Editor: Nadege Follain

Received: 15 November 2022 Keywords: polycaprolactone; biodegradable; porous film; degradation property
Accepted: 1 December 2022
Published: 7 December 2022

Publisher’s Note: MDPI stays neutral

with regard to jurisdictional claims in 1. Introduction
published maps and institutional affil- The application of mulching film could lead to an increase in crop yield by 20–50%
iations. because of its temperature-increasing and moisturizing properties [1]. In China, agricultural
productivity has increased significantly through the application of mulching technology,
mulching film plays an important role in ensuring food security in China [2]. In 2014, the
number of mulching films used in China reached 1.425 million tons, covering an area of
Copyright: © 2022 by the authors.
nearly 20 million hectares. To date, several mulching film materials have become important
Licensee MDPI, Basel, Switzerland.
issues for agricultural production [3]. This number will increase rapidly with the increasing
This article is an open access article
demand for food. Unfortunately, most of the mulching film used today is polyethylene
distributed under the terms and
(PE), and the widespread application of such PE-type mulching film has caused serious
conditions of the Creative Commons
Attribution (CC BY) license (https://
“white pollution” because of the residual film [4–6]. To solve the issue of white pollution,
creativecommons.org/licenses/by/
residual film recycling technology was applied for the prevention of white pollution at the
4.0/).
beginning. However, this technology cannot recycle all the residual film, most of the small

Polymers 2022, 14, 5340. https://doi.org/10.3390/polym14245340 https://www.mdpi.com/journal/polymers

Polymers 2022, 14, 5340 2 of 11

residual films are still in the soil which has a bad effect on further agricultural activities
and underground water.
Replacing traditional polyethylene (PE) films with degradable films is an attractive
way to solve the pollution of residual film in farmland, because this strategy solves the
problem at the source. According to the American Society for Testing and Materials
(ASTM) definition: biodegradable materials are polymer materials that can be degraded
or enzymatically undergo chemical, biological, or physical changes under the action of
microorganisms such as bacteria, fungi, and algae [7]. These materials can be quickly
decomposed and utilized by microorganisms in nature, and the final degradation products
are CO2 and water. The biodegradable film shows its potential of solving the white
pollution problem in the future because of its environmentally friendly properties [8–11].
Although the use of biodegradable film has great potential, it is still in its infancy [12,13]. At
present, it is necessary to strengthen the research on the raw materials, formulations, and
production processes of biodegradable mulching film to improve its quality and reduce
costs in the agricultural sectors [14–16]. In particular, it is necessary to develop special
biodegradable mulching films for certain regions and crops to meet the requirements of
agricultural production diversity.
Up to date, the degradable polymer materials mainly include diacid diol copolyester
(PBS, [17] PBAT, etc.), polyhydroxyalkanoate (PHA), polycaprolactone (PCL) [18], polyhy-
droxybutyrate (PHB) [19], copolymer-polypropylene carbonate (PPC), and polylactic acid
(PLA) [20]. Additionally, Poly(Angelica Lactone) and its copolymer with other monomers,
as a new series of biodegradable polymer, was also studied in detail and they showed good
thermodynamic properties and machinability [21–23]. Compared with other biodegradable
materials, PCL is a biodegradable semi-crystalline aliphatic polyester that has only one
monomer and is synthesized by ring-opening polymerization of β-caprolactone under
the action of catalyst [24,25]. Its chain segment length gives it the thermodynamic char-
acteristics suited for the application of agricultural mulching films. In addition, its glass
transition temperature ranges from −60 ◦ C to 0 ◦ C, which is close to that of glass transition
temperature PE, and its high decomposition temperature makes it much more stable than
other polyesters. Herein, as a biodegradable material, PCL has wide applications including
mulching film, compost bags, release carriers, microencapsulated pharmaceutical prepa-
rations, food packaging materials, surgical sutures, medical equipment, etc. [26–28]. PCL
materials can also be mixed and manufactured with other polymer materials (including
PE) to manufacture differentiated-time degradable strip films.
However, the slow crystallization rate and poor processability of PCL limits its appli-
cation. Considering this, the main research concentrated mostly on blending modification
with other bio-based materials [29–31]. While the research on its degradation performance
has not received sufficient attention [32–34]. The introduction of a porous structure can
change the surface structure of the film, which may further help the regulation of heat
radiation, and is of great significance in improving the thermal insulation performance of
degradable mulch film. In addition, the increase in surface area increases the contact area
between water vapor and agricultural film, which is conducive to the condensation of water
and is of great significance in improving the water retention performance of agricultural
mulching films. In this view, np-PCL degradable film was prepared by thermally induced
phase separation (TIPS). As a result, np-PCL has a less water vapor transmission rate than
common PCL, which is good for preserving moisture. By mulching this kind of np-PCL
film, the soil temperature was increased and the weed mass was reduced obviously when
compared with the common one. As is well known, crop and environmental differences
are closely related to the degradation characteristics of mulching films. For instance, soil
temperatures and water influence the degradation process of biodegradable mulching film
greatly [35]. Biodegradable mulching film is extremely sensitive to soil pH, light conditions
and UV intensity [36,37]. Therefore, thermal stability and degradation performance of
the np-PCL porous film in different solutions and at different degradation times were
Polymers 2022, 14, 5340 3 of 11

investigated. The degrading process was well clarified. These results are helpful for the
further use of this kind of PCL film.

2. Materials and Methods

Chemicals used
The chemical compounds used in the present research were: polycaprolactone, indus-
trial grade; PBAT, industrial grade; PE, industrial grade; trifluoroacetic acid, analytically
pure; hydrochloric acid, analytically pure; sodium hydroxide, analytically pure; deionized
water, homemade.

2.1. Raw Materials

Polycaprolactone was purchased from Jingtian Plastic Raw Materials Co., Ltd. (Dong-
guan, China) with the trade name capa-6800. It possessed a density of 1.15 g/cm3 , a melt
index of 3–10 g/10 min (160 ◦ C/2.16 kg), number average molecular weight of about
8 × 104 and an average melting temperature of 60 ◦ C. PBAT is purchased from Guangzhou
Jinfa Technology Co., Ltd. (Zhuhai, China), with the trade name D300 F20E. Its density
is 1.25 g/cm3 , melting temperature is 130 ◦ C, average molecular weight is 2 × 105 , and
average melting temperature is 110 ◦ C. PE was purchased from Daqing Petrochemical
(Daqing, China). Trifluoroacetic acid, analytically pure; analytical pure hydrochloric acid;
sodium hydroxide, analytically pure; deionized water, homemade. Unless otherwise stated,
all materials and reagents used in the experiment were purchased from Shanghai Macklin
Biochemical Technology Co., Ltd. (Shanghai, China).

2.2. Equipment
The equipment used in this manuscript includes: electric blast drying oven 9077A
(Qingdao Mingbo Environmental Protection Technology Co., Ltd., Qingdao, China); vac-
uum drying oven DZF-6020 (Suzhou Jiangdong Precision Instrument Co., Ltd., Suzhou,
China); scanning electron microscope JSM-5600LV (Japan Electronics Co., Ltd., Tokyo,
Japan); Fourier infrared spectrometer Nicolet 6700 (Thermo Nicolet Corporation, Madison,
WI, USA); thermogravimetric analyzer TG201F1 (Mettler-Toledo Group, Zurich, Switzer-
land); collector-type constant temperature heating magnetic stirrer DF-101 (Shenzhen Sanli
Technology Co., Ltd., Shenzhen, China); electronic balance BS200S-WE2 (Germany Sar-
torius Group, Gottingen, Germany); magnetic heating stirrer B23-2 (Changzhou Nuoji
Instrument Co., Ltd., Changzhou, China); circulating water vacuum pump SHZ-D (222)
(Henan Iread Instrument Equipment Co., Ltd., Zhengzhou, China); Labthink C360-WVTR
(Labthink Instruments Co., Ltd., Jinan, China); Aglient Cary 600-FTIR (Agilent Technolo-
gies Co., Ltd., Santa Clara, CA, USA). The equipment used for measuring water vapor
transmittance is W3/060 water vapor transmittance measurement system of PERME brand.

2.3. Sample Preparation

The weighed polycaprolactone was added to trifluoroacetic acid in a certain proportion,
the temperature was kept at 60 ◦ C, and the speed was moderate so that polycaprolactone
can be dissolved. The status of the dissolution process was observed. After all the raw
materials were dissolved, the solution was poured into a Petri dish. The Petri dish was
then placed in a drying oven to volatilize the solution and make the liquid in the Petri dish
viscous. After the solution in the Petri dish was cooled, the diluent in the solution was
extracted with deionized water as the extractant and pressed into a film. The prepared film
material was then placed in a drying oven and dried to remove the extractant to obtain a
porous film.
Polymers 2022, 14, 5340 4 of 11

2.4. Performance Testing and Structural Characterization

The TG was used to test the thermal stability of the sample. About 1 g of sample
was weighed and placed in a copper crucible at a heating rate of 10 ◦ C/min, a scanning
temperature range of 25–600 ◦ C, and in a nitrogen atmosphere. The surface morphology of
the porous film was observed by scanning electron microscopy (SEM).
Nicolet 6700 Fourier infrared spectrometer was used to analyze the chemical structure
of porous film after degradation. The mass loss method was used to characterize the
degradation of the film material. During the degradation of polymer materials, the products
were carbon dioxide and water. The degraded polymer was dried and weighed to calculate
the mass loss rate of the film. This is the direct method of observing the phenomenon and
characterizing the degradation of polymer materials.
Mass loss rate:
Mn (%) = (M0 − Mn)/M0 × 100%
Mn—Mass loss percentage on day n
M0—Film mass before degradation, g
Mn—Film mass after n days of degradation, g

2.5. The Functional Performance of Mulching

The functional performance for mulching was carried out in May 2021, and the local
rainfall was 560 mm. The width of the three studied films was set at 900 mm, and the
plastic film mulching method was strip mulching. A completely randomized block design
was used in the experiment. Each treatment was about 60 m2 . The mulching crop is
peanut (Baisha1016) with a planting density of 120,000 plants/667 m2 , which is sowed and
mulched with film at the end of April and harvested at the end of September.

3. Results and Discussion

3.1. Thermal Stability Analysis of Porous Film
Thermal stability is a key parameter of polymer materials, which directly determines
the available processing methods and temperature resistance of such polymer materials.
As the raw material of mulching film, the degradable resin must be suitable for twin-screw
granulation and blow molding processes, which were accompanied by high temperature
process. To investigate the thermal stability of the newly prepared np-PCL film, thermo-
gravimetry (TG) and differential thermogravimetric (DT) were carried out. Figure 1 shows
the TG (left) and DT (right) curves of the np-PCL film. As is shown, the weight of the
PCL porous film was unchanged from the beginning of heating to a temperature of about
295 ◦ C. At this stage, the weight loss of the sample was about 2%, and the main weight
loss component was the adsorbed water in the material. After 295 ◦ C, weight loss began
to accelerate gradually, and 295–470 ◦ C was the stage for rapid weight loss. At this stage,
the weight loss of the sample reached about 92%, and a peak of maximum weight loss
appeared at 402 ◦ C. After that, the weight loss of the sample gradually slowed down and
was unchanged from 450 ◦ C to the end temperature of 600 ◦ C. It can be concluded that the
initial decomposition temperature of the np-PCL film is 295 ◦ C and the maximum weight
loss temperature is 402 ◦ C, indicating that the np-PCL film has good thermal stability. Com-
pared with the requirements of twin-screw granulation and blow molding temperature
(within 200 ◦ C), the thermal stability of this material has fully met the requirements of
subsequent processing technology.
Polymers 2022, 14, x FOR PEER REVIEW 5 of 11

Polymers 2022,
Polymers 14, x5340
2022, 14, FOR PEER REVIEW 5 5ofof11
11

Figure 1. Thermogravimetric curve of the PCL porous film (left) and differential thermogravimetric
curve
Figureof1.
1.the PCL porous film (right).
Thermogravimetric curveofofthe
thePCL
PCLporous
porousfilm
film(left)
(left)and
anddifferential
differentialthermogravimetric
thermogravimetric
Figure Thermogravimetric curve
curve of
curve of the
the PCL
PCL porous
porous film
film (right).
(right).
3.2. Analysis of the Degradation Performance of PCL Mulch Film
3.2. Analysis of the Degradation Performance of PCL Mulch Film
Figure 2ofare
3.2. Analysis thethe time-dependent
Degradation Performancefilm ofmass
PCLloss for np-PCL films in three differ-
rateFilm
Mulch
ent pH Figure 2 are the
solutions: time-dependent
NaOH, HCl, and film mass water.
deionized loss rate for np-PCL
Figure 2 (left) films
and in three 2different
Figure (right)
Figure 2 are the time-dependent film mass loss rate for np- PCL films in three differ-
pH
show solutions: NaOH, HCl, and deionized water. Figure 2 (left) and Figure 2 (right) show
ent pHthe results inNaOH,
solutions: two different
HCl, and concentrations
deionized water. of 0.1Figure
and 0.5 mol/L,and
2 (left) respectively.
Figure 2 (right)As is
the results
shown, with in two
the different
increase inconcentrations
degradation of
time, 0.1
theandmass0.5 mol/L,
loss rate respectively.
of the np-PCL As is
film shown,
grad-
show the results in two different concentrations of 0.1 and 0.5 mol/L, respectively. As is
with increases,
ually the increase in degradation time,of the mass loss rateAtofthe
theearly
np-PCL stagefilm gradually
shown,
increases,with theregardless
increase
regardless of inof
the
the kinds
degradation
kinds of solutions
solutions
time, the
used.
used.
massAt lossearly
the rate of the np-PCL
stage (less
(less
than filmthan
10 grad-10
days),
days),
ually the degradation
increases, regardless rate of the
ofnp-PCL np-PCL
the kinds film is
ofissolutionslarge, almost
used.achieving achieving
At the early a
stageofvalue
(less of
than40%.10
the degradation
After that, the mass rateloss
of the
rateofisthe film
relatively large,
slow but almost
still increases overa time.
value This 40%. After
indicates
days),
that,the the degradation
theinitial
massstage
loss rate rate np-PCL
is relativelyisslow film is large,
but still almost
increases over achieving
time. a value of
This indicates 40%.
that
After that, the mass of degradation a process butof hydrolysis
increaseswhich was caused by the
that the initial stageloss rate is relatively
of degradation is a slow
process ofstill
hydrolysis over time.
which was This
caused indicates
by the
penetrated
that solutions. In the later stage, the degradation originates from the degradation
penetrated solutions. In the later stage, the degradation originates from the degradationthe
the initial stage of degradation is a process of hydrolysis which was caused by of
of polymer solutions.
penetrated molecular In chains which
thewhich
later takes a long
stage, time. In originates
comparison with thedegradation
concentra-
polymer molecular chains takes athe longdegradation
time. In comparison from
with the
the concentration
tion
of of 0.1 mol/L solutions, thewhich
degree of degradation in a comparison
solution with a concentration of
of polymer
0.1 mol/L molecular
solutions, chains
the degree takes
of a long time.
degradation in In
a solution withwith the concentra-
a concentration of
0.5
tion mol/L is
of 0.1 mol/L significantly slow.
solutions,slow. Under
the degree alkaline conditions, it can be found that the mass
0.5 mol/L is significantly Underofalkaline
degradation in a solution
conditions, it can with a concentration
be found that the mass of
loss
0.5 rate ofisnp-PCL film isslow.
the largest,
Underfollowed
alkaline by HCl and it H2O. The mass loss
thatratethe of the
lossmol/L significantly
rate of np-PCL film is the largest, followed conditions,
by HCl and H2can be found
O. The mass loss rate mass
of the
np-PCL
loss film
rate of reached
np-PCL film100% after
is the degradation
largest, of
followedofby 60 d. Through experiments, it was found
np-PCL film reached 100% after degradation 60HCl and H2O.experiments,
d. Through The mass loss rate found
it was of the
that
np-PCLthe high reached
or low pH environment will accelerate
of 60 d.the degradation of np- PCL.
that the film
high or low pH 100% after degradation
environment will accelerate Through
the experiments,
degradation of np-PCL.it was found
that the high or low pH environment will accelerate the degradation of np- PCL.

Figure
Figure 2.
2. Degradation
Degradationof
ofthe
the porous
porous film
film in
in 0.1
0.1 mol/L
mol/L(left)
(left)and
and0.5
0.5mol/L
mol/L(right)
(right)solution.
solution.
Figure 2. Degradation of the porous film in 0.1 mol/L (left) and 0.5 mol/L (right) solution.
The
The PCL
PCL is a linear aliphatic
aliphatic polyester
polyesterin inwhich
whichthe theester
esterbond
bonditself
itselfisisvery
very sensitive
sensitive to
acidity
to acidity and alkalinity.
and From
alkalinity. Fromthe point
the pointof view
of view of chemical
of chemical analysis,
analysis, the main
the
The PCL is a linear aliphatic polyester in which the ester bond itself is very sensitive main mechanism
mechanism of
itsacidity
of
to degradation
its degradation is is
that
and alkalinity.the
that ester
the
Fromester bond
the bond
pointonon
the
of molecular
the
viewmolecular chain
of chemical chainis is
hydrolyzed
hydrolyzed
analysis, the main under
under acidic or
acidic
mechanism
alkaline
or alkaline conditions,
conditions, which
which causes
causesthe molecular
the molecular chain
chainto break
to break and produce
and
of its degradation is that the ester bond on the molecular chain is hydrolyzed under acidic produce water-soluble
water-sol-
oligomers
uble
or alkaline and
oligomers monomers
and monomers
conditions, [26].causes
which From the
the perspective
[26]. From of crystallization,
the perspective
molecular chain ofbreak
to andthe
crystallization, molecular
produce chains
the water-sol-
molecular
in the
chains crystalline region
in the crystalline are arranged
region[26]. more
are arranged closely, and
more closely,the water of small molecules is not
uble oligomers and monomers From the perspective of and the water ofthe
crystallization, small mole-
molecular
easy
cules to penetrate. Therefore, the degradation process starts from the amorphous to the
chainsisinnot theeasy to penetrate.
crystalline regionTherefore,
are arranged the more
degradation
closely,process
and thestarts
waterfrom the amor-
of small mole-
crystalline
phous region. At theregion.
early stage ofearly
degradation, small molecules of water first penetrate
cules istonotthe crystalline
easy to penetrate. At the
Therefore, stage
the of degradation,
degradation process small molecules
starts from the of amor-
water
the amorphous region and cause the ester bond to break, which happens easily. After most
phous to the crystalline region. At the early stage of degradation, small molecules of water
 first penetrate the amorphous region and cause the ester bond to break, which h
easily. After most of the amorphous region has been degraded, it begins to degra
the edge to the center of the crystalline region. However, the penetration of wate
Polymers 2022, 14, 5340
cules into the crystal zone is difficult, so the degradation rate is relatively 6 of 11
slow
Hydrolysis of it can produce carboxylate. Therefore, under acidic and alkaline con
the degradation rate of ester bonds is very fast. In an alkaline environment, HO- c
with
of the the carboxylic
amorphous region acidhasproduced
been degraded, by the hydrolysis
it begins reaction
to degrade from and
the edgeis promoted
to the to p
center
in theofpositive
the crystalline region. However,
direction. Therefore, the penetration
the degradationof water molecules
rate of the into PCL
the crystal
porous film
alkaline solution is faster than that in an acid one, and the hydrolysis ofcan
zone is difficult, so the degradation rate is relatively slow [38,39]. Hydrolysis of it the ester
produce carboxylate. Therefore, under acidic and alkaline conditions, the degradation rate
not complete under acidic conditions. Additionally, the role of acid or alkali is
of ester bonds is very fast. In an alkaline environment, HO- can react with the carboxylic
entirely
acid producedclear,by since the decomposition
the hydrolysis reaction andofisthe films was
promoted carriedinout
to proceed the using
positive dilute so
The precise
direction. regulation
Therefore, of functional
the degradation period
rate of the is an film
PCL porous important indicator
in an alkaline solution for
is the su
faster than that in an acid one, and the hydrolysis of the ester
evaluation of degradable plastic mulch films in crop planting. As an important in bond is not complete under
acidic conditions. Additionally, the role of acid or alkali is still not entirely clear, since the
fecting the functional period of degradable plastic film, pH is firstly proposed in t
decomposition of the films was carried out using dilute solutions. The precise regulation
cle, which will
of functional period beisof an great
importantsignificance
indicator for tothe
thesuitability
development of of
evaluation thedegradable
control techno
the functional
plastic mulch films period
in cropof degradable
planting. plastic mulch
As an important film. the functional period
index affecting
of degradable
Figure 3 shows the time-dependent variation in thewhich
plastic film, pH is firstly proposed in this article, masswill lossberate
of great
of the np-P
significance to the development of the control technology for the functional period of
in the soil extract. It is found that the degradation rate is less than that of an alkali
degradable plastic mulch film.
tionFigure
but larger3 shows than the one in acidic
the time-dependent and in
variation neutral
the mass solutions.
loss rate ofThis resultfilm
the np-PCL indicates
croorganisms in the soil could be conducive to film degradation,
in the soil extract. It is found that the degradation rate is less than that of an alkaline which promotes t
radation
solution but of larger
the porousthan the film.
one However,
in acidic and which
neutral specific types
solutions. Thisofresult
microbial
indicatescolonies c
that microorganisms in the soil could be conducive to film
mote degradation rate and capacity, whether these microorganisms are additive degradation, which promotes
the degradation of the porous film. However, which specific types of microbial colonies
gistic, or inhibitory during the degradation process, and how the changes in the ty
can promote degradation rate and capacity, whether these microorganisms are additive,
quantity
synergistic,during the degradation
or inhibitory process process,
during the degradation affect the anddegradation
how the changes process
in the needs
type to be
studied.
and quantity In general,
during the50 to 100 days
degradation are needed
process affect thefor 50% of biodegradable
degradation process needs toplasticbe film
further studied. In general, 50 to 100 days are needed for 50%
soil being reduced. Compared with traditional biodegradable mulching film, the of biodegradable plastic film
in the soil being reduced. Compared with traditional biodegradable mulching film, the
dation rate of such porous biodegradable mulching film is accelerated [40].
degradation rate of such porous biodegradable mulching film is accelerated [40].

Figure 3.3.Degradation
Figure Degradationof the
ofporous film in soil
the porous filmextract.
in soil extract.
3.3. Infrared Analysis of the Porous Film
3.3. Infrared Analysis
The pH has of theinfluence
an important Porous Film
on the stability of polyester materials. By immers-
ing the prepared
The pH hasfilms
an in aqueous solutions
important influenceof acid,
on the alkali, and pure
stability water, the materials.
of polyester effect of By i
environmental pH on the hydrolysis process of np-PCL was well studied. Here, infrared
ing the prepared films in aqueous solutions of acid, alkali, and pure water, the e
spectroscopy was carried out to monitor the surface characteristics of the immersed films
environmental pH on
and the origin infrared the hydrolysis
spectrogram process
of PCL refers of np-PCL
to relevant was[41].
literature well
As studied.
shown in Here, i
− 1 − 1
spectroscopy was carried
Figure 4, the characteristic out
peaks at to monitor
3453 cm and the2966
surface
cm are characteristics of the immerse
attributed to hydroxyl
and R-COOH groups, respectively, and the peak at 1752 cm −1 is the C=O stretching vibra-
and the origin infrared spectrogram of PCL refers to relevant literature [41]. As sh
Figure 4, the characteristic peaks at 3453 cm−1 and 2966 cm−1 are attributed to hydro
R-COOH groups, respectively, and the peak at 1752 cm−1 is the C=O stretching v
peak. These three peaks are structural characteristic peaks of PCL. Under acid and
Polymers 2022, 14, 5340 7 of 11
Polymers 2022, 14, x FOR PEER REVIEW 7 of 11

tion peak. These three peaks are structural characteristic peaks of PCL. Under acid and
conditions, the formed peak at 1557 cm−1 is the characteristic peak of R-COO-, indicating
alkaline conditions, the formed peak at 1557 cm−1 is the characteristic peak of R-COO-,
that the ester bond is broken under acid and alkaline conditions. Moreover, due to the
indicating that the ester bond is broken under acid and alkaline conditions. Moreover, due
ionization of the electrolyte
to the ionization in the solution,
of the electrolyte a characteristic
in the solution, group with
a characteristic a negative
group charge
with a negative
is generated, which causes the ester bond to break more obviously. Under neutral
charge is generated, which causes the ester bond to break more obviously. Under neutral condi-
tions,
conditions, no ionization occurs, so there are no charged functional groups. As a result,rate
no ionization occurs, so there are no charged functional groups. As a result, the the
of ester bond breaking is slow, leading to a slow degradation rate.
rate of ester bond breaking is slow, leading to a slow degradation rate.

Figure 4. FTIR spectra of degradation samples of PCL porous film under acid, alkali and neutral conditions.
Figure 4. FTIR spectra of degradation samples of PCL porous film under acid, alkali and neutral
conditions.
3.4. Morphological Analysis of the Porous Film
The changing of the morphology of the np-PCL can directly reflect the influence of the
3.4. Morphological Analysis of the Porous Film
different pH environments. Figure 5 shows the SEM images of the surface of the np-PCL
The changing
film after 30 days ofofdegradation
the morphology in NaOH,of the
HCl,np-PCL can directly
and deionized waterreflect the influence of
at a concentration of
the different pH environments. Figure 5 shows the SEM
0.5 mol/L. As displayed in Figure 5(a1), the pores are evenly distributed on the images of the surface of surface
the np-
PCL
of thefilm after 30 np-PCL
prepared days of degradation
film with a in NaOH,
size HCl, and
of 200–400 nm.deionized water atofa nano-scale
The formation concentra-
tion
holes is mainly caused by the extraction of volatile solvents during the drying the
of 0.5 mol/L. As displayed in Figure 5a1, the pores are evenly distributed on sur-
process.
face of the prepared np-PCL film with a size of 200–400 nm. The
Figure 5(a2) is the SEM image of the np-PCL film degraded in NaOH solution for 30 days, formation of nano-scale
holes
whichisobvious
mainly showscausedirregular
by the extraction
large holes. of The
volatile solvents
surface of theduring
film isthe drying
uneven, process.
indicating
Figure 5a2 is the SEM image of the np-PCL film degraded in
that the nano-porous film has been partially degraded. Figure 5(a3) is the degradation NaOH solution for 30 days,
which
diagrams obvious showsfilms
of np-PCL irregular largesolutions.
in acidic holes. The As surface of thethe
is shown, filmsurface
is uneven,
of theindicating
np-PCL
that
film the
wasnano-porous
eroded into film has been
irregular voids partially degraded.
in the acidic Figure
solution, but5a3
theisdegradation
the degradation dia-
rate was
grams of np-PCL
significantly lowerfilmsthaninthatacidic solutions.
in the alkaline Assolution.
is shown,Figure
the surface
5(a4) of
is the np-PCL
degradationfilm
was eroded
diagrams of into
np-PCL irregular
films voids in thesolutions.
in neutral acidic solution, but the
The surface degradation
of the rate was
water-treated np-PCLsig-
nificantly
film becomes lower thanthan
flatter that in
a1,thethisalkaline
changesolution.
in surface Figure 5a4 isshould
structure the degradation diagrams
be attributed to the
of np-PCL films
interaction between in neutral
water and solutions.
PCL. The Thehydrophilicity
surface of the of water-treated
polyester makes np-PCL
PCLfilm be-
absorb
comes
a certainflatter
amount than of a1,water
this change
and beinswelling,
surface structure should be attributed
which eventually to the interac-
leads to smaller defects.
Otherwise,
tion between in water
an acid andor PCL.
alkaline Theenvironment,
hydrophilicity PCLof film is degraded
polyester makes mainly by hydrolysis,
PCL absorb a certain
and the of
amount defect
water parts
and are more prone
be swelling, whichto hydrolysis,
eventually leadsso thetopores
smallerwilldefects.
be deepened and
Otherwise,
enlarged; In the deionized water environment, the degradation
in an acid or alkaline environment, PCL film is degraded mainly by hydrolysis, and the process of PCL film is
dominated
defect partsby aremicrobial
more prone degradation,
to hydrolysis,and sothethecontact
poresarea
will between
be deepened microorganisms
and enlarged; andIn
filmdeionized
the plays a decisive
water role in its degradation
environment, rate. The process
the degradation contact area
of PCLbetween
film isprotrusions
dominatedand by
microorganisms
microbial is larger,
degradation, which
and the leads
contactto area
a smoother
between surface after degradation.
microorganisms and film plays a
decisive role in its degradation rate. The contact area between protrusions and microor-
ganisms is larger, which leads to a smoother surface after degradation.
Polymers 2022, 14,
Polymers x FOR
2022, PEER REVIEW
14, 5340 8 of 11
8 of 11

Figure 5. SEM
Figure images
5. SEM imagesofofthe
theoriginal
original PCL degradablemulching
PCL degradable mulching film
film (a1),(a1),
andand
afterafter it is degraded
it is degraded in in
NaOH (a2), HCl (a3), and deionized water (a4) for 30 days.
NaOH (a2), HCl (a3), and deionized water (a4) for 30 days.

AsAs mentionedabove,
mentioned above,the
the structure
structure ofofthe
thenano-porous
nano-porous array is very
array regular
is very and can
regular and can
be prepared in a large area. The cost for the preparation of the nano
be prepared in a large area. The cost for the preparation of the nano microporous microporous arrayarray
structure
structure is is
notnothigh
highandandthe
the process
process is
issimple.
simple.So,So,such
such materials
materials andand
processing methods
processing methods
are suitable for preparing functional agricultural mulching films. The porous structure of
are suitable for preparing functional agricultural mulching films. The porous structure of
the films can afford some important properties, such as absorbability, thermal insulation
theperformance,
films can affordspecialsome important
optical properties,properties, such as
and so on [42,43]. Theabsorbability,
appearance of thermal insulation
these functions
performance,
will help to improve the comprehensive performance of agricultural mulching films. Largefunc-
special optical properties, and so on [42,43]. The appearance of these
tions will help
difference in to improve
region, the comprehensive
different soil environments, performance
different cropof agricultural mulching
functional period needs,films.
Large difference
different in region, different
light environments, soil environments,
and different temperatures and different
humiditycrop functional
are the key factorsperiod
affecting
needs, the large-scale
different promotion of
light environments, degradable
and different plastic mulch films.
temperatures The influence
and humidity of key
are the
different
factors environments
affecting on the degradation
the large-scale promotionprocess of degradable
of degradable plastic
plastic mulchmulch filmThe
films. wasinflu-
clarified
ence through
of different the change rule
environments onofthe
the degradation
micro morphology structure
process in the degradation
of degradable plastic mulch
process of degradable plastic mulch film under different degradation conditions.
film was clarified through the change rule of the micro morphology structure in the deg-
radation processPerformance
3.5. Functional of degradable plastic mulch film under different degradation conditions.
for Mulching
The soil temperature is measured by placing a thermometer at a depth of 5 cm below
3.5.the
Functional
mulchingPerformance for Mulching
films and reading the temperature at 10:00 every day. The water vapor
transmittance is measuredisinmeasured
The soil temperature the laboratory, and theaequipment
by placing usedat
thermometer is athe W3/060
depth of 5water
cm below
vapor transmittance measurement system of PERME brand.
the mulching films and reading the temperature at 10:00 every day. The water vapor trans-
mittance Thermal insulation,
is measured water
in the conservation,
laboratory, and theandequipment
weeding areused
the three
is thebasic functions
W3/060 waterofvapor
agricultural covering materials. To evaluate the performance of the np-PCL mulching films,
transmittance measurement system of PERME brand.
common PCL, polyethylene (PE), and Poly (butyleneadipate-co-terephthalate) (PBAT) films
Thermal
were insulation,
also prepared at thewater conservation,
same thickness and
level for weeding are
comparison. Thethe three basic
functional functions of
performance
agricultural coveringtemperature
including thickness, materials. of
Tosoils,
evaluate the performance
water vapor of the
transmission rate, andnp-PCL mulching
weed biomass
films, common PCL, polyethylene (PE), and Poly (butyleneadipate-co-terephthalate)
of the three agricultural mulching films was listed in Table 1. Obviously, except for the
(PBAT) films were also prepared at the same thickness level for comparison. The func-
tional performance including thickness, temperature of soils, water vapor transmission
rate, and weed biomass of the three agricultural mulching films was listed in Table 1. Ob-
viously, except for the thickness, all the parameters are quite different. This is reflected by
Polymers 2022, 14, 5340 9 of 11

thickness, all the parameters are quite different. This is reflected by the difference in chain
segment structure between polyethylene and polyester. Reasonably, the soil covered by
PE achieved the highest temperature of 18.02 ◦ C, and the np-PCL one was 17.81 ◦ C. In
comparison, PBAT and common PCL film show the soil temperature of 17.50 ◦ C and
17.42 ◦ C, respectively. These results indicate that np-PCL film has better thermal insulation
performance, which may attribute to the porous structure which can hinder the airflow on
the surface of the mulching films.

Table 1. Functional performance for different mulching films.

Temperature Water Vapor

Temperature of Weed Biomass
Thickness (µm) Difference with PE Transmission Rate
Soils (◦ C) (kg m−2 )
Film (◦ C) (gm−2 Day−1 )
PCL porous film 11.09 17.81 −0.21 637 0.35
PCL film 10.93 17.42 0.60 786 0.68
PBAT film 11.05 17.50 −0.52 890 0.63
PE film 10.81 18.02 0 50 0.2

It is well accepted that biodegradable polyesters such as PBAT and PCL are moisture-
sensitive. Thus, the water vapor barrier property is an important parameter that should be
considered when using them as mulch films. So, the water vapor transmission rate (WVTR)
values of the three mulching films were measured and listed in Table 1. The WVTR value of
PE was about 50 gm−2 day−1 . Expectedly, the WVTR value of np-PCL, common PCL, and
PBAT film is one order of magnitude higher than that of PE. It is gratifying that the WVTR
of np-PCL film is about 30% lower than PBAT film and 20% lower than common PCL film.
Restraining weeds is also a major function of agricultural mulching films. As shown in
Table 1, PE film presented the highest percentage of inhibiting weeds, followed by np-PCL
film, PBAT film, and common PCL film. The improvement of the barrier property of the
prepared films is related to the construction of the porous structure on the mulching film
surface. The porous structure is conducive to the regulation of heat radiation and is of
great significance in improving the thermal insulation performance of degradable mulch
film. In addition, the increase in surface area increases the contact area between water
vapor and agricultural film, which is conducive to the condensation of water and is of
great significance in improving the water retention performance of agricultural mulching
films. These results indicate that porous structure design is a new research direction for
conserving soil moisture and suppressing weeds of fully biodegradable mulching films.

4. Conclusions
In this paper, new polycaprolactone (np-PCL) thin mulching films with the nanoporous
structure were prepared by the thermally-induced phase separation (TIPS) method. The
resulting np-PCL film has good thermal stability with an onset thermal decomposition
temperature of 295 ◦ C. On the surface of the prepared np-PCL film, nanopores are evenly
distributed with a size of 200–400 nm, which may afford us excellent water permeability
and thermal insulation properties. The degradation mechanism and rate of the np-PCL
in different pH environments were also studied by infrared spectroscopy. It is proposed
that the alkaline conditions favor the degradation of PCL-based film through the ester
bonds cleavage mechanism. Consequently, the introduction of a nanoporous structure on
the PCL surface (np-PCL) exhibited enhanced temperature-increasing and moisturizing
properties when compared with the PBAT and common PCL mulch films. These results
indicate that the introduction of the porous structure to mulching films is an important way
to improve the performance of degradable mulching films. The relationship between pH
and degradation rate has been clarified, which is of great significance for precise regulation
of degradation period of degradable plastic film. The clarity of alkaline accelerated degra-
dation mechanism will provide an important theoretical basis for prolonging the functional
period of degradable mulch film. The WVTR of np-PCL film is about 30% lower than PBAT
Polymers 2022, 14, 5340 10 of 11

film and 20% lower than common PCL film, which indicated that porous structure design
is a new research direction for conserving soil moisture and suppressing weeds of fully
biodegradable mulching films.

Author Contributions: Conceptualization, J.L. and L.F.; methodology, F.C., F.Z. and Z.S.; vali-dation,
J.L., L.F. and N.Y.; data curation, N.Y., L.Y. and K.L.; writing-original draft preparation, N.Y. and J.L.;
writing-review and editing, J.L. and L.F.; supervision, J.L. and L.F. All authors have read and agreed
to the published version of the manuscript.
Funding: This research was funded by the National Key Research and Development Program of
China (No. 2021YFD1700700), Science and Technology Project of Hainan Province (No. ZDYF2020084),
Science and Technology Project of Inner Mongolia Autonomous Region (2021GG0063), Central Public-
interest Scientific Institution Basal Research Fund (No. BSRF202105), Key scientific and technological
projects of Xinjiang production and Construction Corps (No. 2021AB007), Changzhou Science and
Technology Program (No. CE20202022), Shenyang Science and Technology Plan (22-317-2-04), Ap-
plied Basic Research Plan of Liaoning Province (2022JH2/101300159), Natural Science Foundation
Project of Liaoning Province (2022011123-JH3/107), and LiaoNing Revitalization Talents Program of
China (XLYC1907089, XLYC1807056).
Acknowledgments: Thanks for Liu Qi in Institute of Environment and Sustainable Development in
Agriculture for the help in measurement of polymer’s physical property.
Conflicts of Interest: The authors declare no conflict of interest.

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