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

controlled-release fertilizers (CRFs) can significantly enhance the
Chemical fertilizers play an important role in increasing the output of nutrient utilization [10], increase the crop yield [11] and reduce the
the food crops, the vegetables, the fruits and the oil crops [1–3]. How­ environmental pollution compared with the uncoated fertilizer [12,13].
ever, the excessively low nutrient utilization rate of chemical fertilizers The output and application amount of polymer coated CRFs had
in current season [4,5] resulted in the serious wasting of the fertilizer 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. Journal of Environmental Chemical Engineering 11 (2023) 110591

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

2
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 gauze, weigh and calculate the WARs. The soil humidity and tempera­
SU8020 scanning electron microscope (SEM) and an energy dispersive ture were recorded with a soil temperature & moisture datalogger (TMS,
X-ray spectroscopy (EDX) detector attached to the SEM. The crystallinity TOMST).
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 2.5. Potted oilseed rape applications
strument. The thermostability was measured using a thermogravimetric
analyzer (DTG60A) from Shimadzu with a heating rate of 20 ◦ C/min The pot experiment was carried out to evaluate the effects of HDCFs
within 30–800 ◦ C. The surface roughness, Young modulus and adhesion on the growth of the oilseed rape. Details about the characterization
of the HDCFs coatings was tested by an atomic force microscope (AFM) studies are available in the Supporting information.
[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 3. Results and discussion
business). The water nutrient release characteristics were measured
according to the according to the ISO 18644. The water absorption rate 3.1. Structure and performance of LPAC and HDCFs coatings
(WAR) of the bio-based coating materials were determined by
immersing in water, sampling at regular intervals, wipe it dry with 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. Journal of Environmental Chemical Engineering 11 (2023) 110591

spectrometry and gel permeation chromatography. The main compo­ HDCF60 and HDCF90) can verify the successful formation of the HDCFs
nents of LPAC are polyhydroxyl compounds, such as ethanol, diethylene coatings by the XRD patterns (Fig. 1C).
glycol, triethylene glycol, heptaethylene glycol, acetonyldime­ The FTIR spectra were employed to explore the structure change of
thylcarbinol, butyldimethylcarbinol, 2-hydroxyethyl propionate, diac­ the raw coating materials (siloxane, castor oil, PAPI and LPAC) (Fig. 1D)
etone alcohol, octaethylene glycol, 1-propoxy-2-propanol and 2- and the formed HDCFs coatings (HDCF0, HDCF30, HDCF60 and HDCF90)
isopropoxy-1-propanol. The rich -OH of these compounds provided the (Fig. 1E). For the FTIR spectra of the raw coating materials, the ab­
conditions for the film forming reaction of polyurethane (Fig. 1A and sorption peaks of O-H (ν, 3464 cm− 1) for LPAC, C– – O (ν, 2240 cm− 1)
– N–
Table S2). These hydroxyl groups can be involved in the synthesis of for PAPI, -CH2 (ν, 2928 cm− 1), -CH3 (ν, 2850 cm− 1) and C– – O ( ν,
− 1 − 1
polyurethane. These polyols with different structures contribute to the 1740 cm ) for castor oil, C-C (ν, 1259 cm ) for siloxane can be
formation of complex cross-linked networks. The other substances are observed. For the FTIR spectra of the formed HDCFs coatings, the ab­
inactive components of non-reactive groups, such as 2-pentene, 3- sorption peaks of N-H (ν, 3301 cm− 1), -CH2 (ν, 2921 cm− 1), -CH3 (ν,
penten-2-one, 3-butenoic acid, isobutyl ether, syringic acid, 3-butenoic 2851 cm− 1), C– – O (ν, 1720 cm− 1), C-H (δ, 1512 cm− 1), and C-O-C (ν,
acid, diethoxytetraethylene glycol, 1,4,7,10-tetraoxacyclododecane, 1218 cm− 1) can be observed. It’s worth noting that the absorption peaks
acrolein ethylene acetal and 1-methyl-1-(2-pentyloxy)-1-silacyclopen­ of C–
– N–– O (ν, 2240 cm− 1) for PAPI disappeared in the FTIR spectra of
tane. They do not participate in the envelope reaction and flow out the formed HDCFs coatings, which proved the successful and thorough
with the nutrients from the micropores of the coatings when the fertil­ formation of the HDCFs coatings. Furthermore, the structure showed no
izer nutrient is released. The average molecular weight (Mw) of LPAC is obvious change compared with the four HDCFs coatings (HDCF0,
1316 g/mol, and the small molecular weight verifies the decomposition HDCF30, HDCF60 and HDCF90), which means the introduction of the
of cellulose in the carton. Compounds with molecular weight < 4521 g/ castor oil and the siloxane had no influence for the structure of formed
mol accounted for about 97.74 % of the total composition of LPAC, polyurethane.
while those with molecular weight > 4521 g/mol only accounted for TGA and DTG were used to analyze the thermal stability of the
about 2.26 % (Fig. 1B). The fact that the unchanged peaks position and formed HDCFs coatings (HDCF0, HDCF30, HDCF60 and HDCF90)
crystallinity intensity of the formed HDCFs coatings (HDCF0, HDCF30, (Fig. 1F). The formed HDCFs coatings have three weightlessness stages

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.

4
J. Liu et al. Journal of Environmental Chemical Engineering 11 (2023) 110591

at 250.15–554.78 ◦ C. The first stage is about 250.15–371.62 ◦ C, at even 45.5◦ higher than that of HDCF0 (92.8◦ ). Therefore, the combined
which the polyurethane bonds break into isocyanates and polyols [46]. action of the castor oil and the siloxane can enhance the hydrophobicity
The second stage occurs at 313.82–461.77 ◦ C, and the chains of castor vastly. This will slow the moisture transmissivity and improve the
oil and organic molecules break at this stage [39,46]. The third stage controlled release properties.
(365.46–554.78 ◦ C) is principally the decomposition of hydroxyl and The composition and distribution of the formed HDCFs coatings
polyol residues, and the final carbonization into ash [40]. The 50 % (HDCF0, HDCF30, HDCF60 and HDCF90) were studied by EDX spectra
degradation temperatures (T50%) of HDCF0, HDCF30, HDCF60 and (Fig. 2A3–D3) and EDX maps (Fig. 2A4–D4). Results not only showed the
HDCF90 were 413.07 ◦ C, 416.58 ◦ C, 424.54 ◦ C and 427.02 ◦ C respec­ elements composition on the coating surface, but also reflected the el­
tively, and the maximum weight loss temperature (Tmax) were ements distribution. The C and O elements are evenly distributed in the
410.20 ◦ C, 415.52 ◦ C, 428.86 ◦ C and 473.04 ◦ C respectively. Conse­ coating surface. After the addition of siloxane, Si element also appeared
quently, with the increase of the castor oil content, the thermal stability uniformly in the HDCFs coatings, proving that siloxane was successfully
of the polyurethane membrane was enhanced. This can be attributed to added onto the formed HDCFs coatings and evenly distributed. The Si
the fact that the addition of castor oil caused the higher molecular content of the coating material reduced gradually with the increase of
weight, more compact structure and more crosslinking points of the castor oil content, which is due to the more compact and stable network
formed polyurethane [47,48], which are in good agreement with SEM structure of the formed HDCFs coating by the increasing densification
images (Fig. 3A1–D2). Meanwhile, the residual amount of HDCF0, modification agent content.
HDCF30, HDCF60 and HDCF90 were 23.41 %, 16.23 %, 10.59 % and To confirm the water absorption abilities of the HDCF0, HDCF30,
6.84 % respectively, indicating that castor oil could also improve the HDCF60 and HDCF90, the WARs were measured by weighing in the
thermal degradation performance of the HDCFs films. 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
3.2. Hydrophobicity of the Formed HDCFs coatings 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
The surface morphology of the HDCFs coatings (HDCF0, HDCF30, 0.66 %, respectively. This means the WARs of the formed HDCFs coat­
HDCF60 and HDCF90) were observed by scanning electron microscopy. ings decrease greatly with the increasing castor oil content. The
The surface of the formed HDCFs coatings is smooth and flat with no hydroscopicity of membrane material is highly correlated with its hy­
notches or cracks (Fig. 2A1–D2), which proves the good film-forming drophobicity. The water absorption abilities of the formed HDCFs
property and becomes smoother with the increasing castor oil content. coatings were consistent with the hydrophobicity from the WCAs results
The WCAs were also measured to study the hydrophobicity of HDCF0, (Fig. 2A2–D2). In addition, the WARs of HDCF0 and HDCF30 increased
HDCF30, HDCF60 and HDCF90, respectively (Fig. 2A2–D2). The WCAs of sharply at 12 h, reaching 91.77 % and 38.26 %, respectively. These re­
the above formed HDCFs coatings were all greater than 90◦ (92.8◦ , sults clearly indicate that the addition of the castor oil can reduce the
101.0◦ , 108.4◦ and 138.3◦ ). It should be noted that the amount of hygroscopicity of coating materials, which is a supporting explanation
siloxane added is the same (10 %), but the contact angles are growing for the results of the nutrient release rate of the HDCFs.
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.

5
J. Liu et al. Journal of Environmental Chemical Engineering 11 (2023) 110591

3.3. Compactness of the formed HDCFs coating 3.4. Elasticity of the formed HDCFs coating

The effects of castor oil content on the microstructure of the HDCFs We also used AFM ScanAsyst-HR and PeakForce QNM imaging
coatings (HDCF0, HDCF30, HDCF60 and HDCF90) were observed by modes to study the micromechanics and microstructure of the HDCFs,
scanning electron microscopy (Fig. 3). For the fracture surfaces of the and further analyzed the effect of castor oil on the micromechanical
HDCFs coatings, more compact microstructure can be observed obvi­ properties of HDCFs (Fig. 5). The root mean square roughness of HDCF0,
ously. Significantly reduced micropores can be observed with the HDCF30, HDCF60 and HDCF90 was 39.2, 13.0, 13.0 and 7.77 nm
increased content of castor oil. The fracture surface of the HDCF90 is respectively, and the mean of Young’s modulus was 5025.52, 3175.72,
obviously smooth and flat with minimal micropores (Fig. 3D1 and D2). 2195.23 and 1325.68 MPa, respectively. With the increase of castor oil,
Furthermore, the porosities in the fracture surfaces of HDCF0, HDCF30 both the roughness and elastic modulus of HDCFs showed a decreasing
and HDCF60 were 11.27 %, 2.95 % and 2.57 % respectively, while the trend, which was also evident in the 3D color height image
porosity of HDCF90 was only 0.79 % at a magnification of 20,000 times (Fig. 5A1–D2). The rough bumps on the surface of the coatings may be
(Fig. 3A3–D3). The existence of micropores will make it more quickly caused by binding, voids or stacking generated during the synthesis of
when water into and nutrient out the HDCFs coating because of the fact bio-based polyurethane, which will make the coatings with abundant
that the numbers of micropores can observably affect the controlled micropore and the rapid nutrient loss. Fortunately, the addition of castor
release performance. Therefore, the increased content of castor oil oil reorganized the original structure of polyurethane and made the
would reduce the micropores and make the structure compacter and coatings homogeneous and compact, which was consistent with the
smoother, hence enhancing the performance of HDCFs. results of SEM topography (Fig. 3). Young’s modulus reflects the elas­
In order to reflect the micropore state of the coatings more intui­ ticity to some extent. The larger Young’s modulus will cause the smaller
tively, the 3D reconstruction images and local micropore distribution the elastic modulus. Compared with the HDCF0, the Young’s modulus of
scanning of HDCF0 and HDCF90 were conducted (Fig. 4). At the same HDCF90 reduced by 73.62 %. In addition, the regional distribution of
scale, the pores density of HDCF0 is obviously much larger than that of roughness and Young’s modulus of the HDCF0, HDCF30, HDCF60 and
HDCF90 (Fig. 4A1–A4), which proved that the addition of castor oil HDCF90 showed the inhomogeneity of the bio-based coatings
reduced the micropores of the coatings. The difference of the pore ratio (Fig. 5A4–D4). These results indicate that castor oil can significantly
was also obvious in three-dimensional local pore distribution model. improve the uniformity and elasticity of the coatings and the high
The porosity of HDCF0 is 5.76 % (Fig. 4A1–A2), 1.11 % (Fig. 4B1–B2) and elasticity bio-polyurethane-coating fertilizers was successfully prepared.
2.98 % (Fig. 4B3–B4) respectively, significantly higher than that of The adhesion of HDCF30 was 156.90 nN and the HDCF0, HDCF60 and
HDCF90 by 1.08 % (Fig. 4A3–A4), 0.76 % (Fig. 4C1–C2) and 0.75 % HDCF90 was 120.58, 84.57 and 68.29 nN respectively (Fig. 5A3–D3),
(Fig. 4C3–C4), and the pore volume of HDCF0 is also larger than that of indicating that the low concentration of castor oil will increase the
HDCF90. Clearly, the significant reduction in the number and volume of adhesion of the film, but large amount of castor oil can greatly reduce
HDCF90 micropores can be attributed to the addition of castor oil, which the adhesion. For the HDCF90, the low roughness ensured the uniformity
participated in the formation of the bio-based coating and clogged the of the coating and reduced the micropores, and the high elasticity made
HDCF0 micropores. the film material had good ductility, which made it difficult to be

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

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 siloxane content. Interestingly, the trend was reversed with the more
surface. These factors together resulted in the excellent controlled castor oil addition. For HDCFs with 60:40 and 90:10 of the proportion of
release performance of the HDCF90. the castor oil and LPAC, the nutrient controlled release longevity was
extended in a cliff-like manner. However, with the increase of siloxane,
3.5. Nutrient controlled-release abilities of the HDCFs 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
To study the effects of the different castor oil content and the polyols exhibits the best performance effect (120.45 d). This may be due
siloxane content on the nutrient release characteristics of the HDCFs, the to the fact that the high content of castor oil is able to form a dense
nutrient release longevity of the HDCFs with increasing coating mate­ encapsulated coating with the liquefied products, while the addition of
rials content (2.5 %, 3 %, 3.5 %, 4 % and 4.5 %) were measured by siloxane disrupts the dense nature of the coating. The specific values of
immersing at 25 ◦ C static water (Fig. 6A1–D4). For the HDCFs with 0:100 the nutrient release longevities of the HDCFs are shown in Supporting
of the proportion of the castor oil and LPAC, the nutrient had been information (Table S3). Results showed that the increasing castor oil
dissolved in only 2 h, regardless of the siloxane content and coating content can greatly enhance the nutrient release longevities, and the
contents. (Fig. 6A1–A4). For HDCFs with 30:70 of the proportion of the curve of nutrient release rate changed from inverted L to S shape. The
castor oil and LPAC, the controlled release longevity was extended. longer nutrient release longevity can be observed with the increased
When the coating content was 4.5 %, the release longevity of HDCFs coating materials content. What’s more, in the case of the low concen­
with 0 %, 1 %, 5 % and 10 % of the siloxane of the total polyols were tration of the castor oil, the addition of the siloxane can improve the
0.65, 0.72, 1.22, and 1.22 d, respectively (Fig. 6B1–B4). It could be seen controlled release performance, while in the case of the high concen­
that the controlled release longevity increased with the increase of tration of the castor oil, the addition of the siloxane will destroy the

7
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 the SEM images) (Fig. 3A2–D2). Therefore, the prolonged the nitrogen
performance. release longevity and significantly reduced the initial nitrogen release
The initial nitrogen release rate is also an important index to char­ rate can be obtained.
acterize coating quality, which can indicate the nitrogen release char­ Response surface methodology was employed to describe the re­
acteristics in the initial 24 h soaking in 25 ◦ C water. The HDCFs with lations of the castor oil content and the coating materials content of the
0:100 and 30:70 of the proportion of the castor oil and LPAC released HDCFs on the initial nitrogen release rate (Fig. S4) and the nitrogen
completely in 24 h without controlled release effect. For HDCFs with release longevity (Fig. 7). According to the response value, the three-
60:40 and 90:10 of the proportion of the castor oil and LPAC, the initial dimensional model containing different siloxane content (0 %, 1 %,
release rates were quiet low (0.39–6.23 %) regardless of siloxane con­ 5 %, 10 %) can be written as:
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 z1 = 51.91 − 0.05x − 45.31y + 0.03xy − 0.01x2 + 12.85y2
(90:10 of the proportion of the castor oil and LPAC, 5 % silicone and + 0.01x2y − 0.05xy2 − 1.17y3 (1)
4.5 % coating content) has an initial release longevity of 0.83 %. The z2 = 110.31 − 0.91x − 93.50y + 0.47xy + 25.90y2 − 0.09xy2 − 2.33y3 (2)
specific values of initial release rate are shown in Supporting informa­
tion (Table S3). Worth mentioned was that the HDCFs with 60:40 and z3 = 27.07 + 1.99x − 34.83y − 1.05xy − 0.01x2 + 13.18y2
90:10 of the proportion of the castor oil and LPAC reduced the initial + 0.01x2y + 0.10xy2 − 1.50y3 (3)
release rate and enhanced the controlled release longevity significantly.
z4 = 63.21 − 0.83x − 55.15y + 0.28xy + 15.92y2 − 0.05xy2 − 1.50y3 (4)
The addition of castor oil increased the cross-linking degree, which
made the coatings more compact with lesser micropores (consistent with 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 accurately predicted by regulating and controlling the castor oil content
correspond to nutrient release longevities of different siloxane content of and the coating materials content according to the three-dimensional
HDCFs. For HDCFs with siloxane content of 0 %, 1 % and 5 % of the total model. This precise controlled release model will also be benefit for
polyols, the trend of the corresponding surface is similar to that of the development of the HDCFs for the corps with long-lasting nutrient
HDCFs with siloxane content of 10 % of the total polyols, which again requirements in specific period, which will release nutrients in large
shows that siloxane has little influence on the controlled release per­ quantities in that specific period by adjusting castor oil addition amount
formance. The castor oil is a major influence on release longevities, as and coating materials contents.
evidenced by the steep curve from the 3D model. Furthermore, the
initial nitrogen release rate and the nitrogen release longevity can be

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. Journal of Environmental Chemical Engineering 11 (2023) 110591

3.6. Nutrient controlled release mechanism of the HDCFs 3.7. Oilseed rape applications of the HDCFs

How can the hydrophobic-densified double-modification of the To evaluate the applied effects of the HDCFs, the HDCF60 with 3 %
HDCFs coating significantly enhance the controlled-release longevity? coating materials content (controlled-release longevity: 25.98 days,
For the coating only with hydrophobic modification, there are numerous abbreviated as CN-30) and HDCF90 with 2.5 % coating materials content
micropores with large micropore diameter in the coating (Fig. 3 and (controlled-release longevity: 60.48 days, abbreviated as CN-60) were
Fig. 4). Despite the hydrophobic layer on the surface of the micropores, selected to carried out the potted oilseed rape experiment. The N release
water can still enter into the micropores of the coating and contacted the longevities in soil were carried out simultaneously with the oilseed rape
fertilizer core with liquid state directly when immersed into water, pot experiment (Fig. 9C). When oilseed rape was sown and fertilized, the
which caused the rapid release of nutrients (Fig. 8). As a contrast, for the HDCFs were buried in the pot soil (− 10 cm) at the same time. For the
coating with hydrophobic-densified double-modification, the minimal CN-30, the nitrogen release longevity with 80 % nitrogen release rate
micropores with minute micropore diameter and hydrophobic layer in was 24.75 days. The staged nitrogen release rates for 7, 14 and 21th day
the HDCFs coating can be observed. When immersed into water, water were 20.90 %, 63.58 % and 75.85 % respectively. The relatively quick
can not entirely enter into and soak the micropores of the HDCFs coating release within the 21 days can provide the sufficient nitrogen for seed­
with liquid state. There will be atmosphere column within the micro­ ling stage and thus lack of the nitrogen supply in the subsequent stage.
pores of the HDCFs coatings, function just like the atmosphere “stopper”, For the CN-60, the slower release rate at the initial 14 days (11.92 %)
which can prevent the entrance of the liquid water. The atmosphere and the faster release rate at the subsequent 14–38 days (62.48 %) can
“stopper” in micropore only allows water vapor molecules (instead of be observed, which can provide the sufficient nitrogen supply for the
liquid) to enter the internal urea core of HDCFs (Fig. 8). Therefore, the seedling stage and the maximum nutrient requirement period for the
nutrient release speed can be significantly slow down by reducing water potted oilseed rape. Furthermore, compared with the nitrogen release
accumulation in the internal urea core with hydrophobic-densified longevities for CN-60 at 25 ◦ C static water, those of in soil showed faster
double-modification. nitrogen release rates in the initial stage and slower nitrogen release rate
It is widely believed that hydrophobic modification can effectively in the later stage (> 38 days). This can be attributed to the gradually
improve nutrient controlled release ability. However, in this work, we reduced temperature in the growing period of the potted oilseed rape
can conclude that the controlled release performance is also related to (Fig. S5).
the micropore sizes of the coatings. When the micropore is sufficiently To confirm the effect of the HDCFs on the yield indexes of the oilseed
large and ample, even after hydrophobic modification, the controlled rape, we obtained the fresh biomass of the above-ground oilseed rape at
release performance can be improved to a small extent. Only after seedling stage and harvest stage (yield) with different fertilization
densification modification, when the micropore size becomes very treatments (Fig. 9D). Treatments using HDCFs at seedling stage all had
small, water can only enter the coatings in the form of gaseous water significantly higher fresh biomass than N300 treatment. Compared with
molecules, and the nutrient controlled release performance can be the fresh biomass of the above-ground oilseed rape at harvest stage
greatly improved. (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

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

(71.75 %) vs. N300. This can be attributed to the timely and enough Supporting Information
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 Synthesis reaction and photos of LPAC and HDCFs; scheme of potted
trogen supply due to the premature release. The fresh biomass of the experiment of oilseed rape; the main components and proportions of
above-ground oilseed rape with HDCFs (CN300-30, CN240-30, CN300-60, LPAC measured by GC-MS; 25 ◦ C static water release rate data of the
CN240-60) increase significantly vs. N300, even the treatments with 80% HDCFs with different castor oil and siloxane addition levels: 24-h release
N application amount. Therefore, we can conclude that the just right rate and 80 % release period; water absorption of the HDCFs; the rela­
controlled-release longevity of the controlled-release fertilizer can effi­ tionship model between the N initial release rate with coating materials
ciently improve the oilseed rape yield. This can be also verified by the content and castor oil contents of the HDCFs; soil temperature with
picture of the oilseed rape with different treatment in the seedling stage − 10 cm depth in the growing period of the potted oilseed rape; detailed
and harvest stage (Fig. 9A,B). data of physiological indexes, quality indexes, nitrogen accumulation
Nitrogen utilization efficiencies of the oilseed rapes at the harvest and soil available nitrogen content of the potted oilseed rape; economic
stage were also calculated and analyzed to further evaluate the appli­ benefits of different treatments for the potted oilseed rape.
cation effect of the HDCFs (Fig. 9E). Similar with the yield trend of the
different fertilization treatments, the nitrogen utilization efficiency with CRediT authorship contribution statement
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 Jiahui Liu: Methodology, Writing – original draft. Yuechao Yang:
N300 (6.63 %), even the treatment with 80 % N application amount. Methodology, Project administration, Supervision. Wentao Wang:
More notably, the CN240-60 (22.21 %) showed the highest nitrogen Software. Dongdong Cheng: Methodology. Yuanyuan Yao: Investiga­
utilization efficiency. This is of great significance for the reducing fer­ tion, Formal analysis. Tianlin Shen: Investigation, Formal analysis.
tilizer waste and agricultural pollution and solving the agriculture-food Ting Zhang: Conceptualization, Data curation. Jinpeng Wu: Concep­
security crisis predicted by 2050. tualization, Data curation. Xinning Zhao: Conceptualization, Data
The physiological and quality indexes of oilseed rape with different curation. Jiazhuo Xie: Investigation, Visualization.
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 Declaration of Competing Interest
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 The authors declare that they have no known competing financial
crease due to the controlled release properties of HDCFs, which proved interests or personal relationships that could have appeared to influence
that the HDCFs are effective in reducing the soil nitrogen leaching, the work reported in this paper.
maintaining the soil fertility and promoting the sustainable develop­
ment of the soil environment. The market profit of oilseed rape also Data Availability
highlights the application value of HDCFs more intuitively. Results
showed that all the treatment with HDCFs showed the higher retained Data will be made available on request.
profits vs. N300, even the treatment with 80 % N application amount.
This will be benefit to improve the recognition degree from farmers to Acknowledgments
CRFs and promote the development, popularization and application.
The specific values of the above tests are in the Supporting information This research was funded by the National Natural Science Founda­
(Table S4–S6). tion of China (32002134); the Natural Science Foundation of Shandong
Province (ZR2020QC162); the Research Start-up Project of Shandong
4. Conclusions Agricultural University (72098); the China Postdoctoral Science Foun­
dation (294570); the Key Research and Development Program of
In this work, the hydrophobic-densified double-modified waste- Shandong Province (2021CXGC010810); the Open Research Fund from
carton-based polyurethane-coated controlled-release fertilizers were Kingenta (381332); Young and Innovative Talents Introduction and
developed. The significantly enhanced controlled-release longevity Education Program of Universities in Shandong Province.
(< 2 h to 120.45 days) can be attributed to the obviously reduced
micropore porosities (5.76–1.08 %), the improved hydrophobicity Appendix A. Supporting information
(92.8–138.3◦ ) and the decreased WARs (98.87–0.66 %). The nutrient
release models were established to fast predict the controlled-release Supplementary data associated with this article can be found in the
longevity by adjusting the influence factor. Furthermore, the enhanced online version at doi:10.1016/j.jece.2023.110591.
elasticity (5025.52–1325.68 MPa) of the HDCFs coatings also contrib­
uted to improve the controlled-release abilities. The controlled-release References
mechanism was also clarified: the atmosphere “stopper” in the
“smaller and less” micropores in HDCFs coating only allows water vapor [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
molecules (instead of liquid) slowly permeate into the internal urea core
(2019) 677–685, https://doi.org/10.1016/j.jclepro.2019.02.118.
and significantly enhance the controlled-release longevities. The [2] Q. Wu, Y. Wang, Y. Ding, W. Tao, S. Gao, Q. Li, W. Li, Z. Liu, G. Li, Effects of
dramatically increased oilseed rape yield (71.75 %) showed the efficient 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-
application effect of the HDCFs. All the results indicate that HDCF with
2.
90:10 of the proportion of the castor oil and LPAC and 5 % of the [3] S. Bi, V. Barinelli, M.J. Sobkowicz, Degradable controlled release fertilizer
siloxane of the total polyols exhibits the best performance effect. The composite prepared via extrusion: fabrication, characterization, and release
efficient strategy provided in this work to fabricate eco-friendly waste- 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,
cardboard based CRFs can reduce fertilizer consumption, increase crop A. Soottitantawat, L.H. Lee, S.Y. Tang, Controlled release fertilizers: a review on
yields and foster the end-user confidence in the low-cost and eco- coating materials and mechanism of release, Plants 10 (2) (2021) 238–262,
friendly biowaste-derived controlled-release fertilizers. 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.

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

[6] Y. Wang, Y. Lu, J. Yuan, G. He, Evaluating the risks of nitrogen fertilizer-related of water retention in soil, Mater. Sci. Eng. C 90 (2018) 333–340, https://doi.org/
grain production processes to ecosystem health in China, Resour. Conserv. Recycl. 10.1016/j.msec.2018.04.083.
177 (1–8) (2022), 105982, https://doi.org/10.1016/j.resconrec.2021.105982. [29] S. Zhang, Y. Yang, B. Gao, Y.C. Li, Z. Liu, Superhydrophobic controlled-release
[7] Y. Lyu, X. Yang, H. Pan, X. Zhang, H. Cao, S. Ulgiati, J. Wu, Y. Zhang, G. Wang, fertilizers coated with bio-based polymers with organosilicon and nano-silica
Y. Xiao, Impact of fertilization schemes with different ratios of urea to controlled modifications, J. Mater. Chem. A 5 (37) (2017) 19943–19953, https://doi.org/
release nitrogen fertilizer on environmental sustainability, nitrogen use efficiency 10.1039/c7ta06014a.
and economic benefit of rice production: a study case from Southwest China, [30] S. Liu, Q. Wu, X. Sun, Y. Yue, B. Tubana, R. Yang, H. Cheng, Novel alginate-
J. Clean. Prod. 293 (1–12) (2021), 126198, https://doi.org/10.1016/j. cellulose nanofiber-poly(vinyl alcohol) hydrogels for carrying and delivering
jclepro.2021.126198. nitrogen, phosphorus and potassium chemicals, Int. J. Biol. Macromol. 172 (2021)
[8] J. Guo, J. Fan, F. Zhang, S. Yan, J. Zheng, Y. Wu, J. Li, Y. Wang, X. Sun, X. Liu, 330–340, https://doi.org/10.1016/j.ijbiomac.2021.01.063.
Y. Xiang, Z. Li, Blending urea and slow-release nitrogen fertilizer increases dryland [31] Q. Wang, F. Dong, J. Dai, Q. Zhang, M. Jiang, Y. Xiong, Recycled-oil-based
maize yield and nitrogen use efficiency while mitigating ammonia volatilization, polyurethane modified with organic silicone for controllable release of coated
Sci. Total Environ. 790 (2021), 148058, https://doi.org/10.1016/j. fertilizer, Polymers 11 (3) (2019) 454–468, https://doi.org/10.3390/
scitotenv.2021.148058. polym11030454.
[9] J. Li, Y. Liu, J. Liu, X. Cui, T. Hou, D. Cheng, A novel synthetic slow release [32] Q. Wei, L. Zhang, J. Chen, Z. Tong, X. Zhou, L. Shao, Z. Wu, P. Zhan, F. Wang,
fertilizer with low energy production for efficient nutrient management, Sci. Total N. Liu, H. Lin, H. Dong, Solvent-free coating of crosslinked and hydrophobic lignin-
Environ. 831 (2022), 154844, https://doi.org/10.1016/j.scitotenv.2022.154844. based biocomposite for slow-release fertilizer, Polym. Test. 102 (2021), https://
[10] S. Fertahi, M. Ilsouk, Y. Zeroual, A. Oukarroum, A. Barakat, Recent trends in doi.org/10.1016/j.polymertesting.2021.107335.
organic coating based on biopolymers and biomass for controlled and slow release [33] H. Lu, C. Dun, H. Jariwala, R. Wang, P. Cui, H. Zhang, Q. Dai, S. Yang, H. Zhang,
fertilizers, J. Control. Release 330 (2021) 341–361, https://doi.org/10.1016/j. Improvement of bio-based polyurethane and its optimal application in controlled
jconrel.2020.12.026. release fertilizer, J. Control. Release 350 (2022) 748–760, https://doi.org/
[11] P. Vejan, T. Khadiran, R. Abdullah, N. Ahmad, Controlled release fertilizer: a 10.1016/j.jconrel.2022.08.039.
review on developments, applications and potential in agriculture, J. Control. [34] H. Tian, Z. Li, P. Lu, Y. Wang, C. Jia, H. Wang, Z. Liu, M. Zhang, Starch and castor
Release 339 (2021) 321–334, https://doi.org/10.1016/j.jconrel.2021.10.003. oil mutually modified, cross-linked polyurethane for improving the controlled
[12] L. Liu, T. Shen, Y. Yang, B. Gao, Y.C. Li, J. Xie, Y. Tang, S. Zhang, Z. Wang, J. Chen, release of urea, Carbohydr. Polym. 251 (2021), 117060, https://doi.org/10.1016/
Bio-based large tablet controlled-release urea: synthesis, characterization, and j.carbpol.2020.117060.
controlled-released mechanisms, J. Agric. Food Chem. 66 (43) (2018) [35] J. Xie, Y. Yang, B. Gao, Y. Wan, Y.C. Li, D. Cheng, T. Xiao, K. Li, Y. Fu, J. Xu,
11265–11272, https://doi.org/10.1021/acs.jafc.8b04042. Q. Zhao, Y. Zhang, Y. Tang, Y. Yao, Z. Wang, L. Liu, Magnetic-sensitive
[13] W. Wang, S. Yang, A. Zhang, Z. Yang, Synthesis of a slow-release fertilizer nanoparticle self-assembled superhydrophobic biopolymer-coated slow-release
composite derived from waste straw that improves water retention and agricultural fertilizer: fabrication, enhanced performance, and mechanism, ACS Nano 13 (3)
yield, Sci. Total Environ. 768 (2021), https://doi.org/10.1016/j. (2019) 3320–3333, https://doi.org/10.1021/acsnano.8b09197.
scitotenv.2021.144978. [36] H. Shi, D. Liang, H. Deng, F. Xie, Z. Chen, Y. Chen, Q. Lu, X. Liu, C. Zhang, Bio-
[14] J. Fu, C. Wang, X. Chen, Z. Huang, D. Chen, Classification research and types of based superhydrophobic polymer coatings for slow-release fertilizers via a UV-
slow controlled release fertilizers (SRFs) used – a review, Commun. Soil Sci. Plant curing encapsulation method, Ind. Crops Prod. 188 (2022), https://doi.org/
Anal. 49 (17) (2018) 2219–2230, https://doi.org/10.1080/ 10.1016/j.indcrop.2022.115580.
00103624.2018.1499757. [37] C. Wang, S. Song, Z. Yang, Y. Liu, Z. He, C. Zhou, L. Du, D. Sun, P. Li, Hydrophobic
[15] G. Li, B. Zhao, S. Dong, J. Zhang, P. Liu, W. Lu, Controlled-release urea combining modification of castor oil-based polyurethane coated fertilizer to improve the
with optimal irrigation improved grain yield, nitrogen uptake, and growth of controlled release of nutrient with polysiloxane and halloysite, Prog. Org. Coat.
maize, Agric. Water Manag. 227 (1–13) (2020), 105834, https://doi.org/10.1016/ 165 (2022), https://doi.org/10.1016/j.porgcoat.2022.106756.
j.agwat.2019.105834. [38] M. Sun, H. Guo, J. Zheng, Y. Wang, X. Liu, Q. Li, R. Wang, X. Jia, Hydrophobic
[16] A. Sarkar, D.R. Biswas, S.C. Datta, T. Roy, P.C. Moharana, S.S. Biswas, A. Ghosh, octadecylamine-polyphenol film coated slow released urea via one-step spraying
Polymer coated novel controlled release rock phosphate formulations for co-deposition, Polym. Test. 91 (1–8) (2020), 106831, https://doi.org/10.1016/j.
improving phosphorus use efficiency by wheat in an Inceptisol, Soil Tillage Res. polymertesting.2020.106831.
180 (2018) 48–62, https://doi.org/10.1016/j.still.2018.02.009. [39] X. Liu, Y. Yang, B. Gao, Y. Li, Y. Wan, Environmentally friendly slow-release urea
[17] J. Liao, X. Liu, A. Hu, H. Song, X. Chen, Z. Zhang, Effects of biochar-based fertilizers based on waste frying oil for sustained nutrient release, ACS Sustain.
controlled release nitrogen fertilizer on nitrogen-use efficiency of oilseed rape Chem. Eng. 5 (7) (2017) 6036–6045, https://doi.org/10.1021/
(Brassica napus L.), Sci. Rep. 10 (1) (2020) 1–14, https://doi.org/10.1038/s41598- acssuschemeng.7b00882.
020-67528-y (11063). [40] C. Jia, P. Lu, M. Zhang, Preparation and characterization of environmentally
[18] J. Li, Y. Liu, Y. Tang, J. Shao, T. Xu, R. Ma, Y. Jiang, D. Cheng, Optimizing fertilizer friendly controlled release fertilizers coated by leftovers-based polymer, Processes
management based on controlled-release fertilizer to improve yield, quality, and 8 (4) (2020) 417–431, https://doi.org/10.3390/pr8040417.
reduce fertilizer application on apples, J. Soil Sci. Plant Nutr. 22 (2022) 393–405, [41] Y. Wang, M. Sun, D. Qiao, J. Li, Y. Wang, W. Liu, C. Bunt, H. Liu, J. Liu, X. Yang,
https://doi.org/10.1007/s42729-021-00656-0. Graft copolymer of sodium carboxymethyl cellulose and polyether polyol (CMC-g-
[19] S. Sharma, V.S. Rana, R. Pawar, J. Lakra, V. Racchapannavar, Nanofertilizers for TMN-450) improves the crosslinking degree of polyurethane for coated fertilizers
sustainable fruit production: a review, Environ. Chem. Lett. 19 (2021) 1693–1714, with enhanced controlled release characteristics, Carbohydr. Polym. 272 (2021),
https://doi.org/10.1007/s10311-020-01125-3. 118483, https://doi.org/10.1016/j.carbpol.2021.118483.
[20] A.E. El-Karamity, N.R. Ahmed, A.N. Mohamed, Effect of intercropping of some oil [42] X. Ma, J. Chen, Y. Yang, X. Su, S. Zhang, B. Gao, Y.C. Li, Siloxane and polyether
summer crops with maize under levels of mineral N and nano N fertilizers, Sci. J. dual modification improves hydrophobicity and interpenetrating polymer network
Agric. Sci. 2 (2) (2020) 90–103, https://doi.org/10.21608/sjas.2020.42913.1038. of bio-polymer for coated fertilizers with enhanced slow release characteristics,
[21] H. Tian, Z. Liu, M. Zhang, Y. Guo, L. Zheng, Y.C. Li, Biobased polyurethane, epoxy Chem. Eng. J. 350 (2018) 1125–1134, https://doi.org/10.1016/j.cej.2018.06.061.
resin, and polyolefin wax composite coating for controlled-release fertilizer, ACS [43] J. Xie, Y. Yang, B. Gao, Y. Wan, Y.C. Li, J. Xu, Q. Zhao, Biomimetic
Appl. Mater. Interfaces 11 (5) (2019) 5380–5392, https://doi.org/10.1021/ superhydrophobic biobased polyurethane-coated fertilizer with atmosphere
acsami.8b16030. "outerwear", ACS Appl. Mater. Interfaces 9 (18) (2017) 15868–15879, https://doi.
[22] C. Wang, Z. Lü, J. Li, Z. Cao, B. Wei, H. Li, M. Shang, C. Su, Efficient use of waste org/10.1021/acsami.7b02244.
carton for power generation, tar and fertilizer through direct carbon solid oxide [44] S. Zhang, N. Gao, T. Shen, Y. Yang, B. Gao, Y.C. Li, Y. Wan, One-step synthesis of
fuel cell, Renew. Energy 158 (2020) 410–420, https://doi.org/10.1016/j. superhydrophobic and multifunctional nano copper-modified bio-polyurethane for
renene.2020.05.082. controlled-release fertilizers with “multilayer air shields”: new insight of
[23] F. Zambrano, R. Marquez, H. Jameel, R. Venditti, R. Gonzalez, Upcycling strategies improvement mechanism, J. Mater. Chem. A 7 (16) (2019) 9503–9509, https://
for old corrugated containerboard to attain high-performance tissue paper: a viable doi.org/10.1039/c9ta00632j.
answer to the packaging waste generation dilemma, Resour. Conserv. Recycl. 175 [45] Z. Yu, D. Cheng, B. Gao, Y. Yao, C. Liu, J. Li, C. Wang, J. Xie, S. Zhang, Z. Li,
(1–13) (2021), 105854, https://doi.org/10.1016/j.resconrec.2021.105854. Y. Yang, Bio-based polyurethane based on a dynamic covalent network with
[24] M.J. John, S. Thomas, Biofibres and biocomposites, Carbohydr. Polym. 71 (3) damage tolerance for controlled release of fertilizers, ACS Appl. Mater. Interfaces
(2008) 343–364, https://doi.org/10.1016/j.carbpol.2007.05.040. 14 (50) (2022) 56046–56055, https://doi.org/10.1021/acsami.2c14672.
[25] O. León, D. Soto, A. Antúnez, R. Fernández, J. González, C. Piña, A. Muñoz-Bonilla, [46] C. Wang, S. Song, Z. Yang, Y. Liu, Z. He, C. Zhou, L. Du, D. Sun, P. Li, Hydrophobic
M. Fernandez-García, Hydrogels based on oxidized starches from different modification of castor oil-based polyurethane coated fertilizer to improve the
botanical sources for release of fertilizers, Int. J. Biol. Macromol. 136 (2019) controlled release of nutrient with polysiloxane and halloysite, Prog. Org. Coat.
813–822, https://doi.org/10.1016/j.ijbiomac.2019.06.131. 165 (1–10) (2022), 106756, https://doi.org/10.1016/j.porgcoat.2022.106756.
[26] S. Sun, W. Wang, F. Liu, L. Zhang, X. Fan, Coating layer preparation with mixed [47] Y. Li, C. Jia, X. Zhang, Y. Jiang, M. Zhang, P. Lu, H. Chen, Synthesis and
vegetable oil and nutrient release regulation of fertilizer, Eur. Polym. J. 120 (1–6) performance of bio-based epoxy coated urea as controlled release fertilizer, Prog.
(2019), 109194, https://doi.org/10.1016/j.eurpolymj.2019.08.021. Org. Coat. 119 (2018) 50–56, https://doi.org/10.1016/j.porgcoat.2018.02.013.
[27] X. Peng, J. Ren, L. Zhong, F. Peng, R. Sun, Xylan-rich hemicelluloses-graft-acrylic [48] Y. Chen, W. Li, S. Zhang, A multifunctional eco-friendly fertilizer used keratin-
acid ionic hydrogels with rapid responses to pH, salt, and organic solvents, J. Agric. based superabsorbent as coatings for slow-release urea and remediation of
Food Chem. 59 (15) (2011) 8208–8215, https://doi.org/10.1021/jf201589y. contaminated soil, Prog. Org. Coat. 154 (1–11) (2021), 106158, https://doi.org/
[28] A. Olad, H. Zebhi, D. Salari, A. Mirmohseni, A.R. Tabar, Slow-release NPK fertilizer 10.1016/j.porgcoat.2021.106158.
encapsulated by carboxymethyl cellulose-based nanocomposite with the function

12