Journal of Environmental Chemical Engineering 11 (2023) 110591

Contents lists available at ScienceDirect

Journal of Environmental Chemical Engineering

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

Hydrophobic-densified high-elastic waste-carton-derived

biopolymer-coated fertilizers: Enhanced performance and
controlled-release mechanism
Jiahui Liu a, b, Yuechao Yang a, b, *, Bin Gao c, Wentao Wang d, Dongdong Cheng a, b,
Yuanyuan Yao a, b, Tianlin Shen a, b, Zhen Yu a, b, Ting Zhang a, b, Jinpeng Wu a, b, Xinning Zhao a, b,
Jiaqi Weng a, b, Jiazhuo Xie a, b, *
a
National Engineering Research Center for Efficient Utilization of Soil and Fertilizer Resources, Shandong Agricultural University, Taian, Shandong 271018, China
b
College of Resources and Environment, Shandong Agricultural University, Taian, Shandong 271018, China
c
Department of Civil and Environmental Engineering, Rensselaer Polytechnic Institute, Troy, NY 12180, USA
d
College of Food Science and Engineering, Shandong Agricultural University, Taian, Shandong 271018, China

A R T I C L E I N F O A B S T R A C T

Editor: Chao He Reasonably utilize the recyclable waste cardboard (175 million tons every year) had attracted the increasing
environmental concern. However, the poor hydrophobicity and the loose porous structure of the cardboard-
Keywords: derived coating materials caused the rapid release of nutrients, thereby limiting the development and applica­
Hydrophobic-densified tion of the bio-derived synthetic polymer coated controlled-release fertilizers (BPCFs). In this work, the
Double-modification
hydrophobic-densified double-modified waste-carton-derived controlled-release fertilizers (HDCFs) were devel­
Waste-carton-derived
oped with nontoxic modifying agent and the simple production technology. The controlled release abilities of
Controlled release fertilizers
HDCFs were significantly enhanced (< 2 h to 120.45 days) and the nutrient release prediction models were
established. The enhanced performance was attributed to the improved hydrophobicity and the obviously
compact coating structure characterized by the three-dimensional computerized tomography (5.76–1.08 %).
Furthermore, the enhanced elasticity (5025.52–1325.68 MPa) of the HDCFs coatings also contributed to improve
the controlled-release abilities. The controlled-release mechanism was also clarified: the atmosphere “stopper” in
the “smaller and less” micropores in HDCFs coating only allows water vapor molecules (instead of liquid) slowly
permeate into the internal urea core and significantly enhance the controlled-release longevities. The dramati­
cally increased oilseed rape yield (71.75 %) showed the efficient application effect of the HDCFs. All the results
indicate that HDCF with 90:10 of the proportion of the castor oil and liquefaction polyhydric alcohols from
cardboard (LPAC) and 5 % of the siloxane of the total polyols exhibits the best performance effect. This work
provides the efficient strategy to foster the end-user confidence in the low-cost and eco-friendly biowaste-derived
controlled-release fertilizers.

1. Introduction resource and the environmental pollution [6–9]. Polymer coated

Chemical fertilizers play an important role in increasing the output of
the food crops, the vegetables, the fruits and the oil crops [1–3]. How­
ever, the excessively low nutrient utilization rate of chemical fertilizers
in current season [4,5] resulted in the serious wasting of the fertilizer
controlled-release fertilizers (CRFs) can significantly enhance the
nutrient utilization [10], increase the crop yield [11] and reduce the
environmental pollution compared with the uncoated fertilizer [12,13].
The output and application amount of polymer coated CRFs had
increased rapidly with an annual growth rate of about 6.5 % in recent

Abbreviations: BPCFs, bio-derived synthetic polymer coated controlled-release fertilizers; HDCFs, hydrophobic-densified double-modified waste-carton-derived
controlled-release fertilizers; LPAC, liquefaction polyhydric alcohols from cardboard; CRFs, controlled-release fertilizers; WCAs, water contact angles; WAR, water
absorption rate.
* Corresponding authors at: National Engineering Research Center for Efficient Utilization of Soil and Fertilizer Resources, Shandong Agricultural University,
Taian, Shandong 271018, China.
E-mail addresses: yangyuechao2010@163.com (Y. Yang), jiazhuoxie@sdau.edu.cn (J. Xie).

https://doi.org/10.1016/j.jece.2023.110591
Received 11 April 2023; Received in revised form 13 July 2023; Accepted 17 July 2023
Available online 18 July 2023
2213-3437/© 2023 Published by Elsevier Ltd.
J. Liu et al.
years [14]. In addition, the CRFs also have been applied in a lot of food
crops (e.g. rice, maize, wheat) [15,16], the vegetables (e.g. oilseed rape,
tomato) [17], the fruits (e.g. cherry, apple) [18,19] and the oil crops (e.
g. soybean, peanut) [20] with an obvious increase in yield. Nonetheless,
the expensive and non-renewable petrochemical polymer coating ma­
terials limited the large-scale production and application of the polymer
coated CRFs [21].
Nowadays, about 175 million tons of cardboard are produced and
one-shot applied worldwide each year with the violent development of
the shopping online. Reasonably utilize the recyclable waste carton re­
sources with a lot of cellulose had attracted the increasing environ­
mental concern [22–24]. The main ingredient of waste-carton is
cellulose. The breakthrough of bio-based polymer synthesis technology
has promoted the development of bio-based synthetic polymer coated
CRFs. Several well recognized eco-friendly bio-based materials,
including starch [25], vegetable oil [26], chitosan [27], cellulose [28],
straw [29] and alginate [30] have been widely chosen to produce BPCFs,
which made it possible to develop the waste-carton-derived bio­
polymer-coated fertilizers using the renewable waste cardboard
resources.
However, due to the terrible hydrophobic properties and the loose
structure, the bio-based synthetic polymer coating had the quite poor
water barrier capacity and the accompanying terrible controlled release
quality (usually < 10 days) [31,32], which cannot meet the long-term
requirement of the crops (2–3 months) [33,34]. Therefore, necessary
modifications should be taken to develop the BPCFs with longer
controlled release longevity. The nutrient release process of the polymer
coated controlled-release fertilizer can be divided into three stages: (1)
water contact and permeate into polymer coating materials; (2) water
enter into the fertilizer core through the coating; (3) dissolved nutrient
release out of the coating driven by developing osmotic pressure. In the
first stage, the hydrophobic degree of the coating surface was the
important limiting factor to control the nutrient release. Yang et al.
fabricated the superhydrophobic biopolymer coating by increasing
surface roughness and reducing surface energy. The hydrophobic char­
acteristic (86.1–155.8◦ ) and nutrient release longevity was significantly
improved (twice) compared with the unmodified biopolymer coated
fertilizer [35]. Nevertheless, the superhigh biopolymer coating content
(~ 7 %) still limited the application of the superhydrophobic bio-coated
fertilizers [36,37]. More measures should be taken to enhance the
controlled-release ability at the subsequent stage of the nutrient release
process.
At the second and third stage of the nutrient release process, the
hydrophilic properties and the loose structure of the biopolymer coat­
ings both are the governing factors. Single modification method cannot
effectively improve the controlled release performance. Sun et al. syn­
thesized the hydrophobic coating ODA-PTA urea modified with octa­
decylamine (hydrophobic angle > 100◦ ), but the N release longevity was
only 30 days [38]. Liu et al. modified CRFs with epoxy resin E44, which
only increased the N release life by 35 days (porosity decreased from 10
% to 7.2 %) [39]. Therefore, to improve the controlled release abilities
to the maximum extent, the hydrophobicity and densification of the
biopolymer coating should be enhanced by the hydrophobic-densified
double-modification methods. However, there are two important dis­
advantages still should be solved: (1) The excessive cost, toxic modifying
agent and the complicated process of the modification process limited
the large-scale production and application of the BPCFs; (2) The
controlled-release mechanism of the biopolymer coating after
hydrophobic-densified double-modification should be further clarified.
These provided the motivation to further explore the efficient and the
low-cost BPCFs coating with the hydrophobic-densified double-­
modified pathway.
In this work, the overarching objective was to fabricate the HDCFs
with low-cost waste-carton resources, nontoxic modifying agent and the
simple production technology. The controlled release abilities of HDCFs
were investigated and the nutrient release prediction models were
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Journal of Environmental Chemical Engineering 11 (2023) 110591
established. The hydrophobic surface, the compact structure and the
mechanical property of the formed HDCFs coatings were measured by
the three-dimensional computerized tomography and the atomic force
microscope. The controlled-release mechanism of the HDCFs was also
clarified and the applied effects were evaluated by oilseed rape experi­
ment. This study will contribute to effectively enhance the controlled-
release abilities of the BPCFs and provide technical and theoretical
support for the development of "ultra-thin, low-cost, efficient and
environmentally friendly" bio-derived CRFs.
2. Materials and methods
2.1. Materials
Urea (diameter: 2–4 mm, Shandong Agricultural University Fertilizer
Technology Co., LTD), polyethylene glycol (PEG-1000, Jiangsu Haian
Petrochemical Co. LTD), ethylene glycol (AR, Shandong Xinxiangsheng
Chemical Import and export Co. LTD), concentrated sulfuric acid (AR,
Tianjin Kemiou Chemical Reagent Co., LTD) were used as received.
Castor oil (AR, Wuxi Yatai United Chemical Co. LTD), isocyanate (PAPI)
(PM-200, Yantai Wanhua Polyurethane Co., LTD) and hydroxy-
terminated polydimethylsiloxane (abbreviate as siloxane in this paper,
Industrial Grade, Jinan Gaode Silicone Co., LTD) were used after
removing water with a vacuum rotary evaporator (RE-52AA).
2.2. Preparation of LPAC
The cardboard was put into an oven (Shanghai Yiheng Scientific
Instrument Co., LTD.) and baked at 80 ◦ C for 2 h. Then, the cardboard
was crushed into powder (diameter: 0.15 mm). The cardboard powder
(80 g), ethylene glycol (40 g), polyethylene glycol (360 g) and concen­
trated sulfuric acid (12 g) were put into a 1000 mL three-necked round-
bottom flask with a condensation device. The reaction was proceeded in
170 ◦ C in an oil bath with constant stirring (600 r/min) for 2 h using a
magnetic stirrer. Then the LPAC were obtained.
2.3. Fabrication of the HDCFs
The rotary drum coating process was employed to prepare the
HDCFs. Firstly, 1 kg granular urea were preheated to 65 ◦ C in the drum
coating machine (WKY-300, Qingzhou Jingcheng Medical Equipment
Manufacturing Co., LTD.) for 30 min. Then, a certain amount of coating
materials containing the LPAC, PAPI, castor oil (densification modifier)
and siloxane (hydrophobic modifier) were blended evenly and poured
into the surface of urea particles. Finally, the coated fertilizer can be
obtained after the solidification of the coated materials [29,40]. HDCFs
with different coating materials contents (2.5 %, 3.0 %, 3.5 %, 4.0 % and
4.5 %) can be prepared by repeated the above coating process. By
adjusting the amount of the modified reagents, different kinds of the
HDCFs can be obtained: The siloxane content was 0 %, 1 %, 5 %, 10 % of
the total polyols, the proportion of the castor oil and LPAC was 0:100,
30:70, 60:40, 90:10. Worth mentioned, the HDCFs with 4.5 % of the
coating contents, 10 % of the siloxane of the total polyols and 0:100,
30:70, 60:40, 90:10 of the proportion of the castor oil and LPAC are
named HDCF0, HDCF30, HDCF60 and HDCF90 respectively in this work
(Scheme 1). The relevant reaction equations and photos of LPAC and
HDCFs are shown in Supporting information (Fig. S1–S2).
2.4. Characterization
The composition and molecular weight of LPAC were investigated by
a GCMS-qp2010 Ultra (GC-MS) [41] and a Shimadzu LC20 gel perme­
ation chromatograph (GPC) [35,42] for aqueous phase. The structure of
the raw materials (siloxane, castor oil, PAPI and LPAC) and the HDCFs
coatings (HDCF0, HDCF30, HDCF60 and HDCF90) were analyzed using a
Bruker TENSOR II Fourier transform infrared spectrometer (FTIR) [42,
J. Liu et al. Journal of Environmental Chemical Engineering 11 (2023) 110591

Scheme 1. The diagram of the HDCFs coating: HDCF0, controlled-release fertilizers only with hydrophobic modification; HDCF90, controlled-release fertilizers with
hydrophobic-densified double-modification.

43], while the surface morphologies were observed using a Hitachi
SU8020 scanning electron microscope (SEM) and an energy dispersive
X-ray spectroscopy (EDX) detector attached to the SEM. The crystallinity
of the HDCFs coating was studied by a D8 Advance X-ray diffractometer
(XRD). Water contact angles (WCAs) [44] of all sample surfaces were
determined using an American OCA15E contact angle measuring in­
strument. The thermostability was measured using a thermogravimetric
analyzer (DTG60A) from Shimadzu with a heating rate of 20 ◦ C/min
within 30–800 ◦ C. The surface roughness, Young modulus and adhesion
of the HDCFs coatings was tested by an atomic force microscope (AFM)
[45], and the spatial structure of the membrane shell was demonstrated
by CT scan from phoenix v|tome|x m micron focus CT (Baker Hughes
business). The water nutrient release characteristics were measured
according to the according to the ISO 18644. The water absorption rate
(WAR) of the bio-based coating materials were determined by
immersing in water, sampling at regular intervals, wipe it dry with
gauze, weigh and calculate the WARs. The soil humidity and tempera­
ture were recorded with a soil temperature & moisture datalogger (TMS,
TOMST).
2.5. Potted oilseed rape applications
The pot experiment was carried out to evaluate the effects of HDCFs
on the growth of the oilseed rape. Details about the characterization
studies are available in the Supporting information.
3. Results and discussion
3.1. Structure and performance of LPAC and HDCFs coatings
To clarify the substance composition and component content of
LPAC, the LPAC was detected by gas chromatography mass

Fig. 1. (A) GC-MS chromatogram and (B) GPC curve of LPAC; (C) XRD patterns of the HDCFs; (D) FTIR spectra of the raw coating materials for the CRFs: siloxane,
castor oil, PAPI and LPAC; (E) FTIR spectra and (F) TGA and DTG curve of the formed HDCFs coating: HDCF0, HDCF30, HDCF60 and HDCF90, respectively.

3
J. Liu et al.
spectrometry and gel permeation chromatography. The main compo­
nents of LPAC are polyhydroxyl compounds, such as ethanol, diethylene
glycol, triethylene glycol, heptaethylene glycol, acetonyldime­
thylcarbinol, butyldimethylcarbinol, 2-hydroxyethyl propionate, diac­
etone alcohol, octaethylene glycol, 1-propoxy-2-propanol and 2-
isopropoxy-1-propanol. The rich -OH of these compounds provided the
conditions for the film forming reaction of polyurethane (Fig. 1A and
Table S2). These hydroxyl groups can be involved in the synthesis of
polyurethane. These polyols with different structures contribute to the
formation of complex cross-linked networks. The other substances are
inactive components of non-reactive groups, such as 2-pentene, 3-
penten-2-one, 3-butenoic acid, isobutyl ether, syringic acid, 3-butenoic
acid, diethoxytetraethylene glycol, 1,4,7,10-tetraoxacyclododecane,
acrolein ethylene acetal and 1-methyl-1-(2-pentyloxy)-1-silacyclopen­
tane. They do not participate in the envelope reaction and flow out
with the nutrients from the micropores of the coatings when the fertil­
izer nutrient is released. The average molecular weight (Mw) of LPAC is
1316 g/mol, and the small molecular weight verifies the decomposition
of cellulose in the carton. Compounds with molecular weight < 4521 g/
mol accounted for about 97.74 % of the total composition of LPAC,
while those with molecular weight > 4521 g/mol only accounted for
about 2.26 % (Fig. 1B). The fact that the unchanged peaks position and
crystallinity intensity of the formed HDCFs coatings (HDCF0, HDCF30,
Fig. 2. SEM images of the coating surface with (A1–D1) 30 magnification and fertilizer photos, and (A2–D2) 100 magnification and WCAs; EDX spectra (A3–D3) and
(A4–D4) EDX maps corresponding to the SEM images for surface elemental compositions and distributions of HDCF0, HDCF30, HDCF60 and HDCF90 coatings,
respectively.
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Journal of Environmental Chemical Engineering 11 (2023) 110591
HDCF60 and HDCF90) can verify the successful formation of the HDCFs
coatings by the XRD patterns (Fig. 1C).
The FTIR spectra were employed to explore the structure change of
the raw coating materials (siloxane, castor oil, PAPI and LPAC) (Fig. 1D)
and the formed HDCFs coatings (HDCF0, HDCF30, HDCF60 and HDCF90)
(Fig. 1E). For the FTIR spectra of the raw coating materials, the ab­
sorption peaks of O-H (ν, 3464 cm− 1) for LPAC, C– – O (ν, 2240 cm− 1)
– N–
for PAPI, -CH2 (ν, 2928 cm− 1), -CH3 (ν, 2850 cm− 1) and C– – O ( ν,
− 1 − 1
1740 cm ) for castor oil, C-C (ν, 1259 cm ) for siloxane can be
observed. For the FTIR spectra of the formed HDCFs coatings, the ab­
sorption peaks of N-H (ν, 3301 cm− 1), -CH2 (ν, 2921 cm− 1), -CH3 (ν,
2851 cm− 1), C– – O (ν, 1720 cm− 1), C-H (δ, 1512 cm− 1), and C-O-C (ν,
1218 cm− 1) can be observed. It’s worth noting that the absorption peaks
of C–
– N–– O (ν, 2240 cm− 1) for PAPI disappeared in the FTIR spectra of
the formed HDCFs coatings, which proved the successful and thorough
formation of the HDCFs coatings. Furthermore, the structure showed no
obvious change compared with the four HDCFs coatings (HDCF0,
HDCF30, HDCF60 and HDCF90), which means the introduction of the
castor oil and the siloxane had no influence for the structure of formed
polyurethane.
TGA and DTG were used to analyze the thermal stability of the
formed HDCFs coatings (HDCF0, HDCF30, HDCF60 and HDCF90)
(Fig. 1F). The formed HDCFs coatings have three weightlessness stages
J. Liu et al.
at 250.15–554.78 ◦ C. The first stage is about 250.15–371.62 ◦ C, at
which the polyurethane bonds break into isocyanates and polyols [46].
The second stage occurs at 313.82–461.77 ◦ C, and the chains of castor
oil and organic molecules break at this stage [39,46]. The third stage
(365.46–554.78 ◦ C) is principally the decomposition of hydroxyl and
polyol residues, and the final carbonization into ash [40]. The 50 %
degradation temperatures (T50%) of HDCF0, HDCF30, HDCF60 and
HDCF90 were 413.07 ◦ C, 416.58 ◦ C, 424.54 ◦ C and 427.02 ◦ C respec­
tively, and the maximum weight loss temperature (Tmax) were
410.20 ◦ C, 415.52 ◦ C, 428.86 ◦ C and 473.04 ◦ C respectively. Conse­
quently, with the increase of the castor oil content, the thermal stability
of the polyurethane membrane was enhanced. This can be attributed to
the fact that the addition of castor oil caused the higher molecular
weight, more compact structure and more crosslinking points of the
formed polyurethane [47,48], which are in good agreement with SEM
images (Fig. 3A1–D2). Meanwhile, the residual amount of HDCF0,
HDCF30, HDCF60 and HDCF90 were 23.41 %, 16.23 %, 10.59 % and
6.84 % respectively, indicating that castor oil could also improve the
thermal degradation performance of the HDCFs films.
3.2. Hydrophobicity of the Formed HDCFs coatings
The surface morphology of the HDCFs coatings (HDCF0, HDCF30,
HDCF60 and HDCF90) were observed by scanning electron microscopy.
The surface of the formed HDCFs coatings is smooth and flat with no
notches or cracks (Fig. 2A1–D2), which proves the good film-forming
property and becomes smoother with the increasing castor oil content.
The WCAs were also measured to study the hydrophobicity of HDCF0,
HDCF30, HDCF60 and HDCF90, respectively (Fig. 2A2–D2). The WCAs of
the above formed HDCFs coatings were all greater than 90◦ (92.8◦ ,
101.0◦ , 108.4◦ and 138.3◦ ). It should be noted that the amount of
siloxane added is the same (10 %), but the contact angles are growing
with the increase of the castor oil. The WCA of HDCF90 (138.3◦ ) was
Fig. 3. SEM images of the fracture surface with (A1–D1) 2000 × magnification and (A2–D2) 20,000 × magnification, (A3–D3) intensity and pore area counted from
the SEM images of the HDCF0, HDCF30, HDCF60 and HDCF90, respectively.
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Journal of Environmental Chemical Engineering 11 (2023) 110591
even 45.5◦ higher than that of HDCF0 (92.8◦ ). Therefore, the combined
action of the castor oil and the siloxane can enhance the hydrophobicity
vastly. This will slow the moisture transmissivity and improve the
controlled release properties.
The composition and distribution of the formed HDCFs coatings
(HDCF0, HDCF30, HDCF60 and HDCF90) were studied by EDX spectra
(Fig. 2A3–D3) and EDX maps (Fig. 2A4–D4). Results not only showed the
elements composition on the coating surface, but also reflected the el­
ements distribution. The C and O elements are evenly distributed in the
coating surface. After the addition of siloxane, Si element also appeared
uniformly in the HDCFs coatings, proving that siloxane was successfully
added onto the formed HDCFs coatings and evenly distributed. The Si
content of the coating material reduced gradually with the increase of
castor oil content, which is due to the more compact and stable network
structure of the formed HDCFs coating by the increasing densification
modification agent content.
To confirm the water absorption abilities of the HDCF0, HDCF30,
HDCF60 and HDCF90, the WARs were measured by weighing in the
increasing soak period (Fig. S3). WARs reflect water barrier capabilities.
The bigger WARs represent the poor water barrier capabilities. The
water and the dissolved nutrient can pass the coatings quickly, thereby
promoting the rapid release of nutrients. After 36 h, the WARs of HDCF0,
HDCF30, HDCF60 and HDCF90 were 98.87 %, 44.69 %, 4.84 % and
0.66 %, respectively. This means the WARs of the formed HDCFs coat­
ings decrease greatly with the increasing castor oil content. The
hydroscopicity of membrane material is highly correlated with its hy­
drophobicity. The water absorption abilities of the formed HDCFs
coatings were consistent with the hydrophobicity from the WCAs results
(Fig. 2A2–D2). In addition, the WARs of HDCF0 and HDCF30 increased
sharply at 12 h, reaching 91.77 % and 38.26 %, respectively. These re­
sults clearly indicate that the addition of the castor oil can reduce the
hygroscopicity of coating materials, which is a supporting explanation
for the results of the nutrient release rate of the HDCFs.
J. Liu et al.
3.3. Compactness of the formed HDCFs coating
The effects of castor oil content on the microstructure of the HDCFs
coatings (HDCF0, HDCF30, HDCF60 and HDCF90) were observed by
scanning electron microscopy (Fig. 3). For the fracture surfaces of the
HDCFs coatings, more compact microstructure can be observed obvi­
ously. Significantly reduced micropores can be observed with the
increased content of castor oil. The fracture surface of the HDCF90 is
obviously smooth and flat with minimal micropores (Fig. 3D1 and D2).
Furthermore, the porosities in the fracture surfaces of HDCF0, HDCF30
and HDCF60 were 11.27 %, 2.95 % and 2.57 % respectively, while the
porosity of HDCF90 was only 0.79 % at a magnification of 20,000 times
(Fig. 3A3–D3). The existence of micropores will make it more quickly
when water into and nutrient out the HDCFs coating because of the fact
that the numbers of micropores can observably affect the controlled
release performance. Therefore, the increased content of castor oil
would reduce the micropores and make the structure compacter and
smoother, hence enhancing the performance of HDCFs.
In order to reflect the micropore state of the coatings more intui­
tively, the 3D reconstruction images and local micropore distribution
scanning of HDCF0 and HDCF90 were conducted (Fig. 4). At the same
scale, the pores density of HDCF0 is obviously much larger than that of
HDCF90 (Fig. 4A1–A4), which proved that the addition of castor oil
reduced the micropores of the coatings. The difference of the pore ratio
was also obvious in three-dimensional local pore distribution model.
The porosity of HDCF0 is 5.76 % (Fig. 4A1–A2), 1.11 % (Fig. 4B1–B2) and
2.98 % (Fig. 4B3–B4) respectively, significantly higher than that of
HDCF90 by 1.08 % (Fig. 4A3–A4), 0.76 % (Fig. 4C1–C2) and 0.75 %
(Fig. 4C3–C4), and the pore volume of HDCF0 is also larger than that of
HDCF90. Clearly, the significant reduction in the number and volume of
HDCF90 micropores can be attributed to the addition of castor oil, which
participated in the formation of the bio-based coating and clogged the
HDCF0 micropores.
Fig. 4. Three-dimensional (3D) global reconstruction images of half of the membrane shell of the HDCF0 (A1–A2), HDCF90 (A3–A4), and 3D local pore distribution
model of the HDCF0 (B1–B4), HDCF90 (C1–C4) obtained by CT scan (blue and green are the pores).
6
Journal of Environmental Chemical Engineering 11 (2023) 110591
3.4. Elasticity of the formed HDCFs coating
We also used AFM ScanAsyst-HR and PeakForce QNM imaging
modes to study the micromechanics and microstructure of the HDCFs,
and further analyzed the effect of castor oil on the micromechanical
properties of HDCFs (Fig. 5). The root mean square roughness of HDCF0,
HDCF30, HDCF60 and HDCF90 was 39.2, 13.0, 13.0 and 7.77 nm
respectively, and the mean of Young’s modulus was 5025.52, 3175.72,
2195.23 and 1325.68 MPa, respectively. With the increase of castor oil,
both the roughness and elastic modulus of HDCFs showed a decreasing
trend, which was also evident in the 3D color height image
(Fig. 5A1–D2). The rough bumps on the surface of the coatings may be
caused by binding, voids or stacking generated during the synthesis of
bio-based polyurethane, which will make the coatings with abundant
micropore and the rapid nutrient loss. Fortunately, the addition of castor
oil reorganized the original structure of polyurethane and made the
coatings homogeneous and compact, which was consistent with the
results of SEM topography (Fig. 3). Young’s modulus reflects the elas­
ticity to some extent. The larger Young’s modulus will cause the smaller
the elastic modulus. Compared with the HDCF0, the Young’s modulus of
HDCF90 reduced by 73.62 %. In addition, the regional distribution of
roughness and Young’s modulus of the HDCF0, HDCF30, HDCF60 and
HDCF90 showed the inhomogeneity of the bio-based coatings
(Fig. 5A4–D4). These results indicate that castor oil can significantly
improve the uniformity and elasticity of the coatings and the high
elasticity bio-polyurethane-coating fertilizers was successfully prepared.
The adhesion of HDCF30 was 156.90 nN and the HDCF0, HDCF60 and
HDCF90 was 120.58, 84.57 and 68.29 nN respectively (Fig. 5A3–D3),
indicating that the low concentration of castor oil will increase the
adhesion of the film, but large amount of castor oil can greatly reduce
the adhesion. For the HDCF90, the low roughness ensured the uniformity
of the coating and reduced the micropores, and the high elasticity made
the film material had good ductility, which made it difficult to be
J. Liu et al.
Fig. 5. Height images (A1–A4), elastic modulus images (B1–B4), adhesion images (C1–C4) and the normal distribution of roughness and Young’s modulus (A4–D4)
measured by AFM of the HDCF0, HDCF30, HDCF60 and HDCF90, respectively.
broken, and the low adhesion made the water not easy to stay on the film
surface. These factors together resulted in the excellent controlled
release performance of the HDCF90.
3.5. Nutrient controlled-release abilities of the HDCFs
To study the effects of the different castor oil content and the
siloxane content on the nutrient release characteristics of the HDCFs, the
nutrient release longevity of the HDCFs with increasing coating mate­
rials content (2.5 %, 3 %, 3.5 %, 4 % and 4.5 %) were measured by
immersing at 25 ◦ C static water (Fig. 6A1–D4). For the HDCFs with 0:100
of the proportion of the castor oil and LPAC, the nutrient had been
dissolved in only 2 h, regardless of the siloxane content and coating
contents. (Fig. 6A1–A4). For HDCFs with 30:70 of the proportion of the
castor oil and LPAC, the controlled release longevity was extended.
When the coating content was 4.5 %, the release longevity of HDCFs
with 0 %, 1 %, 5 % and 10 % of the siloxane of the total polyols were
0.65, 0.72, 1.22, and 1.22 d, respectively (Fig. 6B1–B4). It could be seen
that the controlled release longevity increased with the increase of
7
Journal of Environmental Chemical Engineering 11 (2023) 110591
siloxane content. Interestingly, the trend was reversed with the more
castor oil addition. For HDCFs with 60:40 and 90:10 of the proportion of
the castor oil and LPAC, the nutrient controlled release longevity was
extended in a cliff-like manner. However, with the increase of siloxane,
the controlled release longevity was shortened. HDCF with 90:10 of the
proportion of the castor oil and LPAC and 5 % of the siloxane of the total
polyols exhibits the best performance effect (120.45 d). This may be due
to the fact that the high content of castor oil is able to form a dense
encapsulated coating with the liquefied products, while the addition of
siloxane disrupts the dense nature of the coating. The specific values of
the nutrient release longevities of the HDCFs are shown in Supporting
information (Table S3). Results showed that the increasing castor oil
content can greatly enhance the nutrient release longevities, and the
curve of nutrient release rate changed from inverted L to S shape. The
longer nutrient release longevity can be observed with the increased
coating materials content. What’s more, in the case of the low concen­
tration of the castor oil, the addition of the siloxane can improve the
controlled release performance, while in the case of the high concen­
tration of the castor oil, the addition of the siloxane will destroy the
J. Liu et al. Journal of Environmental Chemical Engineering 11 (2023) 110591

Fig. 6. The cumulative N release rate of (A1–D1) 0 % of the siloxane of the total polyols and 0:100, 30:70, 60:40, 90:10 of the proportion of the castor oil and LPAC,
respectively; (A2–D2) 1 % of the siloxane of the total polyols and 0:100, 30:70, 60:40, 90:10 of the proportion of the castor oil and LPAC, respectively; (A3–D3) 5 % of
the siloxane of the total polyols and 0:100, 30:70, 60:40, 90:10 of the proportion of the castor oil and LPAC, respectively; (A4–D4) 10 % of the siloxane of the total
polyols and 0:100, 30:70, 60:40, 90:10 of the proportion of the castor oil and LPAC, respectively.

original compact structure and reduce the controlled release
performance.
The initial nitrogen release rate is also an important index to char­
acterize coating quality, which can indicate the nitrogen release char­
acteristics in the initial 24 h soaking in 25 ◦ C water. The HDCFs with
0:100 and 30:70 of the proportion of the castor oil and LPAC released
completely in 24 h without controlled release effect. For HDCFs with
60:40 and 90:10 of the proportion of the castor oil and LPAC, the initial
release rates were quiet low (0.39–6.23 %) regardless of siloxane con­
tents (0 %, 1 %, 5 %, 10 %) and coating contents (2.5 %, 3.0 %, 3.5 %,
4.0 %, 4.5 %). The HDCFs with the longest controlled release longevity
(90:10 of the proportion of the castor oil and LPAC, 5 % silicone and
4.5 % coating content) has an initial release longevity of 0.83 %. The
specific values of initial release rate are shown in Supporting informa­
tion (Table S3). Worth mentioned was that the HDCFs with 60:40 and
90:10 of the proportion of the castor oil and LPAC reduced the initial
release rate and enhanced the controlled release longevity significantly.
The addition of castor oil increased the cross-linking degree, which
made the coatings more compact with lesser micropores (consistent with
the SEM images) (Fig. 3A2–D2). Therefore, the prolonged the nitrogen
release longevity and significantly reduced the initial nitrogen release
rate can be obtained.
Response surface methodology was employed to describe the re­
lations of the castor oil content and the coating materials content of the
HDCFs on the initial nitrogen release rate (Fig. S4) and the nitrogen
release longevity (Fig. 7). According to the response value, the three-
dimensional model containing different siloxane content (0 %, 1 %,
5 %, 10 %) can be written as:
z1 = 51.91 − 0.05x − 45.31y + 0.03xy − 0.01x2 + 12.85y2
+ 0.01x2y − 0.05xy2 − 1.17y3 (1)
z2 = 110.31 − 0.91x − 93.50y + 0.47xy + 25.90y2 − 0.09xy2 − 2.33y3 (2)
z3 = 27.07 + 1.99x − 34.83y − 1.05xy − 0.01x2 + 13.18y2
+ 0.01x2y + 0.10xy2 − 1.50y3 (3)
z4 = 63.21 − 0.83x − 55.15y + 0.28xy + 15.92y2 − 0.05xy2 − 1.50y3 (4)
where, x represents the castor oil contents, y represents the coating

8
J. Liu et al. Journal of Environmental Chemical Engineering 11 (2023) 110591

Fig. 7. The relationship between the N release longevity (A1–A4: 0 %, 1 %, 5 %, 10 % of the siloxane of the total polyols, respectively) with coating materials content
and castor oil contents of the HDCFs, respectively; The contours of the N release longevity (B1–B4: 0 %, 1 %, 5 %, 10 % of the siloxane of the total polyols,
respectively) with coating materials content and castor oil contents of the HDCFs, respectively.

materials contents; x and y are independent variables, while z1–z4
correspond to nutrient release longevities of different siloxane content of
HDCFs. For HDCFs with siloxane content of 0 %, 1 % and 5 % of the total
polyols, the trend of the corresponding surface is similar to that of
HDCFs with siloxane content of 10 % of the total polyols, which again
shows that siloxane has little influence on the controlled release per­
formance. The castor oil is a major influence on release longevities, as
evidenced by the steep curve from the 3D model. Furthermore, the
initial nitrogen release rate and the nitrogen release longevity can be
accurately predicted by regulating and controlling the castor oil content
and the coating materials content according to the three-dimensional
model. This precise controlled release model will also be benefit for
the development of the HDCFs for the corps with long-lasting nutrient
requirements in specific period, which will release nutrients in large
quantities in that specific period by adjusting castor oil addition amount
and coating materials contents.

Fig. 8. The controlled-release mechanism of the HDCFs coating: (A) only with hydrophobic modification and (B) with hydrophobic-densified double-modification.

9
J. Liu et al.
3.6. Nutrient controlled release mechanism of the HDCFs
How can the hydrophobic-densified double-modification of the
HDCFs coating significantly enhance the controlled-release longevity?
For the coating only with hydrophobic modification, there are numerous
micropores with large micropore diameter in the coating (Fig. 3 and
Fig. 4). Despite the hydrophobic layer on the surface of the micropores,
water can still enter into the micropores of the coating and contacted the
fertilizer core with liquid state directly when immersed into water,
which caused the rapid release of nutrients (Fig. 8). As a contrast, for the
coating with hydrophobic-densified double-modification, the minimal
micropores with minute micropore diameter and hydrophobic layer in
the HDCFs coating can be observed. When immersed into water, water
can not entirely enter into and soak the micropores of the HDCFs coating
with liquid state. There will be atmosphere column within the micro­
pores of the HDCFs coatings, function just like the atmosphere “stopper”,
which can prevent the entrance of the liquid water. The atmosphere
“stopper” in micropore only allows water vapor molecules (instead of
liquid) to enter the internal urea core of HDCFs (Fig. 8). Therefore, the
nutrient release speed can be significantly slow down by reducing water
accumulation in the internal urea core with hydrophobic-densified
double-modification.
It is widely believed that hydrophobic modification can effectively
improve nutrient controlled release ability. However, in this work, we
can conclude that the controlled release performance is also related to
the micropore sizes of the coatings. When the micropore is sufficiently
large and ample, even after hydrophobic modification, the controlled
release performance can be improved to a small extent. Only after
densification modification, when the micropore size becomes very
small, water can only enter the coatings in the form of gaseous water
molecules, and the nutrient controlled release performance can be
greatly improved.
Fig. 9. The picture of the oilseed rape in the (A) seedling stage and (B) harvest stage; (C) The N release rate of the HDCFs in planting soil; (D) The fresh biomass of the
above-ground plant and (E) the N utilization efficiency of the oilseed rape with different fertilization treatment. All treatments were repeated three times to take
the mean.
10
Journal of Environmental Chemical Engineering 11 (2023) 110591
3.7. Oilseed rape applications of the HDCFs
To evaluate the applied effects of the HDCFs, the HDCF60 with 3 %
coating materials content (controlled-release longevity: 25.98 days,
abbreviated as CN-30) and HDCF90 with 2.5 % coating materials content
(controlled-release longevity: 60.48 days, abbreviated as CN-60) were
selected to carried out the potted oilseed rape experiment. The N release
longevities in soil were carried out simultaneously with the oilseed rape
pot experiment (Fig. 9C). When oilseed rape was sown and fertilized, the
HDCFs were buried in the pot soil (− 10 cm) at the same time. For the
CN-30, the nitrogen release longevity with 80 % nitrogen release rate
was 24.75 days. The staged nitrogen release rates for 7, 14 and 21th day
were 20.90 %, 63.58 % and 75.85 % respectively. The relatively quick
release within the 21 days can provide the sufficient nitrogen for seed­
ling stage and thus lack of the nitrogen supply in the subsequent stage.
For the CN-60, the slower release rate at the initial 14 days (11.92 %)
and the faster release rate at the subsequent 14–38 days (62.48 %) can
be observed, which can provide the sufficient nitrogen supply for the
seedling stage and the maximum nutrient requirement period for the
potted oilseed rape. Furthermore, compared with the nitrogen release
longevities for CN-60 at 25 ◦ C static water, those of in soil showed faster
nitrogen release rates in the initial stage and slower nitrogen release rate
in the later stage (> 38 days). This can be attributed to the gradually
reduced temperature in the growing period of the potted oilseed rape
(Fig. S5).
To confirm the effect of the HDCFs on the yield indexes of the oilseed
rape, we obtained the fresh biomass of the above-ground oilseed rape at
seedling stage and harvest stage (yield) with different fertilization
treatments (Fig. 9D). Treatments using HDCFs at seedling stage all had
significantly higher fresh biomass than N300 treatment. Compared with
the fresh biomass of the above-ground oilseed rape at harvest stage
(yield) of the N300, those of N0, N240, CN300-30, CN240-30, CN300-60,
CN240-60 increase − 62.10 %, − 20.29 %, 40.82 %, 28.81 %, 71.75 %
and 50.40 % respectively. The CN300-60 showed the best increment
J. Liu et al.
(71.75 %) vs. N300. This can be attributed to the timely and enough
nitrogen supply of the CN-60 in the whole growing period of the oilseed
rape, while those treatments using common urea lack the sufficient ni­
trogen supply due to the premature release. The fresh biomass of the
above-ground oilseed rape with HDCFs (CN300-30, CN240-30, CN300-60,
CN240-60) increase significantly vs. N300, even the treatments with 80%
N application amount. Therefore, we can conclude that the just right
controlled-release longevity of the controlled-release fertilizer can effi­
ciently improve the oilseed rape yield. This can be also verified by the
picture of the oilseed rape with different treatment in the seedling stage
and harvest stage (Fig. 9A,B).
Nitrogen utilization efficiencies of the oilseed rapes at the harvest
stage were also calculated and analyzed to further evaluate the appli­
cation effect of the HDCFs (Fig. 9E). Similar with the yield trend of the
different fertilization treatments, the nitrogen utilization efficiency with
HDCFs treatments (CN300-30, CN240-30, CN300-60, CN240-60) was
10.55 %, 12.26 %, 14.33 % and 22.21 %, which are higher than that of
N300 (6.63 %), even the treatment with 80 % N application amount.
More notably, the CN240-60 (22.21 %) showed the highest nitrogen
utilization efficiency. This is of great significance for the reducing fer­
tilizer waste and agricultural pollution and solving the agriculture-food
security crisis predicted by 2050.
The physiological and quality indexes of oilseed rape with different
fertilization treatments at seedling stage and harvest stage were also
tested. The plant height, chlorophyll value, leaf area of CN-30 and CN-60
treatments were significantly higher than those of common urea treat­
ments, and this promoting effect has no effect on crop quality. Moreover,
the nitrate nitrogen of the CN-30 and CN-60 treatments all showed in­
crease due to the controlled release properties of HDCFs, which proved
that the HDCFs are effective in reducing the soil nitrogen leaching,
maintaining the soil fertility and promoting the sustainable develop­
ment of the soil environment. The market profit of oilseed rape also
highlights the application value of HDCFs more intuitively. Results
showed that all the treatment with HDCFs showed the higher retained
profits vs. N300, even the treatment with 80 % N application amount.
This will be benefit to improve the recognition degree from farmers to
CRFs and promote the development, popularization and application.
The specific values of the above tests are in the Supporting information
(Table S4–S6).
4. Conclusions
In this work, the hydrophobic-densified double-modified waste-
carton-based polyurethane-coated controlled-release fertilizers were
developed. The significantly enhanced controlled-release longevity
(< 2 h to 120.45 days) can be attributed to the obviously reduced
micropore porosities (5.76–1.08 %), the improved hydrophobicity
(92.8–138.3◦ ) and the decreased WARs (98.87–0.66 %). The nutrient
release models were established to fast predict the controlled-release
longevity by adjusting the influence factor. Furthermore, the enhanced
elasticity (5025.52–1325.68 MPa) of the HDCFs coatings also contrib­
uted to improve the controlled-release abilities. The controlled-release
mechanism was also clarified: the atmosphere “stopper” in the
“smaller and less” micropores in HDCFs coating only allows water vapor
molecules (instead of liquid) slowly permeate into the internal urea core
and significantly enhance the controlled-release longevities. The
dramatically increased oilseed rape yield (71.75 %) showed the efficient
application effect of the HDCFs. All the results indicate that HDCF with
90:10 of the proportion of the castor oil and LPAC and 5 % of the
siloxane of the total polyols exhibits the best performance effect. The
efficient strategy provided in this work to fabricate eco-friendly waste-
cardboard based CRFs can reduce fertilizer consumption, increase crop
yields and foster the end-user confidence in the low-cost and eco-
friendly biowaste-derived controlled-release fertilizers.
11
Journal of Environmental Chemical Engineering 11 (2023) 110591
Supporting Information
Synthesis reaction and photos of LPAC and HDCFs; scheme of potted
experiment of oilseed rape; the main components and proportions of
LPAC measured by GC-MS; 25 ◦ C static water release rate data of the
HDCFs with different castor oil and siloxane addition levels: 24-h release
rate and 80 % release period; water absorption of the HDCFs; the rela­
tionship model between the N initial release rate with coating materials
content and castor oil contents of the HDCFs; soil temperature with
− 10 cm depth in the growing period of the potted oilseed rape; detailed
data of physiological indexes, quality indexes, nitrogen accumulation
and soil available nitrogen content of the potted oilseed rape; economic
benefits of different treatments for the potted oilseed rape.
CRediT authorship contribution statement
Jiahui Liu: Methodology, Writing – original draft. Yuechao Yang:
Methodology, Project administration, Supervision. Wentao Wang:
Software. Dongdong Cheng: Methodology. Yuanyuan Yao: Investiga­
tion, Formal analysis. Tianlin Shen: Investigation, Formal analysis.
Ting Zhang: Conceptualization, Data curation. Jinpeng Wu: Concep­
tualization, Data curation. Xinning Zhao: Conceptualization, Data
curation. Jiazhuo Xie: Investigation, Visualization.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data Availability
Data will be made available on request.
Acknowledgments
This research was funded by the National Natural Science Founda­
tion of China (32002134); the Natural Science Foundation of Shandong
Province (ZR2020QC162); the Research Start-up Project of Shandong
Agricultural University (72098); the China Postdoctoral Science Foun­
dation (294570); the Key Research and Development Program of
Shandong Province (2021CXGC010810); the Open Research Fund from
Kingenta (381332); Young and Innovative Talents Introduction and
Education Program of Universities in Shandong Province.
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.jece.2023.110591.
References
[1] Y. Sun, R. Hu, C. Zhang, Does the adoption of complex fertilizers contribute to
fertilizer overuse? Evidence from rice production in China, J. Clean. Prod. 219
(2019) 677–685, https://doi.org/10.1016/j.jclepro.2019.02.118.
[2] Q. Wu, Y. Wang, Y. Ding, W. Tao, S. Gao, Q. Li, W. Li, Z. Liu, G. Li, Effects of
different types of slow- and controlled-release fertilizers on rice yield, J. Integr.
Agric. 20 (6) (2021) 1503–1514, https://doi.org/10.1016/s2095-3119(20)63406-
2.
[3] S. Bi, V. Barinelli, M.J. Sobkowicz, Degradable controlled release fertilizer
composite prepared via extrusion: fabrication, characterization, and release
mechanisms, Polymers 12 (2) (2020), https://doi.org/10.3390/polym12020301.
[4] D. Lawrencia, S.K. Wong, D.Y.S. Low, B.H. Goh, J.K. Goh, U.R. Ruktanonchai,
A. Soottitantawat, L.H. Lee, S.Y. Tang, Controlled release fertilizers: a review on
coating materials and mechanism of release, Plants 10 (2) (2021) 238–262,
https://doi.org/10.3390/plants10020238.
[5] P. Omara, L. Aula, F. Oyebiyi, W.R. Raun, World cereal nitrogen use efficiency
trends: review and current knowledge, Agrosyst. Geosci. Environ. 2 (1) (2019) 1–8,
https://doi.org/10.2134/age2018.10.0045.
J. Liu et al.
[6] Y. Wang, Y. Lu, J. Yuan, G. He, Evaluating the risks of nitrogen fertilizer-related
grain production processes to ecosystem health in China, Resour. Conserv. Recycl.
177 (1–8) (2022), 105982, https://doi.org/10.1016/j.resconrec.2021.105982.
[7] Y. Lyu, X. Yang, H. Pan, X. Zhang, H. Cao, S. Ulgiati, J. Wu, Y. Zhang, G. Wang,
Y. Xiao, Impact of fertilization schemes with different ratios of urea to controlled
release nitrogen fertilizer on environmental sustainability, nitrogen use efficiency
and economic benefit of rice production: a study case from Southwest China,
J. Clean. Prod. 293 (1–12) (2021), 126198, https://doi.org/10.1016/j.
jclepro.2021.126198.
[8] J. Guo, J. Fan, F. Zhang, S. Yan, J. Zheng, Y. Wu, J. Li, Y. Wang, X. Sun, X. Liu,
Y. Xiang, Z. Li, Blending urea and slow-release nitrogen fertilizer increases dryland
maize yield and nitrogen use efficiency while mitigating ammonia volatilization,
Sci. Total Environ. 790 (2021), 148058, https://doi.org/10.1016/j.
scitotenv.2021.148058.
[9] J. Li, Y. Liu, J. Liu, X. Cui, T. Hou, D. Cheng, A novel synthetic slow release
fertilizer with low energy production for efficient nutrient management, Sci. Total
Environ. 831 (2022), 154844, https://doi.org/10.1016/j.scitotenv.2022.154844.
[10] S. Fertahi, M. Ilsouk, Y. Zeroual, A. Oukarroum, A. Barakat, Recent trends in
organic coating based on biopolymers and biomass for controlled and slow release
fertilizers, J. Control. Release 330 (2021) 341–361, https://doi.org/10.1016/j.
jconrel.2020.12.026.
[11] P. Vejan, T. Khadiran, R. Abdullah, N. Ahmad, Controlled release fertilizer: a
review on developments, applications and potential in agriculture, J. Control.
Release 339 (2021) 321–334, https://doi.org/10.1016/j.jconrel.2021.10.003.
[12] L. Liu, T. Shen, Y. Yang, B. Gao, Y.C. Li, J. Xie, Y. Tang, S. Zhang, Z. Wang, J. Chen,
Bio-based large tablet controlled-release urea: synthesis, characterization, and
controlled-released mechanisms, J. Agric. Food Chem. 66 (43) (2018)
11265–11272, https://doi.org/10.1021/acs.jafc.8b04042.
[13] W. Wang, S. Yang, A. Zhang, Z. Yang, Synthesis of a slow-release fertilizer
composite derived from waste straw that improves water retention and agricultural
yield, Sci. Total Environ. 768 (2021), https://doi.org/10.1016/j.
scitotenv.2021.144978.
[14] J. Fu, C. Wang, X. Chen, Z. Huang, D. Chen, Classification research and types of
slow controlled release fertilizers (SRFs) used – a review, Commun. Soil Sci. Plant
Anal. 49 (17) (2018) 2219–2230, https://doi.org/10.1080/
00103624.2018.1499757.
[15] G. Li, B. Zhao, S. Dong, J. Zhang, P. Liu, W. Lu, Controlled-release urea combining
with optimal irrigation improved grain yield, nitrogen uptake, and growth of
maize, Agric. Water Manag. 227 (1–13) (2020), 105834, https://doi.org/10.1016/
j.agwat.2019.105834.
[16] A. Sarkar, D.R. Biswas, S.C. Datta, T. Roy, P.C. Moharana, S.S. Biswas, A. Ghosh,
Polymer coated novel controlled release rock phosphate formulations for
improving phosphorus use efficiency by wheat in an Inceptisol, Soil Tillage Res.
180 (2018) 48–62, https://doi.org/10.1016/j.still.2018.02.009.
[17] J. Liao, X. Liu, A. Hu, H. Song, X. Chen, Z. Zhang, Effects of biochar-based
controlled release nitrogen fertilizer on nitrogen-use efficiency of oilseed rape
(Brassica napus L.), Sci. Rep. 10 (1) (2020) 1–14, https://doi.org/10.1038/s41598-
020-67528-y (11063).
[18] J. Li, Y. Liu, Y. Tang, J. Shao, T. Xu, R. Ma, Y. Jiang, D. Cheng, Optimizing fertilizer
management based on controlled-release fertilizer to improve yield, quality, and
reduce fertilizer application on apples, J. Soil Sci. Plant Nutr. 22 (2022) 393–405,
https://doi.org/10.1007/s42729-021-00656-0.
[19] S. Sharma, V.S. Rana, R. Pawar, J. Lakra, V. Racchapannavar, Nanofertilizers for
sustainable fruit production: a review, Environ. Chem. Lett. 19 (2021) 1693–1714,
https://doi.org/10.1007/s10311-020-01125-3.
[20] A.E. El-Karamity, N.R. Ahmed, A.N. Mohamed, Effect of intercropping of some oil
summer crops with maize under levels of mineral N and nano N fertilizers, Sci. J.
Agric. Sci. 2 (2) (2020) 90–103, https://doi.org/10.21608/sjas.2020.42913.1038.
[21] H. Tian, Z. Liu, M. Zhang, Y. Guo, L. Zheng, Y.C. Li, Biobased polyurethane, epoxy
resin, and polyolefin wax composite coating for controlled-release fertilizer, ACS
Appl. Mater. Interfaces 11 (5) (2019) 5380–5392, https://doi.org/10.1021/
acsami.8b16030.
[22] C. Wang, Z. Lü, J. Li, Z. Cao, B. Wei, H. Li, M. Shang, C. Su, Efficient use of waste
carton for power generation, tar and fertilizer through direct carbon solid oxide
fuel cell, Renew. Energy 158 (2020) 410–420, https://doi.org/10.1016/j.
renene.2020.05.082.
[23] F. Zambrano, R. Marquez, H. Jameel, R. Venditti, R. Gonzalez, Upcycling strategies
for old corrugated containerboard to attain high-performance tissue paper: a viable
answer to the packaging waste generation dilemma, Resour. Conserv. Recycl. 175
(1–13) (2021), 105854, https://doi.org/10.1016/j.resconrec.2021.105854.
[24] M.J. John, S. Thomas, Biofibres and biocomposites, Carbohydr. Polym. 71 (3)
(2008) 343–364, https://doi.org/10.1016/j.carbpol.2007.05.040.
[25] O. León, D. Soto, A. Antúnez, R. Fernández, J. González, C. Piña, A. Muñoz-Bonilla,
M. Fernandez-García, Hydrogels based on oxidized starches from different
botanical sources for release of fertilizers, Int. J. Biol. Macromol. 136 (2019)
813–822, https://doi.org/10.1016/j.ijbiomac.2019.06.131.
[26] S. Sun, W. Wang, F. Liu, L. Zhang, X. Fan, Coating layer preparation with mixed
vegetable oil and nutrient release regulation of fertilizer, Eur. Polym. J. 120 (1–6)
(2019), 109194, https://doi.org/10.1016/j.eurpolymj.2019.08.021.
[27] X. Peng, J. Ren, L. Zhong, F. Peng, R. Sun, Xylan-rich hemicelluloses-graft-acrylic
acid ionic hydrogels with rapid responses to pH, salt, and organic solvents, J. Agric.
Food Chem. 59 (15) (2011) 8208–8215, https://doi.org/10.1021/jf201589y.
[28] A. Olad, H. Zebhi, D. Salari, A. Mirmohseni, A.R. Tabar, Slow-release NPK fertilizer
encapsulated by carboxymethyl cellulose-based nanocomposite with the function
12
Journal of Environmental Chemical Engineering 11 (2023) 110591
of water retention in soil, Mater. Sci. Eng. C 90 (2018) 333–340, https://doi.org/
10.1016/j.msec.2018.04.083.
[29] S. Zhang, Y. Yang, B. Gao, Y.C. Li, Z. Liu, Superhydrophobic controlled-release
fertilizers coated with bio-based polymers with organosilicon and nano-silica
modifications, J. Mater. Chem. A 5 (37) (2017) 19943–19953, https://doi.org/
10.1039/c7ta06014a.
[30] S. Liu, Q. Wu, X. Sun, Y. Yue, B. Tubana, R. Yang, H. Cheng, Novel alginate-
cellulose nanofiber-poly(vinyl alcohol) hydrogels for carrying and delivering
nitrogen, phosphorus and potassium chemicals, Int. J. Biol. Macromol. 172 (2021)
330–340, https://doi.org/10.1016/j.ijbiomac.2021.01.063.
[31] Q. Wang, F. Dong, J. Dai, Q. Zhang, M. Jiang, Y. Xiong, Recycled-oil-based
polyurethane modified with organic silicone for controllable release of coated
fertilizer, Polymers 11 (3) (2019) 454–468, https://doi.org/10.3390/
polym11030454.
[32] Q. Wei, L. Zhang, J. Chen, Z. Tong, X. Zhou, L. Shao, Z. Wu, P. Zhan, F. Wang,
N. Liu, H. Lin, H. Dong, Solvent-free coating of crosslinked and hydrophobic lignin-
based biocomposite for slow-release fertilizer, Polym. Test. 102 (2021), https://
doi.org/10.1016/j.polymertesting.2021.107335.
[33] H. Lu, C. Dun, H. Jariwala, R. Wang, P. Cui, H. Zhang, Q. Dai, S. Yang, H. Zhang,
Improvement of bio-based polyurethane and its optimal application in controlled
release fertilizer, J. Control. Release 350 (2022) 748–760, https://doi.org/
10.1016/j.jconrel.2022.08.039.
[34] H. Tian, Z. Li, P. Lu, Y. Wang, C. Jia, H. Wang, Z. Liu, M. Zhang, Starch and castor
oil mutually modified, cross-linked polyurethane for improving the controlled
release of urea, Carbohydr. Polym. 251 (2021), 117060, https://doi.org/10.1016/
j.carbpol.2020.117060.
[35] J. Xie, Y. Yang, B. Gao, Y. Wan, Y.C. Li, D. Cheng, T. Xiao, K. Li, Y. Fu, J. Xu,
Q. Zhao, Y. Zhang, Y. Tang, Y. Yao, Z. Wang, L. Liu, Magnetic-sensitive
nanoparticle self-assembled superhydrophobic biopolymer-coated slow-release
fertilizer: fabrication, enhanced performance, and mechanism, ACS Nano 13 (3)
(2019) 3320–3333, https://doi.org/10.1021/acsnano.8b09197.
[36] H. Shi, D. Liang, H. Deng, F. Xie, Z. Chen, Y. Chen, Q. Lu, X. Liu, C. Zhang, Bio-
based superhydrophobic polymer coatings for slow-release fertilizers via a UV-
curing encapsulation method, Ind. Crops Prod. 188 (2022), https://doi.org/
10.1016/j.indcrop.2022.115580.
[37] C. Wang, S. Song, Z. Yang, Y. Liu, Z. He, C. Zhou, L. Du, D. Sun, P. Li, Hydrophobic
modification of castor oil-based polyurethane coated fertilizer to improve the
controlled release of nutrient with polysiloxane and halloysite, Prog. Org. Coat.
165 (2022), https://doi.org/10.1016/j.porgcoat.2022.106756.
[38] M. Sun, H. Guo, J. Zheng, Y. Wang, X. Liu, Q. Li, R. Wang, X. Jia, Hydrophobic
octadecylamine-polyphenol film coated slow released urea via one-step spraying
co-deposition, Polym. Test. 91 (1–8) (2020), 106831, https://doi.org/10.1016/j.
polymertesting.2020.106831.
[39] X. Liu, Y. Yang, B. Gao, Y. Li, Y. Wan, Environmentally friendly slow-release urea
fertilizers based on waste frying oil for sustained nutrient release, ACS Sustain.
Chem. Eng. 5 (7) (2017) 6036–6045, https://doi.org/10.1021/
acssuschemeng.7b00882.
[40] C. Jia, P. Lu, M. Zhang, Preparation and characterization of environmentally
friendly controlled release fertilizers coated by leftovers-based polymer, Processes
8 (4) (2020) 417–431, https://doi.org/10.3390/pr8040417.
[41] Y. Wang, M. Sun, D. Qiao, J. Li, Y. Wang, W. Liu, C. Bunt, H. Liu, J. Liu, X. Yang,
Graft copolymer of sodium carboxymethyl cellulose and polyether polyol (CMC-g-
TMN-450) improves the crosslinking degree of polyurethane for coated fertilizers
with enhanced controlled release characteristics, Carbohydr. Polym. 272 (2021),
118483, https://doi.org/10.1016/j.carbpol.2021.118483.
[42] X. Ma, J. Chen, Y. Yang, X. Su, S. Zhang, B. Gao, Y.C. Li, Siloxane and polyether
dual modification improves hydrophobicity and interpenetrating polymer network
of bio-polymer for coated fertilizers with enhanced slow release characteristics,
Chem. Eng. J. 350 (2018) 1125–1134, https://doi.org/10.1016/j.cej.2018.06.061.
[43] J. Xie, Y. Yang, B. Gao, Y. Wan, Y.C. Li, J. Xu, Q. Zhao, Biomimetic
superhydrophobic biobased polyurethane-coated fertilizer with atmosphere
"outerwear", ACS Appl. Mater. Interfaces 9 (18) (2017) 15868–15879, https://doi.
org/10.1021/acsami.7b02244.
[44] S. Zhang, N. Gao, T. Shen, Y. Yang, B. Gao, Y.C. Li, Y. Wan, One-step synthesis of
superhydrophobic and multifunctional nano copper-modified bio-polyurethane for
controlled-release fertilizers with “multilayer air shields”: new insight of
improvement mechanism, J. Mater. Chem. A 7 (16) (2019) 9503–9509, https://
doi.org/10.1039/c9ta00632j.
[45] Z. Yu, D. Cheng, B. Gao, Y. Yao, C. Liu, J. Li, C. Wang, J. Xie, S. Zhang, Z. Li,
Y. Yang, Bio-based polyurethane based on a dynamic covalent network with
damage tolerance for controlled release of fertilizers, ACS Appl. Mater. Interfaces
14 (50) (2022) 56046–56055, https://doi.org/10.1021/acsami.2c14672.
[46] C. Wang, S. Song, Z. Yang, Y. Liu, Z. He, C. Zhou, L. Du, D. Sun, P. Li, Hydrophobic
modification of castor oil-based polyurethane coated fertilizer to improve the
controlled release of nutrient with polysiloxane and halloysite, Prog. Org. Coat.
165 (1–10) (2022), 106756, https://doi.org/10.1016/j.porgcoat.2022.106756.
[47] Y. Li, C. Jia, X. Zhang, Y. Jiang, M. Zhang, P. Lu, H. Chen, Synthesis and
performance of bio-based epoxy coated urea as controlled release fertilizer, Prog.
Org. Coat. 119 (2018) 50–56, https://doi.org/10.1016/j.porgcoat.2018.02.013.
[48] Y. Chen, W. Li, S. Zhang, A multifunctional eco-friendly fertilizer used keratin-
based superabsorbent as coatings for slow-release urea and remediation of
contaminated soil, Prog. Org. Coat. 154 (1–11) (2021), 106158, https://doi.org/
10.1016/j.porgcoat.2021.106158.