International Journal of Biological Macromolecules 231 (2023) 123334

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International Journal of Biological Macromolecules

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

Reduced nutrient release and greenhouse gas emissions of lignin-based

coated urea by synergy of carbon black and polysiloxane
Xiaojuan Chen, Tao Guo, Xiao Mo, Lidan Zhang, Rongfeng Wang, Yunna Xue, Xiaolin Fan,
Shaolong Sun *
College of Natural Resources and Environment, South China Agricultural University, Guangzhou, Guangdong 510642, China

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

Keywords: An advanced hydrophobic lignin-based polyurethane coated urea (HLPCU) was successfully developed by syn­
Synergy ergy of carbon black (CB) and polysiloxane. In this work, CB and polysiloxane were employed to modify the
Carbon black and polysiloxane liquefied lignin-based polyurethane (LLPU) and improve it's the hydrophobicity. The effects of polysiloxane
Lignin-based polyurethane
contents and coating rates on the nutrient release of HLPCU were thoroughly investigated. The lignin was
Coated urea
degraded into polyol with a low molecular weight. FT-IR, XPS and EDX results confirmed that polysiloxane was
grafted to the LLPU. The water contact angle (WCA) of the HLPUs (89.39◦ –98.68◦ ) gradually increased as the
polysiloxane content rose (5 %–15 %). However, when the polysiloxane content further increased to 20 %, the
WCA of the HLPUs rapidly declined (90.82◦ ). A proper amount of polysiloxane molecules could increase thermo-
physical properties of LLPU. The almost no pores were observed on the section micrograph of the HLPCU ob­
tained by synergy of CB and polysiloxane. Synergy between CB and polysiloxane could significantly improve
hydrophobicity and then enhance N release longevity of HLPCU (polysiloxane content of 15 %, coating rates of 7
%) up to 44 days. Compared to traditional urea, HLPCU could improve total N use efficiency the cabbage. The
HLPCU and HLPCU85 treatments (15 % weight loss with fertilization) reduced the greenhouse effect of N2O, CO2
and CH4 and finally reduced GWP, especially for HLPCU85 treatment. This work will supply an advanced
approach and process technology for progress of HLPCU and sustainable agriculture.

1. Introduction
A common practical problem in agriculture is that the effective uti­
lization availability of chemical fertilizers is generally low. It not only
wastes fertilizer resources, but also causes environmental pollution.
Therefore, in agricultural production, the improvement of fertilizer
utilization rate has become an urgent problem to be solved, especially
the improvement of nitrogen fertilizer (N) utilization rate [1]. In fact,
the main ways of chemical fertilizers loss include NH3 volatilization,
nitrate leaching and gas emission, such as N2O, NO and N2 [2]. N2O is
mainly generated during nitrification and denitrification in soil, which
has a direct influence on the greenhouse gas emissions due to its rela­
tively higher global warming potential. For fertilizer transformation,
coated fertilizers (CFs) are ideal strategy to address these issues. The
research and application of CFs is considered as a way to reduce envi­
ronmental harm and improve nutrient utilization efficiency [3]. CFs is
composed of coated materials (CMs) and core fertilizers, and CMs
mainly comes from organic polymer materials (OPMs) (e.g. resins) and
inorganic materials (e.g. sulfur). Currently, compared with many inor­
ganic materials, OPM is used with good sustained-release performance,
such as polysulfone, polystyrene, etc. However, most OPM comes from
petroleum, which limits its large-scale development and application.
Thus, it is important particularly to prepare degradable and cheap CM
with renewable resources as raw materials.
In recent years, researchers have mainly focused on developing bio-
based raw material to produce environmentally friendly and degradable
CFs, such as vegetable oil [4], chitosan [5–7], cellulose [8], and starch
[9]. However, most of bio-based raw material is expensive and hydro­
philic, which greatly limits their practical applications. In fact, lignin, as
a cheap natural macromolecular compound, is mainly produced in pulp
and biomass refining industry [10]. In addition, lignin has many
branches and complex molecular structure with various functional
groups [11]. These functional groups (e.g., hydroxyl groups) can
directly affect the reactivity of lignin. Therefore, lignin has a good

* Corresponding author.
E-mail address: sunshaolong328@scau.edu.cn (S. Sun).

https://doi.org/10.1016/j.ijbiomac.2023.123334
Received 6 December 2022; Received in revised form 7 January 2023; Accepted 15 January 2023
Available online 20 January 2023
0141-8130/© 2023 Elsevier B.V. All rights reserved.
X. Chen et al.
potential to develop CFs because of its special chemical properties and
extensive sources. Currently, non-modification lignins were mixed with
other components (e.g., ethylcellulose, alkenyl succinic anhy-dride,
rosin) to obtain CFs, and about 80 % of the nutrients was released for
the Controlled release ureas (CRUs) [12–14]. Most CRUs emerged a poor
sustained-release property by using the non-modification lignin as
coated material. In addition, the coating hydrophobicity could be
enhanced by modifications, thereby improving the hydrophobicity of
coating and then sustained slow-release property of CFs [15–17].
Therefore, the research and development of lignin-based coated fertil­
izer needs to further improve its nutrient utilization efficiency and
reduce the production cost, thus helping to improve its large-scale
application.
Lignin and its derivatives can be used as polyols to form lignin-based
polyurethanes (LPUs) due to the abundant hydroxyl groups in their
molecular structures [18]. To enhance the compatibility and reactivity
between lignin and polyurethane matrices, various chemical methods
were applied to lignin modification, such as etherification [19], esteri­
fication [20] and liquefaction processes [21,22]. Among them,
compared to pyrolysis or gasification treatment, liquefaction is usually
carried out under relatively mild situations. Liquefaction is an efficient
and convenient method to convert lignocellulosic component into small
molecular compounds that can be applied in biochemical products [23].
Lignin can be liquefied into biopolyols and subsequently synthesized
into LPU, which is used as a coating for CFs. Nevertheless, the nutrient
release properties of LPU-based coated fertilizers (LPCFs) are unsatis­
factory. The main reason for this phenomenon is that there are many
micropores in the coating shell and hydrophilic groups in chemical
constitution, resulting in a short nutrient release life of LPCFs.
To surmount the shortcomings of lignin-based CMs, hydrophobic
groups were grafted onto or mixed with hydrophobic and thermally
stable additives to elevate the quality of CFs [24–27]. Particularly,
compared with fluorinated materials, silicones and nanoparticles with
less environmental impact were applied in super-hydrophobic coatings,
super-hydrophobic cotton fabrics, and oil/water separation [28,29]. A
bio-mimetic super-hydrophobic bio-based polyurethane (BPU) CFs was
obtained by enhancing surface roughness with micrometer-nanoscale
diatomite-SiO2 structure and reducing surface energy with grafting
with fluoroalkylsilanes of PU coating. The total release rate of CFs pre­
pared was 80 % after 66.3 days [30]. A novel BPU was also developed by
using liquefied cotton straw and obtained CFs with excellent nutrient
release performance. The BPU was further modified by using siloxane
and polyether to enhance the hydrophobicity and lower the micropore
size. The total release rate after 38 days was 80 % by hydro-static release
test [31]. Moreover, the decomposition of silicone in the soil produces
elemental silicon, which promotes crop growth. However, the slow-
release properties of CFs developed by bio-based polymer coatings are
limited and need to be further improved. Therefore, it is crucial to
develop novel eco-friendly lignin-based CMs with super-hydrophobic
surfaces, which facilitate the synchronization of nutrient release from
CF and crop nutrient demand.
In the present study, a novel hydrophobic lignin-based polyurethane
coated urea (HLPCU) was successfully developed by synergy of carbon
black (CB) and polysiloxane. Lignin was first liquefied to obtain lignin
polyols, which were then used to produce liquefied lignin-based poly­
urethane (LLPU). Subsequently, the LLPU was further modified by
synergy of carbon black and polysiloxane to enhance the hydrophobicity
and lower the micropore size. The effects of polysiloxane contents and
coating rates on the nutrient release of HLPCU were investigated thor­
oughly. The physicochemical characteristics of CMs and HLPCU were
also systematically assessed. The application of HLPCU in crop pro­
duction, nitrogen use efficiency and greenhouse gas benefit were further
evaluated by pot experiments. This work will supply an advanced
approach and process technology for progress of HLPCU and sustainable
agriculture.
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International Journal of Biological Macromolecules 231 (2023) 123334
2. Materials and methods
2.1. Materials
Alkali lignin with hydroxyl contents 4.2 mmol/g based on 31P NMR
spectroscopy (AL) was collected by Shandong Xinglong Paper (Group)
Co., Ltd. Urea (46.4 % N) was obtained from Luxi Chemical Group Co.,
Ltd. Polymethylene polyphenylene isocyanate (PAPI, 31 wt% NCO) and
carbon black (CB) were purchased from the Xuzhou Yang New Materials
Co., Ltd. Poly(ε-capro-lactone) diol (PCLD, hydroxyl value 200 mg
KOH⋅g− 1, average Mn-530) was obtained from Shanghai Xushuo Bio­
logical Technology Co., Ltd. Anhydrous pyridine, Deuterated chloro­
form (99.8 %), Phthalic anhydride (99.7 %), Tin 2-ethylhexanoate (95
%, wt%) and hydroxyl terminated polydimethylsiloxane as the poly­
siloxane were provided Shanghai Macklin Biochemical Co., Ltd. Cyclo­
hexanol, Polyethylene glycol (PEG, hydroxyl value 290 mg KOH⋅g− 1,
average Mn-400, 99 %), glycerol (99 %), and sulfuric acid (H2SO4: 98 %,
v/v) were supplied from Tianjin Damao Chemical Reagent Factory Co.,
Ltd.
2.2. Preparation, yield and hydroxyl number and of liquefied lignin
The specific solution (SS) was prepared by mixing PEG400 (150.0 g),
PCLD (75.0 g), glycerol (56.25 g) and H2SO4 (7.5 g) in a round-bottomed
flask of 1000 mL outfitted with a flux condenser under motor-driven
stirrer condition. After 15 min, the SS was first preheated to 140 ◦ C
and then was turned on by the reflux condenser. The agitator driven by
the motor was controlled in 300 rpm. Subsequently, the lignin (112.5 g)
was poured into the SS and reacted for 50 min. After the reaction, the
liquefied lignin (LL) was obtained from the kettle for analysis and used
as one of the lignin-based material (Fig. 1a). In summary, the yield (98.5
%) of LL was obtained under the above methods.
2.3. Characterization of AL and LL
To analyze the hydroxyl content of AL, 31P NMR spectra of AL was
performed as previously reported. 20 mg ALs were dissolved in 0.5 mL of
anhydrous pyridine and deuterated chloroform (1.6:1, v/v) under stir­
ring. This was followed by the addition of 0.1 mL cyclohexanol (10.85
mg/mL in anhydrous pyridine and deuterated chloroform 1.6:1, v/v) as
an internal standard, and 0.1 mL chromium acetylacetonate solution (5
mg/mL in anhydrous pyridine and deuterated chloroform 1.6:1, v/v) as
relaxation reagent. Finally, the mixture were reacted with 0.1 mL
phosphorylating reagent 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphos­
pholate was transferred into a 5 mm NMR tube for analysis [32].
The LL was filtered while acetone was constantly added under vac­
uum. The aim was to facilitate the filtration process and to drag the
liquefied product. The remained solid fraction was oven dried at 105 ◦ C
for 24 h. Acetone was removed at 49 ◦ C by rotary evaporator under
reduced pressure. All liquefaction experiments were performed in
duplicate. The yield of liquefaction reaction was calculated as follows:
Yield = (1 − m/m0 ) × 100
where: Yield = yield % of LL; m0 = amount of lignin used in liquefaction
(g); m = solid residue of liquefaction (g).
The hydroxyl value (OHn) of LL was determined according to stan­
dard ASTM D4274 (2005). 0.5–1.0 g sample was dissolved in 25 mL of
phthalate reagent (115 g of phthalic anhydride dissolved in 700 mL of
pyridine), under reflux for 1 h at 115 ◦ C. Then 50 mL of pyridine was
added through the condenser. The mixture was titrated with 2 N sodium
hydroxide solution (NaOH) using a pH meter.
The hydroxyl value is defined as the amount of KOH in milligram
equivalent to the OH content in 1 g of liquefied product (mg KOH⋅g− 1).
The hydroxyl value of liquefaction reaction was calculated as fol­
lows:
X. Chen et al.
Fig. 1. Schematic diagram of the fabrication process of LL (a), LLPU (b) and HLPUs (c). FT-IR spectra of AL, LL (d), LLPU, CLPU and HLPUs (e).
OHn = ((B − A) × M × 56.1 )/W + An
where: OHn = hydroxyl value (mg KOH⋅g− 1); A = volume of the 2 N.
NaOH solution to titrate the sample (mL); B = volume of the 2 N
NaOH solution to titrate the blank (mL); M = molarity of 2 M NaOH
solution; 56.1 = molecular weight of KOH; W = amount of sample (g);
An = acid number KOH⋅g− 1.
The molecular weight distribution and composition of LL were
assessed using a Shimadzu-LC20/RID-20 Gel Permeation Chromato­
graph (GPC). FT-IR spectra of the AL, and LL were recorded on a Bruker
spectrophotometer (VERTEX 70, Germany) with a resolution of 4000
cm− 1. A KBr disk containing 0.1 % finely ground ALs was used for
determination. An average of 16 scans ranging from 400 cm− 1 to 4000
cm− 1 was applied.
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International Journal of Biological Macromolecules 231 (2023) 123334
2.4. Preparation of the LPCU, CLPCU and HLPCU
The liquefied lignin-based polyurethane (LLPU) coated urea (LPCU)
was produced by coating urea with the consisting of LL and PAPI
(Fig. 1b). Specifically, the granular fertilizer (3–5 mm, 500 g) was
moved into a rotating drum and then pretreated at 75 ◦ C for 10 min.
After preheating, a thick liquid mixture (TLM) was prepared by stirring
together 5 g of LLPU and PAPI with a-CNO/-OH molar ratio of 1.15:1.00
for 1 min. Finally, the TLM was poured slowly into the rolling particle at
300 rpm. It was then cured at 75 ◦ C for 6 min to form coated urea after
spraying the TLM evenly on the surface of the urea. Among, the weight
of CMs was about 1 % of the weight of urea. Based on different coating
rates (3, 5 and 7 wt% of urea), three LPCUs were finally obtained
through the above steps, which were namely LPCU-3, LPCU-5 and LPCU-
7, respectively. The same process was applied in coat urea by using CB
X. Chen et al.
and LLPU. LL (19.3 g) and CB (0.7 g) were mixed at 70 ◦ C for 15 min by
magnetic stirring to obtain a CB/LL mixture (CLM). The mixture of CLM
(2.3 g) and PAPI (2.7 g) were poured slowly into granular fertilizer at
300 rpm for 5 min. After spraying the mixed coating evenly on the
surface of granular fertilizer, it was then cured at 75 ◦ C for 5 min to
obtain single-layer CB/LLPU (CLPU) coated urea (CLPCU). Similarly,
based on different coating rates (3, 5 and 7 wt% of urea), three CLPCUs
were namely CLPCU-3, CLPCU-5 and CLPCU-7, respectively. In addi­
tion, the hydrophobic LLPU (HLPU, Fig. 1c) coated urea (HLPCU) were
acquired by adopting the mixture of PAPI, LL, CB and polysiloxane.
Specifically, CB, LL, and polysiloxane were mixed at 70 ◦ C for 15 min by
magnetic stirring to obtain a CB/LL/polysiloxane mixture (CLPM). The
CLPM and PAPI (5 g) were dropped onto the surface of the rotating
granular fertilizer. Based on the same approach, different HLPCUs were
produced by varying the polysiloxane content (polysiloxane/LL: 5, 10,
15, and 20 wt%) and coating rates (3, 5, and 7 wt% of urea), respec­
tively. Among them, the HLPUs of different polysiloxane content termed
HLPU5, HLPU10, HLPU15 and HLPU20, respectively. Meanwhile, the
HLPCUs were namely HLPCU5-3, HLPCU5-5, HLPCU5-7, HLPCU10-3,
HLPCU10-5, HLPCU10-7, HLPCU15-3, HLPCU15-5, HLPCU15-7,
HLPCU20-3, HLPCU20-5, and HLPCU20-7, respectively.
2.5. Characterization of LLPU, CLPU and HLPUs
FT-IR spectra of the LLPU, CLPU and HLPUs were recorded on a
Bruker spectrophotometer (VERTEX 70, Germany) with a resolution of
4000 cm− 1. The surface elemental compositions and distribution of
coating materials were measured by an Escalab 250Xi X-ray photo­
electron spectrometer (XPS, Thermo Scientific K-Alpha, USA) and an
energy dispersive X-ray (EDX) spectroscopy detector attached to the
SEM (EVO10, Carl Zeiss, Germany). Dynamic mechanical analysis
(DMA) was performed using a Netzsch DMA 242C DMA analyzer to
evaluate the thermo-mechanical properties and the cross-linking degree
of the LLPU, CLPU and HLPUs. The size of the rectangular specimens
used for DMA was 20.0 mm × 6.0 mm × 0.5 mm (length × width ×
thickness). The experiment was conducted as follows: isothermal at 5 ◦ C
for 3 min, and then heating to 125 ◦ C at a heat rate of 5 ◦ C min− 1 with a
film tension mode and frequency of 1 Hz. Water contact angle (WCA) of
the LLPU, CLPU and HLPUs were performed by sessile-drop method
using the contact angle goniometer (JC2000C1, Biolin Scientific,
Finland) under room temperature and statistical analysis were repeated
three times for averaging. Water absorption (WA) of the LLPU, CLPU,
and HLPUs were weighed (M0) and immersed in 300 mL of distilled
water at room temperature (25 ◦ C). After 24 h, the LLPU, CLPU and
HLPUs was taken out, and the excess water on the surface was removed
with paper. Then record the weight of the LLPU, CLPU and HLPUs (M1).
The WA of the LLPU, CLPU and HLPUs were calculated with the formula
WA = (M1/M0–1) × 100 %, where M1 is the final weight of the LLPU,
CLPU and HLPUs after WA, and M0 is the initial weight of the LLPU,
CLPU and HLPUs.
2.6. Nutrient release characteristics of LPCU, CLPCU and HLPCU
The nutrient release performance of the LPCU, CLPCU and HLPCUs
were measured at room temperature in water. Specifically, a 10.0 g
LPCU, CLPCU and HLPCU were placed into plastic bottle (250 mL)
containing distilled water (200 mL). The N release rate of LPCU, CLPCU
and HLPCU were evaluated after 1, 3, 5, 7, 14, 28, 35, 42 and 49 days
based on data of the N concentration [33]. The cumulative nutrient
release of LPCU, CLPCU and HLPCU after 24 h immersion (i.e., the initial
release percentage) was also assessed. The morphologies of LPCU,
CLPCU, and HLPCUs were also recorded by scanning electron micro­
scopy (SEM) (EVO10, Carl Zeiss, Germany). To evaluate the sections of
LPCU, CLPCU and HLPCUs, the samples were cut in half and then coated
with gold layer for SEM analysis. The optimal HLPCU was weighed and
placed in a nylon mesh bag with the same specification (10 cm × 3 cm,
4
International Journal of Biological Macromolecules 231 (2023) 123334
100 mesh), and then buried in a 10 cm deep soil layer. The test lasted for
180 days and the relative humidity was fixed at 65 %. The clean and
dried CMs was obtained from HLPCUs every 2 months by removing
residues using tap water and water using oven at 80 ◦ C. The degradation
rate of CMs in the HLPCUs indicated the biodegradability in soil burial
test. The degradation rate was investigated based on the equation: N =
(M0-Mt)/M0 × 100 %, where M0 is the quality of HLPCUs at the initial
stage and Mt is the weight of HLPCUs on day.
2.7. Plant materials and experimental design
Based on the optimal nutrient release result, the effect of HLPCU on
plant growth was evaluated by using the cabbage (seeds were purchased
from Shouhe co., ltd.) in the test station of university. To evaluate the
effects of HLPCU on cabbage growth, N use efficiency, and greenhouse
gas emissions from the soil, simulation experiments were set up. Pot
experiment (3.5 kg of soil) was conducted from November 9, 2021 to
January 9, 2022 in greenhouse (the relative humidity and average
temperature in the greenhouse were 56 % and 20 ◦ C, respectively). The
physicochemical properties of soil were as follows: organic matter 6.80
g⋅kg− 1, pH 6.45, available N 59.00 mg⋅kg− 1, available P 19.61 mg⋅kg− 1,
available K 77.46 mg⋅kg− 1. Four treatments were set by a single factor
random block design and named without N (CK), blank control with
traditional urea (TU, 0.32 g N⋅kg− 1 soil), and test with HLPCU (poly­
siloxane content of 15 %, 100 % fertilization) and HLPCU85 (15 %
weight loss with fertilization) as N fertilizer. The nitrogen application
rate of each treatment was the same, and it was repeated 5 times. P and K
fertilizers were added in the form of superphosphate (0.25 g P2O5⋅kg− 1
soil) and potassium chloride (0.25 g K2O⋅kg− 1 soil) as basal application
to ensure that the same N, P and K content in all of treatments.
At the beginning of the experiment, the moisture content in soil was
kept in 60 % of the soil moisture holding capacity. The N2O, CO2 and
CH4 were obtained from the sealed static box (height 70 cm × diameter
40 cm). The amount of N2O, CO2 and CH4 released at the given treat­
ment conditions was detected. The N2O, CO2 and CH4 emissions were
measured on 1, 3, 5, 10, 15, 20, 30, 40, 50 and 60 days by manually
collecting 100 mL air samples at 5, 10, and 15 min using a highly gas-
tight foil collection bag (100 mL, Beekman Bio, China) through the
septum.
Calculation of N2O (CO2 and CH4) emission flux [34]:
F = ρ × H × (dc/dt) × 273/(273 + T) × 60
where F is N2O (CO2 and CH4) emission flux(mg− 1⋅m− 1⋅h− 1), ρ is the gas
density under standard conditions, H (m) represents the height of static
opaque chambers, dc/dt is the rate of gas accumulation inside the
chamber (μL⋅L− 1⋅min− 1), and T (◦ C) is the mean air temperature inside
the chamber.
The formula for calculating the cumulative amount of greenhouse
gas emissions:
/
∑n
C= (Fi+1 + Fi ) 2 × (ti+1 − ti ) × 24
i=1
where C is the cumulative emission of greenhouse gases, mg⋅N2O⋅m− 2,
mg⋅CO2⋅m− 2 or mg⋅CH4⋅m− 2; F is the emission flux of greenhouse gases,
mg⋅N2O⋅m− 2⋅h− 1, mg⋅CO2⋅m− 2⋅h− 1 or mg C⋅m− 2⋅h− 1; i is the first gas
collected; n is the total number of collections.
GWP was calculated based on a 100-year horizon as suggested by the
IPCC using the equation:
GWP = CH4 emissions × 28 + N2 O emissions × 298 + CO2 emissions
GHGI was used to express the GWP per unit grain yield, as described
in Shang et al. [35]:
GHGI = GWP/yield.
X. Chen et al.
To evaluate effective N content of soil, soil (2 g) was put into a plastic
bottle (250 mL) containing 0.01 mol⋅L− 1 CaCl2 solution (100 mL) and
then shaken at 250 rpm for 1 h. The NH+ 4 -N and NO3 -N were measured
−
using a flow analyzer (CFA, AMD France). Plant dry biomass was also
recorded via oven drying at 75 ◦ C after harvesting the plants. The cab­
bage plant height, stem thickness, SPAD value, above-ground dry
weight, subterranean dry weight, N uptake and N used efficiency were
also evaluated and calculated.
2.8. Statistical analysis
All statistical analyses were conducted and analyzed according to the
procedure depicted in a recent literature [36].
3. Results and discussion
3.1. Composition and general property of AL and LL as well as structural
analysis of the AL, LL, LLPU, CLPU, and HLPU
The GPC analysis of the AL and LL were assessed and the data were
listed in Table 1. The molecular number-average (Mn) weight of the AL
was 1487 g⋅mol− 1, the molecular weight-average (Mw) was 3693
g⋅mol− 1, and polydispersity coefficient (Mw/Mn) was 2.48 (Table 1).
The Mn (699 g⋅mol− 1), Mw (1119 g⋅mol− 1) and Mw/Mn (1.60) of the LL
obtained simultaneously decreased after the AL liquefaction progress.
This was mainly caused by the polyhydric alcohol solvent liquefying the
AL. During the liquefaction process, AL was degraded into smaller
molecules. In addition, the LL with hydroxyl value (343 mg KOH⋅g− 1)
easily reacted with isocyanate to obtain LLPU. In short, the Mw
confirmed that sample was degraded into polyol with a low molecular
weight and sufficient OH groups during the liquefaction process, which
facilitated the synthesis of polyurethane materials for the preparation of
CFs.
The FT-IR spectra of AL, LL, LLPU, CLPU and HLPU revealed that
chemical changes during lignin liquefaction and the syntheses process of
LLPU and HLPUs (Fig. 1). FT-IR spectra of AL and LL were shown in
Fig. 1d. For AL, the intense bands at 1612, 1515, and 1427 cm− 1
attributed to aromatic skeletal vibrations and the C-H deformation [37].
An obvious band in LL was the sharp hydroxyl at 3380–3490 cm− 1 [38].
Another strong band in LL at 2887 cm− 1 was associated with C-H
stretching, but the band was weaker in AL [38]. The rise of these peaks
in the LL spectrum indicated the dissociation of ether bonds after
liquefaction process [39]. In addition, a main difference in AL and LL
was the presence of bands at the 1722 cm− 1 in LL due to C– – O groups in
PCLD [40].
A small band presented in 2243 cm− 1 (-CNO) and the bands at 3400
− 1
cm (-OH) was disappeared in the spectrum of LLPU, indicating that
the incomplete reaction between PAPI (-CNO) and LL (-OH) (Fig. 1e).
Meanwhile, the characteristic band of LLPU appeared at 3329 cm− 1
corresponding to N-H [40]. In addition, the addition of CB hardly
changed the chemical structure of LLPU. However, the addition of a
small amount of polysiloxane slightly changed on the chemical structure
of LLPU. With increasing the amount of polysiloxane added, additional
enhanced absorption bands at 1258 and 800 cm− 1 in the all spectra of
HLPUs correspond to the enhanced stretching vibrations of Si-O and -Si
(CH3)2, suggesting that the polysiloxane was grafted to the LLPU [41].
Notably, the bands at 2243 cm− 1 (-CNO groups in PAPI) were vanished
in the all spectra of HLPUs, indicating that PAPI was consumed
completely after the reaction with polyols. In short, the HLPUs were
Table 1
The GPC results of AL and LL.
Sample Mn (g⋅mol− 1) Mw (g⋅mol− 1) Mw/Mn Hydroxyl value
3
AL 1487 3.693 × 10 2.48 − HLPU15 and HLPU 20 were 7.80 MPa, 9.71 MPa, 8.59 MPa and 7.96
LL 699 1.119 × 103 1.60 343 mg KOH⋅g−
International Journal of Biological Macromolecules 231 (2023) 123334
prepared successfully via reactions of LL, CB, polysiloxane and PAPI
under the given conditions.
3.2. The analysis the properties of LLPU, CLPU and HLPU
The hydrophobicity of the LLPU, CLPU and HLPCU were evaluated
by determining their WCA and WA as shown in Fig. 2. Under the same
condition, compared with LLPU (77.92◦ ), the CLPU exhibited higher
WCAs (86.54◦ ) (Fig. 2a). One possible cause was that the hydrophobic
CB resulted in reduced the entrance of water due to congestion of the
pores in LLPU. It is worth noting that the WCA of the HLPUs
(89.39◦ –98.68◦ ) gradually increased as the polysiloxane content rose (5
%–15 %). The increment of WCA was mainly due to the transference of
Si-O-Si to the surface of HLPUs during the curing process, which reduced
the surface free energy of CMs [42]. Meanwhile, the enhanced WCA was
attributed to the fact that more Si-O-Si migrated to the surface of the
HLPUs under the condition of higher polysiloxane content (15 wt%)
[43]. Specifically, LLPU phase separation could occur at the molecular
level by adding polymerized siloxane. In other words, microphase sep­
aration was formed on the molecular chain. Therefore, in the process of
polymer synthesis, low surface chain segments (polysiloxane) were
more likely to be enriched on the LLPU surface, resulting in their
enhanced hydrophobicity of polymer [44]. However, when the poly­
siloxane content further increased to 20 %, the WCA of the HLPUs
rapidly declined (90.82◦ ). These phenomena were probably that the
formation of voids or micro cavities triggered via huge phase separation.
In addition, the reduced WCA might also be related to the limited
transference of blocked polysiloxane in polysiloxane-DLPU chains and
the lack of enrichment of HLPU in the CMs [45]. In short, synergy be­
tween hydrophobic CB and polysiloxane chains with low surface energy
could limit the entrance of water.
To further evaluate the hydrophobicity of the LLPU, CLPU and
HLPCU, the WA of the CMs was identified and displayed in Fig. 2b. The
WAs value of the CLPU decreased by 19.34 % as compared to the LLPU.
The polysiloxane content for preparation CMs played a crucial role in
adjusting the WAs value. Specifically, the WA of HLPCU gradually
decreased from 18.39 % to 11.36 % as the polysiloxane content (5–15
%) increased. Similarly, when the polysiloxane content was further
increased to 20 %, the WA of the HLPCU distinctly elevated to 15.32 %
[46].
DMA was used to further evaluate the impact of polysiloxane con­
tents on the thermo-physical capabilities (stiffness and viscoelastic
properties) of the CMs (LLPU, CLPU and HLPU) (Fig. 2). The storage
modulus (E'), glass transition temperature (Tg), and cross-linking density
(ve) were listed in Table 2. The temperature connected with the
maximum peak in the tan δ curve is identified as the Tg of the corre­
sponding CMs [47]. A similar phenomenon was found for E' and loss
factor (tan δ) in all CMs. The E' of the CMs appeared a slight decreased as
the temperature increased. The E' of CMs level-offed and reached the
rubbery plateau under the higher temperature conditions (Fig. 2c). The
maximum peak (Tg) was only detected in the tan δ versus temperature
curves, indicating the homogeneous nature of all LLPU, CLPU and
HLPUs prepared (Fig. 2d) [48].
Under the same conditions, compared with LLPU, the E', Tg and ve of
the CLPU exhibited higher values (Table 2). This might be related to the
enhanced hard segment content by adding CB. Moreover, the E', Tg and
ve of HLPU showed first increased and then decreased with the poly­
siloxane content raised. The increasing trend was probably related to the
enhanced the microphase separation of the soft segment and the hard
segment by aggregation of the hard segment of the system under the
relatively low polysiloxane content conditions [49]. Likewise, the
decreasing trend was mainly attributed to reduce compatibility between
soft segment and hard segment under the high polysiloxane content
conditions [50]. Besides, the storage modulus of HLPU5, HLPU10,
1
MPa, respectively (Table 2). The peak of loss factor (tan δ) variable and
5
X. Chen et al. International Journal of Biological Macromolecules 231 (2023) 123334

Fig. 2. WCA (a), WA (b), storage moduli (E', c) and loss factor (tan δ, d) of LLPU, CLPU and HLPUs.

LLPU. As compared with E' and Tg, a similar variation trend was
Table 2
observed in ve. Among them, with compared to the ve of LLPU (695.28
E', Tg, and ve of different treatments.
mol⋅m− 3), HLPU10 (1136.49 mol⋅m− 3) and HLPU15 (1016.98 mol⋅m− 3)
Sample E' (MPa) Tg (◦ C) ve (mol⋅m− 3) increased by 1.63 and 1.46 times, respectively. This effect was mainly
LLPU 5.76 19.0 695.28 related to the improvement of micro-phase separation of polyurethane
CLPU 6.46 21.2 774.64 by adding appropriate amount of polysiloxane. A proper amount of
HLPU5 7.80 24.5 926.18 polysiloxane molecules could restrict the shift of polymer chain, which
HLPU10 9.71 29.4 1136.49
HLPU15 8.59 25.5 1016.98
led to the increase of E' and Tg in HLPU.
HLPU20 7.96 21.8 952.80 The surface elemental composition and corresponding elemental
valence states of LLPU, CLPU and HLPU15 were analyzed by XPS
(Fig. 3). As shown in Fig. 3a, O1 (531.40 eV), N1 (398.3 eV)) and C1
shifted toward high temperature as the polysiloxane contents increased (283.74 eV) on the XPS spectrum of LLPU were observed. As compared
in the CMs. The Tg of LLPU, CLPU, HLPU5, HLPU10, HLPU15 and to the binding energy of C1 in LLPU (283.74 eV), the binding energy of
HLPU20 were 19 ◦ C, 21.20 ◦ C, 24.5 ◦ C, 29.4 ◦ C 25.5 ◦ C and 21.8 ◦ C, C1 in CLPU obtained by adding CB was slightly raised to 284.01 eV.
respectively (Table 2). In addition, the ve of all the CMs was evaluated Furthermore, compared with the XPS spectra of LLPU and CLPU, the Si2s
based on a previous paper. The following equation according to the (154.98 eV) and Si2p (100.18 eV) were also observed in the HLPU15,
rubber elastic dynamics theory is used to calculate the ve [51,52]: indicating that polysiloxane molecules was successfully loaded into
As shown in Table 2, the ve of all the coating material was evaluated LLPU (Fig. 3b). The EDX spectra (3c1-e1) and maps (3c2-e2) were used
using the following equation from the rubbery plateau modulus through to determine the surface elemental compositions and distributions of
the kinetic theory of rubber elasticity. LLPU, CLPU and HLPU15 (Fig. 3). As can be seen, large amounts of C and
E' = 3veRT O were simultaneously appeared on the LLPU (3c1 and 3c2) and CLPU
(3d1 and 3d2). As expected, the amounts of C in CLPU obtained by
Where Tg is the glass-transition temperature, T is the absolute temper­ adding CB were higher than that of the LLPU. After the polysiloxane
ature at Tg + 40 ◦ C, E' is the storage modulus at Tg + 40 ◦ C, and R is the modification, the Si element uniformly distributed and appeared on the
gas constant. surfaces of HLPU15 (3e1 and 3e2). The appearance of Si element
The ve of CLPU increased by 89 mol⋅m− 3 compared to LLPU. This confirmed the successful preparation of HLPU15 by using polysiloxane.
increasing trend was attributed to physical interactions between CB and The surface and section morphologies of the CFs play an important
role on influencing the nutrient release efficiency [56]. To inspect the

6
X. Chen et al. International Journal of Biological Macromolecules 231 (2023) 123334

Fig. 3. XPS spectra of LLPU, CLPU (a) and HLPU15 (b) coatings. EDX spectra (c1-e1) and maps (c2-e2) of LLPU, CLPU, and DLPU15 coatings, respectively.

7
X. Chen et al.
morphology changes of CMs caused through a variety of technologies,
the surface (a1: LPCU; b1: CLPCU; c1: HLPCU15) and section (a2: LPCU;
b2: CLPCU; c2: HLPCU15) images of LPCU, CLPCU and HLPCU15 were
recorded via SEM images (Fig. 4). Concretely, the surface of LPCU,
CLPCU and HLPCU15 showed smooth surface morphology, whereas
different degrees of pores appeared in different samples. Specifically, a
large number and volume of pores were found in the section micrograph
of the LPCU (a2). These pores were easily entered by water, which led to
the rapid release of nutrients from CFs. After adding CB to the CM of
LLPU, the number and volume of pores of the CLPCU decreased simul­
taneously, suggesting CB modification could slow the N release by
reducing the pores (b2). It was worth noting that almost no pores were
observed on the section micrograph of the HLPCU15 obtained by syn­
ergy of CB and polysiloxane (c2).The nutrient release rate of the
HLPCU15 decreased rapidly due to more Si-O-Si hydrophobic groups. In
brief, the synergy of CB and polysiloxane was beneficial to delay the
nutrient release rate of the CFs.
3.3. The N release properties of LPCU, CLPCU and HLPCU and
degradation rate of HLPCU
The N release performance of the LPCU, CLPCU and HLPCUs were
significantly influenced under the various coating rates and polysiloxane
Fig. 4. SEM images of LPCU (a1: 1000×; a2: 3000×), CLPCU (b1: 1000×; b2: 3000×) and HLPCU15 (c1: 1000×; c2: 3000×). Among them, a1, b1, and c1 appeared
surface images, whereas a2, b2, and c2 showed section images.
8
International Journal of Biological Macromolecules 231 (2023) 123334
content conditions. The longevity of LPCU increased from 3 days to 13
days and 20 days when the coating rates were raised from 3 % to 5 % and
7 %, respectively (Fig. 5a-c). However, the longevity of LPCU did not up
to the quality standard. Fortunately, the N release longevity of CLPCUs
and HLPCUs were obviously longer than that of LPCUs. A strong positive
sense was obtained between the N release longevity of CLPCUs (6–27
days) and the coating rates (3–7 %). Thus, the CB modification could
improve hydrophobicity and then enhance N release characteristics of
coated fertilizers. As can be seen, the rate of N release from HLPCUs was
considerably slower than those of LPCU and CLPCU. Meanwhile, the
longevity of HLPCUs was also closely related to the coating rates and
polysiloxane content. The coating rate was positive correlated to the
longevity of HLPCUs. A strong positive correlation was also observed
between the N releases longevity of HLPCUs and polysiloxane content
(5 %–15 %) under same coating rates condition. However, when the
polysiloxane content further increased to 20 %, the N releases longevity
rapidly declined, which was probably related to the decreased WCA.
Based on optimal polysiloxane content (15 %), the N cumulative release
rate of HLPCUs dropped sharply from 17.06 % to 2.14 % and 1.24 % as
the coating rates increased from 3 % to 5 % and 7 % after the 24 h of
incubation, respectively. Simultaneously, a strong positive correlation
was also observed between the N release longevity of HLPCUs (8–44
days) and coating rates (3–7 %). It was interesting to note that the curve
X. Chen et al.
Fig. 5. The N cumulative release rate of coated fertilizers in water at 25 ◦ C. Release curves of LPCU, CLPCU and HLPCUs (polysiloxane content of 5, 10, 15 and 20 %)
with 3 % (a), 5 % (b), and 7 % (c) of coatings. The degradation rate of HLPCU15 in soil (d).
of HLPCUs changed from “C” to “S” with the coating rates increased
from 3 % to 7 % under the polysiloxane content of 15 % condition
(Fig. 5a-c). In conclusion, HLPCU15 with the longest N release longevity
was obtained under coating rates of 7 % condition. This was mainly due
to synergy between hydrophobic CB and polysiloxane chains with low
surface energy, which limited the rapid loss of nutrients.
To evaluate the biodegradability of CMs, the degradation rate of
HLPCU15 in soil was detected and result was presented in Fig. 6d.
Specifically, the degradation rate of HLPCU15 at 60 days, 120 days and
180 days were 9.16 %, 19.13 % and 33.40 %, respectively, suggesting
that CMs was a degradable and environmentally friendly material.
Similar phenomena were also found in the biodegradability of woods
(eucalyptus and pine)-PEG-400-based PU and lignin-poly(ε-capro­
lactone)-based PU [53,54]. This process might also be closely inter­
linked to the hydrolysis of ester bonds in the CMs in the HLPCU.
Generally, soil is rich in microorganisms (bacteria and fungi), which can
facilitate the degradation of CMs in HLPCU [55]. In summary, the CMs
of HLPCU emerged excellent biodegradability under conditions of mi­
crobial abundance in the soil.
3.4. Performance of HLPCU as fertilizer for cabbage growth
To further verify the growth-promoting effect of HLPCU on plants,
pot experiment and growth index measurement of cabbage were carried
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International Journal of Biological Macromolecules 231 (2023) 123334
out (Fig. 6a). The plant height, stem thickness, SPAD value, above-
ground and underground dry weight of the three fertilization treat­
ments (TU, HLPCU and HLPCU85) were markedly higher than that of CK
after 60 days (Table 3). In comparison to TU, the height, stem thickness,
SPAD value, above-ground and subterranean dry weight of cabbage
plant obtained from HLPCU treatment increased by 29.68 %, 21.64 %,
15.34 %, 32.19 % and 49.36 %, respectively. There were no significant
differences between the height, stem thickness, SPAD value, above-
ground and subterranean dry weight of HLPCU85 and TU in different
treatments. The total N accumulation of HLPCU treatment (0.86
mg⋅pot− 1) was higher than that of the TU treatment (0.59 mg⋅pot− 1)
(Fig. 6b). There were no significant differences for total N accumulation
between HLPCU85 and TU treatments. Similarly, the total N use effi­
ciency of HLPCU (67.16 %) and HLPCU85 (68.36 %) treatments were
significantly higher than that of the TU treatment (43.15 %) (Fig. 6c).
These results clearly demonstrated that HLPCU and HLPCU85 treat­
ments promoted effectively the growth of cabbage plant. Moreover,
HLPCU and HLPCU85 treatments could reduce N losses and improve
cabbage total N use efficiency. Compared with TU and HLPCU treat­
ments, HLPCU85 treatment could increase the yield under the condition
of 15 % reduction of fertilizer application. Because HLPCU treatment
had long-lasting characteristics and good sustained-release ability, it
could consecutively meet the growth of plants [57]. Hence, it had a wide
practical application value in green agriculture and horticulture.
X. Chen et al.
Fig. 6. The optical photo of potted cabbage (a), and different treatments on N accumulation (b), and N used efficiency (c) of cabbage, respectively. Effects of different
treatment on dynamic changes in soil NO−3 -N (d) and NH+ 4 -N (e). The different lowercase letters indicate significant differences among treatments (p < 0.05).
The content of NO−3 -N and NH+ 4 -N of the root zone soil were signif­
icantly different in the various treatments and plant growth stages
(Fig. 6d-e). In the various growth stages of cabbage, compared to CK
treatment, the NO−3 -N and NH+ 4 -N content of TU, HLPCU and HLPCU85
treatments were raised obviously in the root zone. The NO−3 -N (84.28
mg⋅kg− 1) content of TU treatment was distinctly higher than HLPCU
(49.02 mg⋅kg− 1) and HLPCU85 (40.18 mg⋅kg− 1) treatments on the 15th
day (Fig. 6d). In the following time, the NO−3 -N content of TU treatment
showed a sharp decreasing trend. The reduced NO−3 -N content after TU
treatment was mainly attributed to a large amount of N2O volatilization
by forming a high ammonia pressure [58]. However, there was no sig­
nificant difference in NO−3 -N content between the HLPCU and HLPCU85
treatment for the root zone. Notably, compared to TU treatment, the
NO−3 -N content of HLPCU and HLPCU85 treatments reached the
maximum on the 30th day, which increased by 80.84 % and 43.21 %,
respectively. The enhancement of NO−3 -N content was attribute to
10
International Journal of Biological Macromolecules 231 (2023) 123334
postponing of N dissolution and release in HLPCU treatment [59].
However, after 30 days, the NO−3 -N content of HLPCU and HLPCU85
treatments appeared a reduced tendency, but both were still consider­
ably higher than that in the TU treatment. This downward trend was
ascribed to the nitrogen absorbed by cabbage from the soil. As compared
to the NO−3 -N content, a similar phenomenon was found for NH+ 4 -N
content in the root zone soil under different treatments conditions
(Fig. 7e). To sum up, these data implied that the HLPCU was beneficial
to enhance use efficiency of fertilizer and promote growth of crop.
3.5. Greenhouse gas emissions in soil with different treatments
The emission flux of soil greenhouse gas (N2O, CO2 and CH4) in each
treatment during the whole growth period of cabbage was shown in
Fig. 7. As can be seen, the N2O, CO2 and CH4 emission flux of each
fertilization treatment was higher than that of CK treatment. The N2O
X. Chen et al. International Journal of Biological Macromolecules 231 (2023) 123334

Table 3
Plant height, stem thickness, SPAD, above-ground and subterranean dry weight
and GHGI of different treatments.
Sample Plant Stem SPAD Above- Subterranean
height thickness value ground dry weight (g)
(cm) (mm) dry weight
(g)

CK 27.03 0.82 ± 38.13 4.92 ± 1.56 ± 0.23d

± 1.03c 0.11c ± 1.09c 0.70d
TU 43.47 2.68 ± 40.23 26.59 ± 7.01 ± 0.65b
± 2.13b 0.10b ± 2.15b 1.20bc
HLPCU 56.37 3.26 ± 46.40 35.15 ± 10.47 ± 1.01a
± 1.27a 0.13a ± 1.30a 1.08a
HLPCU85 47.50 2.82 ± 45.03 28.51 ± 7.99 ± 0.88b
± 1.42b 0.09b ± 1.35b
1.24ab

Note: Means within the same column followed by different letters are signifi­
cantly different. The Duncan multiple range tests, p < 0.05.

emission flux by TU treatment began to increase significantly on the

10th day (0.08–0.14 kg⋅m− 2⋅h− 1) and the emission peak appeared on the
15th day (0.14 kg⋅m− 2⋅h− 1). After 15 days, the N2O emission flux by TU
treatment showed a rapid decline (Fig. 7a). Compared with TU treat­
ment, HLPCU significantly reduced and delayed the N2O emission peak.
It was worth noting that the emission flux of NO2 by HLPCU85 treatment
was significantly lower than that of HLPCU treatment. The higher soil N
content in the early stages was found after application due to quick
release under ordinary fertilizer treatment. This phenomenon provided
sufficient substrate for nitrification, which improved soil nitrification
and then promoted denitrification [60]. Hence, the N2O emissions
reached a peak at the early stages of fertilizer application. However, N in
the HLPCU was only released slowly through the pores, which led to
slow increase of soil nitrogen and kept it at a certain concentration. In a
word, the peak value of N2O emission was weakened through HLPCU
and delayed for 15 days.
Within 5 days after fertilization, the CO2 emission flux of each
treatment showed a decreasing trend (Fig. 7b). The CO2 emission flux of
the TU treatment reached 149.14 kg⋅m− 2⋅h− 1 on the 15th day.
Compared with TU treatment, the CO2 emission flux of HLPCU and
HLPCU85 treatments were reduced by 31.27 % and 42.20 %, respec­
tively. The emission flux of CH4 showed a decreasing trend within 15
days after all fertilizations (Fig. 7c). Each fertilization treatment reached
the peak on the 30th day. The emission flux of CH4 by TU, HLPCU and
HLPCU85 treatments were 0.036, 0.024 and 0.020 kg⋅m− 2⋅h− 1,
respectively. Subsequently, the emission fluxes of each fertilization
treatment presented a downward trend.
During the whole growth period of cabbage, the cumulative emis­
sions of N2O, CO2 and CH4 in each treatment were in the order: TU >
HLPCU > HLPCU85 > CK (Table 4). Compared with TU treatment, the
cumulative emissions of N2O, CO2 and CH4 in HLPCU treatment were
significantly decreased by 24.75 %, 30.02 %, and 16.69 %, whereas
HLPCU85 reduced by 44.64 %, 39.31 % and 32.27 %, respectively. The
results demonstrated that the HLPCU and HLPCU85 treatments could
significantly reduce the emission of greenhouse gases from soil, espe­
cially the reduction of N2O by the HLPCU and HLPCU85 treatments Fig. 7. Emissions flux of daily N2O (a), CO2 (b) and CH4 (c) emissions from soil
[61]. Similar findings have been reported that the cumulative N2O of different treatments.
emissions decreased by 30.5 %–89.3 % by the CFs treatment [62,63]. At
the 100-year scale, the GWP per unit mass of N2O was 298 times that of HLPCU and HLPCU85 could effectively reduce the N2O, CO2 and CH4
CO2. Compared with the mean values of TU treatment, the GWP data of cumulative emissions from soil (Fig. 8) [64,65].
HLPCU and HLPCU85 treatments were reduced by 29.02 % and 40.18
%, respectively (Table 4). The HLPCU and HLPCU85 treatments reduced 4. Conclusions
the greenhouse effect of N2O, CO2 and CH4 in both short and long time
scales and finally reduced GWP, especially for HLPCU85 treatment. The hydrophobic coating material by synergy of CB and polysiloxane
From the perspective of cabbage production, the greenhouse gas GHGI was successfully prepared to lignin-based coat fertilizer. During the
of each fertilization treatment was still in line with GWP. Compared with liquefaction process, AL was degraded into smaller molecules. The LLPU
TU treatment, the GHGI of HLPCU and HLPCU85 were significantly was further modified by synergy of carbon black and polysiloxane to
reduced by 56.22 % and 52.31 %, respectively (Table 4). To sum up,

11
X. Chen et al. International Journal of Biological Macromolecules 231 (2023) 123334

Table 4
Greenhouse gas emissions accumulation, GWP and GHGI of different treatments.
Sample Cumulative emissions (mg NO2⋅m− 2) Cumulative emissions (mg CO2 ⋅m− 2) Cumulative emissions (mg CH4 ⋅m− 2) GWP GHGI
(kg CO2⋅hm− 2) (kg CO2⋅kg− 1)

CK 18.18 40,332.13 14.71 45,558.52 8.07

TU 81.23 102,102.49 28.49 124,425.29 9.73
HLPCU 61.12 71,453.35 23.73 88,315.59 4.26
HLPCU85 44.97 61,970.36 19.29 74,427.44 4.64

Fig. 8. Reduced nutrient release and greenhouse gas emissions of lignin-based coated urea by synergy of carbon black and polysiloxane.

reduce the micropore size and improve the hydrophobicity. The poly­ BPU bio-based polyurethane
siloxane was grafted to the LLPU. The WCA of the HLPUs LL liquefied lignin
(89.39◦ –98.68◦ ) gradually increased as the polysiloxane content rose (5 LPU lignin-based polyurethane
%–15 %). However, when the polysiloxane content further increased to LLPU liquefied lignin-based polyurethane
20 %, the WCA of the HLPUs rapidly declined (90.82◦ ). A proper amount CB carbon black
of polysiloxane molecules could restrict the shift of polymer chain, SS specific solution
which led to the increase of E' and Tg in HLPU. It was worth noting that PCLD poly(ε-capro-lactone) diol
almost no pores were observed on the section micrograph of the PEG polyethylene glycol
HLPCU15 obtained by synergy of CB and polysiloxane. Compared with CLM CB/LL mixture
LPCU, HLPCU15 with the longest N release longevity (44 days) was TLM thick liquid mixture
obtained under coating rates of 7 % condition. The HLPCU emerged LPCU lignin-based polyurethane coated urea
excellent biodegradability in the soil. HLPCU and HLPCU85 could CLPU carbon black/lignin-based polyurethane
improve total N use efficiency, thereby promoting the growth of cab­ HLPU hydrophobic lignin-based polyurethane
bage. Meanwhile, HLPCU and HLPCU85 could effectively reduce the CLPCU carbon black/lignin-based polyurethane coated urea
N2O, CO2 and CH4 cumulative emissions from soil, especially for CLPM CB/LL/polysiloxane mixture
HLPCU85 treatment. The data provided a theoretical foundation for HLPCU hydrophobic lignin-based polyurethane coated urea
development of CFs. E' storage modulus
Tg glass transition temperature
Abbreviations GPC gel permeation chromatograph
SEM scanning electron microscopy
N nitrogen WCA water contact angle
CFs coated fertilizers WA water absorption
CMs coated materials DMA dynamic mechanical analysis
OPMs organic polymer materials XPS X-ray photoelectron spectrometer
CRUs controlled release ureas EDX energy dispersive X-ray
LPUs lignin-based polyurethanes

12
X. Chen et al.
CRediT authorship contribution statement
[18]
Xiaojuan Chen: Investigation, Writing-Original draft preparation.
Tao Guo: Investigation. Xiao Mo: Investigation. Lidan Zhang: Re­
sources. Rongfeng Wang: Resources, Yunna Xue: Resources, Valida­
[19]
tion. Xiaolin Fan: Formal analysis, Project administration, Super vision.
Shaolong Sun: Conceptualization, Methodology, Resources, Writing-
Reviewing and Editing, Project administration.
[20]
Declaration of competing interest
[21]
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
[22]
the work reported in this paper.
Data availability
[23]
No data was used for the research described in the article.
[24]
Acknowledgement
This work was supported by the National Natural Science Foundation
of China (22178137) and the earmarked fund for CARS (CARS-31).
[25]
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