Chemical Engineering Journal 381 (2020) 122704

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Chemical Engineering Journal

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Degradable polyester/urea inclusion complex applied as a facile and T

environment-friendly strategy for slow-release fertilizer: Performance and
mechanism
⁎ ⁎ ⁎
Hai-Mu Yea, , Hong-Fang Lia, Cai-Shui Wanga, Jingxiang Yangb, , Guoyong Huanga, ,
Xiaoyu Menga, Qiong Zhoua
a
State Key Laboratory of Heavy Oil Processing and Department of Materials Science and Engineering, College of New Energy and Materials Science, China University of
Petroleum, Beijing 102249, PR China
b
Department of Chemistry and Molecular Design Institute, New York University, 100 Washington Square East, Room 1001, New York City, NY 10003, United States

H I GH L IG H T S G R A P H I C A L A B S T R A C T

• Polyester/urea inclusion complexes

are developed as slow-release fertili-
zers.
• Inclusion complex fertilizer is pro-
duced by simple one-step blending.
• Urea release rate can be decreased by
tens to thousands of times in inclusion
complex.
• The correlation between crystal-
lizability and slow-release perfor-
mance is presented.
• A slow-release model is proposed.

A R T I C LE I N FO A B S T R A C T

Keywords: Most manufacturing technologies of slow-release urea fertilizers are solvent-assisted and consequently compli-
Slow-release fertilizer cated. Therefore, the development of a solvent-free and facile approach has been actively pursued. Herein, the
Urea inclusion complexes (ICs) of environmentally degradable polyester and urea prepared by one-step blending are
Degradable polyester developed as slow-release urea fertilizers for the first time. Three kinds of polyesters, poly(butylene succinate)
Inclusion complex
(PBS), poly(ethylene succinate) (PES) and poly(propylene succinate) (PPS) are involved. Compared with neat
Release mechanism
urea, the IC fertilizers exhibit much lower and more adjustable release rates, which can decrease from tens to
thousands of times by varying factors such as granular size, compactness and polyester species. Interestingly, the
crystallizability of polyester is demonstrated to play an important role in controlling the slow-release perfor-
mance, the weaker crystallizability of polyester chains results in the longer release time of IC fertilizer. Analysis
of release profiles reveals that the urea component in IC fertilizers displays a second-order release process first
and then a zero-order behavior at the late stage. Microstructure assay suggests that the insoluble polyester chains
freed from urea frameworks crystallize and sheath the rest of IC upon contact with water. Consequently, a
sophisticated release model of urea from IC fertilizer is proposed. The degradation of polyester component and
the promotion effect of IC fertilizer on maize growth are also studied in the lab.

⁎
Corresponding authors.
E-mail addresses: yehaimu@cup.edu.cn (H.-M. Ye), jy2091@nyu.edu (J. Yang), huanggy@cup.edu.cn (G. Huang).

https://doi.org/10.1016/j.cej.2019.122704
Received 12 June 2019; Received in revised form 22 August 2019; Accepted 1 September 2019
Available online 03 September 2019
1385-8947/ © 2019 Elsevier B.V. All rights reserved.
H.-M. Ye, et al.
1. Introduction
To satisfy the request of increasing food supply and improving life
quality of growing global population, agriculture – the most essential
basic foundation – is bound to consume ever-larger quantities of che-
mical fertilizers. The world’s demand for use of fertilizer nutrient is
anticipated to grow from 184.02 million tonnes (Mt) in 2015 to 201.66
Mt in 2020 [1]. Meanwhile, the low use efficiency of chemical fertilizer
has been a severe issue globally, inefficient usage of fertilizer results in
not only a great economic waste but also many environmental problems
such as solid, water and gas pollution [2–6]. Particularly, the total
utilization of nitrogen fertilizer (N fertilizer, the largest quantity used
fertilizer on the earth [1]) is reported to be as low as 30–50% thanks to
the easy loss paths through volatilization, leaching, and runoff in
agricultural production [7–9].
Slow-release fertilizer has provided a way to improve the utilization
and ease the environmental impact of fertilizer while maintaining or
even boosting crop yield [10–12]. Therefore, the slow-release of urea –
the widely-used N fertilizer due to its high N content (46%) and low
cost – has always been in the spotlight of researchers. Currently, coating
or encapsulation is the most conventional approach to produce
polymer-related slow-release urea fertilizers [13–15]. The coated ma-
terials have been developed by using various polymers from non-en-
vironmentally degradable polymers (e.g., polyolefins, polyurethane,
and polysulfonate) [16–19] to degradable polymers (e.g., poly-
saccharides and aliphatic polyesters) [20–24]. Though the non-de-
gradable polymers are now in more practically-used cases, much at-
tention is being shifted to the degradable polymers, so as to avoid
contaminating the environment by accumulation of coated materials
[25]. However, the current processing techniques for coating urea with
degradable polymers are somehow complicated or require using of
plenty of organic solvents, which is less sustainable [15,26–28]. So,
much simple and green chemical engineering approaches for producing
degradable polymer-assisted, efficient slow-release fertilizers are de-
sired to be put forward.
Inclusion complexes (ICs) formed between urea and polymers have
been widely discovered and used to study the properties and crystal-
lization behaviors of isolated polymer chains [29,30]. The host urea
molecules construct crystalline frameworks having long and persistent
channels where the guest polymer chains are located. The interactions
between the host and the guest are generally realized via van der Waals
forces and hydrogen-bonds [29], reflecting the easy construction of IC.
Often, urea is the major component in different ICs, showing a mass
fraction higher than 60%. When removing the urea frameworks, the
insoluble polymer chains coalesce and crystallize [30], which plausibly
form barrier preventing the fast dissolution of urea from the rest of IC.
As a cue, we found that it usually took more than several hours to
complete the removal of urea when soaking IC in water [31]. Thus, the
polymer/urea IC is of high potential to be applied as slow-release fer-
tilizer.
We have implemented the technology for easily and environment-
friendly producing of different degradable polyester/urea ICs by using
industrial equipment [31]. Consequently, the main objectives of this
study are to study the slow-release performance, clarify the influence
factors, and surmise the release mechanism of urea from polyester/urea
IC fertilizer.
2. Experimental section
2.1. Materials
Urea granules (AR grade), 1,1,2,2-tetrachloroethane and petroleum
ether were purchased from Shanghai Aladdin Bio-Chem Technology Co.
Poly(butylene succinate) (PBS) was supplied by Showa Denko K. K. Poly
(ethylene succinate) (PES) and poly(propylene succinate) (PPS) were
prepared through a two-step reaction of esterification and
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Chemical Engineering Journal 381 (2020) 122704
Table 1
Number-average molecular weights (Mn) and polydispersity indexes (Đ) of
three polyesters.
Polyesters Mn (kg/mol) Đ
PBS 55.7 2.00
PES 15.1 1.59
PPS 12.1 1.78
polycondensation in melt state by using tetra-n-butyltitanate (TBT) as
catalyst [32]. These two lab-synthesized polyesters were used after
purification. The information of number-weight molecular weights (Mn)
and polydispersity indexes (Đ) of polyesters are tabulated in Table 1.
2.2. Preparation of ICs
A semi-solid blending method was used to produce the polyester/
urea ICs [31]. (1) Brabender approach: polyester was first sheared in an
internal mixer (W50EHT, Brabender, Germany) at 120 rpm and 120 °C
for 5 min, then urea was added for further 10 min blend. The product
was cooled to room temperature, smashed and sieved into two frac-
tions, 0.9–2 mm and 2–4 mm. The adding weight ratio of polymer/urea
was set at 1:2, which is slightly higher than the stoichiometric ratio of
pure polyester/urea IC [31,33]. The product prepared by using Bra-
bender internal mixer was marked as “B-polyester/urea IC”. (2) Twin-
screw extruder approach: a certain amount of polyester and urea with a
weight ratio of 1:2 was first physically mixed, then added into a desktop
and self-cycling twin-screw extruder (WLG-10G, Shanghai Xinshuo,
China) at 120 °C for blending at a rotation speed of 240 rpm. After
10 min the product was extruded as long solid rods with a diameter of
3 mm. The rods were cut into cylinders of 3 mm in length. The product
prepared by using twin-screw extruder was marked as “T-polyester/
urea IC”.
2.3. Characterization
Differential scanning calorimetry (DSC) tests were performed on a
NETZSCH 204F1 instrument equipped with an intercooler under an
inert atmosphere of nitrogen. Sample of ~3.0 mg was sealed in an
aluminum pan and heated from 20 to 160 °C at a rate of 10 °C/min.
Thermogravimetric analysis (TGA) tests were conducted on a SHIMA-
DZU DTG-60 instrument. Sample of ~10.0 mg was placed in an open
aluminum pan and heated from 40 to 550 °C at a rate of 20 °C/min
under an inert atmosphere of nitrogen. Scanning electron microscope
(SEM) imaging was performed on a HITACHI SU8010 scanning mi-
croscope operated at an accelerating voltage of 5 kV. The samples were
sputter-coated with thin layers of gold before observation, and the
magnification was adjusted to optimally examine the morphology
characteristics. Polarized optical microscope (POM, LEICA DM2500P)
was used to monitor the morphology evolution of polyester/urea ICs
during release. A small piece of inclusion complex was immersed in a
Petri dish containing deionized water, and the morphology was in-situ
captured at regular time intervals. Waters 1515 gel permeation chro-
matography (GPC, American) was utilized to measure the molecular
information of raw polyesters and degraded PBS. HPLC grade chloro-
form was used as the elution solvent. The densities of ICs were mea-
sured by soaking them in a gradient serial of mixtures of 1,1,2,2-tet-
rachloroethane and petroleum ether.
2.4. N release test in water
Granules of IC (containing 1.0 g urea) or urea (1.0 g) wrapped in
nylon gauze were placed into 100 mL of deionized water at 25 °C and
the water was gently stirred with a magnetic bar at a speed of 30 rpm.
The systems were sealed with plastic films to avoid water evaporation.
H.-M. Ye, et al.
The amounts of N released at required time intervals were measured
according to the Kjeldahl method (ASTM International) [34]. The urea
concentration in solution was determined by a TU-1901 UV–Vis spec-
trophotometry (Beijing Pgeneral, China) based on the pre-established
standard curve.
2.5. N release test in soil column
Granules of ICs (containing 0.5 g urea) or urea (0.5 g) were placed in
the middle layer of a soil column. The soil columns with 30 mm in
diameter and 150 mm in height were prepared using air-dried soil with
particle size between 1 and 2 mm under suitable compactness. To
evaluate the slow-release effect, deionized water was continuously
pumped into the soil column from the top of a glass tube at a rate of
3 mL/min and the eluted solutions at appropriate intervals were col-
lected and measured by UV–Vis spectrophotometry. The experiment
was carried out at 25 °C.
2.6. Pot trial
The promotion of IC fertilizers on seed germination and early-stage
seedling growth of maize was investigated by comparing with neat urea
group and control group (without urea). For IC and urea groups, fer-
tilizer containing 0.056 g available urea content was mixed with 10.0 g
soil, then the mixture was placed in the bottom half of a plastic cup
(4.5 cm in diameter and 7.0 cm in depth) which was filled by another
70.0 g soil. Two maize seeds with similar size were planted in each cup
(4.0 cm under the soil top) to grow for 5 weeks at 25 °C. Every day,
20 mL of deionized water was sprayed on the top of cup each. The
growth indexes of plants including leaf width, plant height, root length,
and fresh weight were obtained based on three parallel experiments.
Fig. 1. (A) Schematic diagram of the production processes of polyester/urea ICs. (B) and (C) show the DSC curves of IC products, polyesters and urea, respectively.
(D) Shows the TGA curves of PBS, urea, and PBS/urea IC. The abbreviation of “i.p.” means the initial percentage, i.e., 100%. The twin-screw extrusion products
showed the same thermal properties as the corresponding Brabender products.
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Chemical Engineering Journal 381 (2020) 122704
3. Results and discussion
3.1. Formation of polyester/urea IC fertilizers
Fig. 1A sketches the production processes of polyester/urea IC by
using (quasi-) industrial equipment. Granules of IC fertilizer were di-
rectly prepared by simply blending polyester and urea at a specified
temperature (i.e., 120 °C). Granular size of product could be easily
manipulated via sieving operation or changing extrusion die, while no
solvent was required to assist the incorporation of polyester component.
The melting points (Tms) of as-obtained samples at 138–144 °C
(Fig. 1B) were higher than those of neat polyesters (114 °C for PBS and
103 °C for PES shown in Fig. 1C, the Tm of raw PPS was 55 °C during the
first heating process, as shown in Fig. S1) and urea (134 °C), which
indeed confirmed the formation of polyester/urea ICs [31,33,35,36]. X-
ray diffractograms (Fig. S2) also showed that all ICs adopted hexagonal
crystal modification as previously reported [33,35], different from the
raw materials. And the interaction between polyester chain and urea
channel was van der Waals force [33]. Slight difference of Tms between
these three polyester/urea ICs was originated from the distinct average
ester group densities in their backbones and crystallizability [36].
To evaluate whether any urea was lost during the IC preparation,
TGA data were used to figure out the composition in IC (Fig. 1D). On
the basis of the distinct temperature ranges between the first de-
gradation stage of urea (160–290 °C) and the thermal degradation of
PBS (> 310 °C), the mass fraction of urea in IC was calculated at 67.6%,
almost the same as the initial mass feeding ratio of polyester/urea at
1:2. PBS/urea IC prepared from a mass feeding ratio of polyester/urea
at 1:3 was assayed to contain 75.3% of urea (Fig. S3). Therefore, urea
was hardly lost when preparing the ICs.
3.2. Slow-release performance of IC fertilizer
N release behaviors of polyester/urea ICs were investigated using
two rapid methodologies, the water dissolution rate method (Fig. 2)
H.-M. Ye, et al. Chemical Engineering Journal 381 (2020) 122704

Fig. 2. (A) The schematic diagram of water dissolution apparatus and the release profiles of (B) neat urea and B-PBS/urea ICs with different size distributions, (C)
different B-polyester/urea ICs, and (D) different T-polyester/urea ICs.

Fig. 3. (A) The schematic diagram of continuous soil column leaching apparatus and (B) the slow-release profiles of urea and B-polyester/urea ICs.

and the soil column leaching method (Fig. 3).
The total dissolution time of urea granules (2–4 mm) in gently-
stirred water was less than 10 min, while the whole release time of urea
component from B-PBS/urea IC with a size distribution of 0.9–2 mm
reached ~2 h (Fig. 2B). The release time of B-PBS/urea IC fertilizer
increased to ~8 h when the size was increased to 2–4 mm. Compared
with neat urea, the release rate of urea in IC fertilizer with similar size
could be reduced by ~48 times. The slow-release performance was
remarkably regulated by changing the size of IC granules: the larger size
led to the longer release time. When the PBS within IC fertilizer was
replaced by PES or PPS, the release rate of IC also changed obviously
(Fig. 2C). B-PPS/urea IC showed a longer release time than B-PBS/urea
IC (~12 h versus ~8 h), while B-PES/urea IC displayed a worse
performance (~4h).
The slow-release performances of T-polyester/urea ICs produced by
twin-screw extruder were also assayed (Fig. 2D). The densities of B-
PBS/urea and T-PBS/urea fertilizers were measured as 1.25 and 1.28 g/
cm3, respectively (Table S1). Because of higher compactness, the T-
PBS/urea IC exhibited a much longer release time of 8 days, which was
over one thousand times slower than that of neat urea. Furthermore, T-
PPS/urea IC possessed even slower release ability than T-PBS/urea IC,
showing a release time over two thousand times of neat urea (14 days).
Therefore, the slow-release rate of polyester/urea IC fertilizers can be
reduced in a large range from twelve to over two thousand times to fit
the growth periods of various plants via varying processing approach,
granular size and polyester species. After the polyester/urea ICs were

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H.-M. Ye, et al. Chemical Engineering Journal 381 (2020) 122704

Table 2
The fitting kinetic parameters of experimental data of different IC fertilizers by
using the second-order model.
Sample B-PBS/urea IC B-PES/urea IC B-PBS/urea IC B-PPS/urea IC
0.9–2 mm 2–4 mm 2–4 mm 2–4 mm

Adj. R2 0.995 0.996 0.992 0.990

K (min−1) 5.2 × 10−1 3.0 × 10−1 1.0 × 10−1 8.8 × 10−2

Sample T-PES/urea IC T-PBS/urea IC T-PPS/urea IC

3 mm 3 mm 3 mm

Adj. R2 0.988 0.992 0.980

K (min−1) 3.3 × 10−2 1.6 × 10−2 6.1 × 10−3

released for long enough, DSC and TGA curves of the residual polyester
components were measured (Fig. S4). The thermal analyses revealed
the complete removal of urea, which furthers the utilization of IC fer-
tilizers compared with some partially-released fertilizers [11,37].
To unravel the release kinetics of urea component within IC ferti-
lizers, various dissolution models [38], including first-order, second-
order, Higuchi, and Korsmeyer-Peppas, were used to fit the experi-
mental data presented above. It was found that the second-order model
(Eq. (1)) could fit these release profiles well with coefficient of de-
termination (adj. R2) ≥ 0.980 (Fig. S5 and Table 2).
Mt
= Kt
M∞ (M∞ − Mt )
where Mt is the cumulative N release percentage at time t, and M∞ the
final N release percentage. M∞ is 100% here according to TGA and DSC
results in Fig. S4. K is the characteristic release rate constant of IC
fertilizer. In Table 2, the change of K values proved again that granular
size, polyester species and processing approach could be easily used to
manipulate the slow-release performance of IC fertilizers.
To optimize and shorten the experiment period, fertilizers of B-
polyester/urea IC (0.9–2 mm) were used in the following sections if not
specialized. The continuous soil column leaching evaluation of IC fer-
tilizers are shown in Fig. 3. The neat urea was run out within 10 min,
while the B-PBS/urea IC only released ~50% in the first 10 min and
completed the release in three more hours. The release rate of urea in IC
fertilizer was reduced by ~36 times compared to that of neat urea, and
the decline degree was more notable than the result obtained by water
dissolution rate method aforementioned (~24 times). The soil column
leaching results also demonstrated the remarkable dependence of re-
lease time of IC fertilizers on the polyester species. B-PPS/urea IC dis-
played the longest release time (~5h) while B-PES/urea IC showed the
shortest time (~1.5 h). Thus, the IC fertilizers could have good slow-
release performance and adjustable release periods of nutrition supply
in soil environment.
3.3. Slow-release mechanism
Fig. 4 depicts the DSC curves of different layers of a B-PBS/urea IC
fertilizer granule after release in water for 30 min. The surface layer
showed two Tms at ~136 °C and ~142 °C respectively corresponding to
the coalesced crystals of PBS and the remaining PBS/urea IC [33]. No
melting phenomenon of separate urea was detected, indicating the re-
leased urea was immediately taken away by water when carried off
from IC. The higher melting enthalpy of the intermediate layer at
~142 °C indicated that more IC existed than in the surface layer of
granule and, correspondingly, the amount of coalesced crystals of PBS
was less in the intermediate layer, showing smaller melting enthalpy at
~136 °C. The single melting point of core layer at ~142 °C indicated the
well-maintained IC structure without water erosion. Therefore, urea
component was released from the surface to the interior of IC granule.
Besides, the coalesced polyester chains sheathed the remaining IC in
both outer (partial) and inner parts of the granule, which essentially
Fig. 4. DSC curves of different granular layer profiles of PBS/urea IC fertilizer
after N release for 30 min in water.
endowed the IC fertilizer with slow-release feature.
To further clarify the release behavior, thin layers of IC fertilizers
were immersed into deionized water for in-situ POM observation. As
shown in the row A of Fig. 5, the release of urea started from the edge
(1) (or surface) of B-PBS/urea IC and then proceeded gradually into the
interior based on the enhancing evolution of birefringence originated
from the instant crystallization of coalesced PBS chains. Similar phe-
nomenon was observed in some drug/polymer IC systems [39,40]. The
crystallization rate of coalesced chains seemed faster during the release
of B-PES/urea IC (row B) compared to that of B-PBS/urea IC. But, PPS
chains coalesced from IC (row C) showed extremely weak crystal-
lizability, as the change of birefringence signal was hardly captured. An
important and common feature during the release processes of ICs was
that no obvious change of shape and size of IC granules occurred. As the
mass fractions of polyesters were only 1/3 in these granules, the
structure left should be highly porous (confirmed in Fig. 6), which
provided voids for water to enter and further dissolve the urea com-
ponent of IC in granular interior. The denudation of urea from IC fra-
meworks and the subsequent traveling route of dissolved urea through
porous structure to the outside of granule should be the main reason for
the second-order release kinetics studied above.
Fig. 6 shows the micromorphology of polyester/urea IC granules
before and after release of urea component. Though the B-PBS/urea IC
exhibited a compact surface, a large number of long voids with
~100–200 nm wide were generated after the removal of urea. Dissol-
ving of urea frameworks provided opportunity for the crystallization
among PBS chains that were previously isolated in adjacent urea
channels of ICs, hence resulted in the formation of voids. The voids in
residual PES granule were similar to those of PBS, but with even larger
size (Fig. 6B′). However, the PPS/urea IC granule displayed distin-
guishing morphology after release of urea, where less voids with rather
smooth edge and diameter of ~1–2 μm were found (Fig. 6C′).
The distinct morphologies of voids in different final granules might
be stemmed from the difference in crystallization behavior of polyester
chains escaping from urea frameworks. From the DSC curves in Fig. 1C,
it was clear that PBS and PES have stronger crystallizability than PPS.
So, it is speculated that PBS and PES chains could crystallize adjacently
fast after being freed from ICs, and therewith led to the formation of a
large number of voids. However, the freed PPS chains could not crys-
tallize immediately while kept amorphous instead. They flowed locally
and fused together, then slowly crystallized. As a result, the number of
voids decreased and the size increased. We measured the Tms of as-
coalesced polyester samples (Fig. S4) and found those of PBS, PES and
PPS were 138, 124 and 46 °C, respectively, demonstrating that both

5
H.-M. Ye, et al.
Fig. 5. In-situ POM images of the releasing processes of (A) B-PBS/urea, (B) B-PES/urea and (C) B-PPS/urea IC fertilizers in deionized water under 25 °C. The layer
thickness is about 100 μm and the scale bars are all 100 μm.
coalesced PBS and PES chains formed extended-chain crystals [33,41],
corresponding to their quick crystallization. The coalesced PPS chains
displayed slow crystallization and could only form common folded-
chain crystals, showing a lower Tm and enthalpy than raw material (Fig.
S1). Thereby, the slow-release performance of IC fertilizer should have
correlation with the polyester’s crystallizability. The coalesced PPS
chains had time enough long to move and fuse, then provided denser
sheath and better sealing effect for the remaining IC than PBS and PES
chains, which helped PPS/urea IC displaying the best slow-release
performance among these three IC fertilizers. With larger voids, PES/
urea IC showed worse slow-release performance than PBS/urea IC fer-
tilizer. T-polyester/urea ICs prepared by twin-screw extruder had much
more compact structure than B-polyester/ICs, resulting in the smaller
voids after urea release (Fig. 6D′–F′) and much longer release times
(Fig. 2D).
Even when some release of urea had progressed in the intermediate
layer, some IC still existed in the surface layer (Fig. 4). Thus, urea
component in IC fertilizer was not simply gradually dissolved from the
outside in. A sophisticated slow-release process must be considered. For
the late stage of release profiles (e.g. cumulative N > 90%) shown in
Fig. 2, the release curves could be fit better by a zero-order model,
which has been widely used to describe the release kinetics of coated
and membrane controlled form systems [38,42], than the second-order
model.
On the basis of the results achieved aforementioned, the slow-re-
lease mechanism of polyester/urea IC fertilizer is proposed in Fig. 7.
The IC fertilizer granules start to release urea outside in when being
contacted with water and a large number of voids form due to the
coalescence and crystallization of freed polyester chains. The porous
structure complicates the internal nutrient release pathway and acts as
a physical barrier to prevent the release of urea from the inner region
[43,44]. The larger fertilizer size and more compact fertilizer structure
benefits the longer release time. Meanwhile, the walls of voids are not
just built by pure polyester but a core-sheath structure, where dense
sheath of polyester chains protects ICs in each small region. The sheath
of polymer chains on IC structure prolongs the release time. Further-
more, the crystallizability of coalesced polymer chains strongly de-
termines the microstructure (i.e., compactness) of polymer sheath, and
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Chemical Engineering Journal 381 (2020) 122704
thereby the slow-release performance.
3.4. Degradation of polyester component
Both hydrolytic and compost degradation properties of aliphatic
polyesters have been previously confirmed [45,46]. The products of
degradation can be accommodated by the environment and even pos-
sibly benefit the output of plants. Here, we used GPC to confirm the
degradation of PBS component during the release of IC fertilizer in
water at 25 °C. Fig. 8 shows that the Mn of PBS decreased from initial
55.7 to 47.4 kg/mol after half month and continuously declined to
10.2 kg/mol after 3 months. Though such a degradation process was not
obtained in the real environment, complex factors (e.g., microorgan-
isms [47]) in the nature would further accelerate the degradation rate.
Therefore, the polyester/urea IC fertilizers can avoid the secondary
pollution to the environment.
3.5. Growth of maize seedlings
The growth promotion effect of B-PBS/urea IC fertilizer on the
growth of maize seedlings was evaluated in the lab and the results are
statistically charted in Fig. 9. These three groups of five-week-old
seedlings showed distinct growth indexes. Nitrogen fertilizer re-
markably promoted the growth of maize, resulting in the better growth
indexes of seedlings than the control. Meanwhile, the growth pro-
moting ability of IC fertilizer on maize was stronger than neat urea, and
the average indexes of leaf width, root length, plant height, and fresh
weight increased 4%, 9%, 4%, and 21%, respectively. The significant
increase of fresh weight directly revealed the promoting formation of
organic content due to the better utilization of nitrogen nutrient in IC
than neat urea. During the daily watering, the N fertilizer was gradually
dissolved and absorbed by plants with the water flow, but nutrient
possibly lost at the same time. At the early stage, neat urea granules
released more N fertilizer, which exceeded the absorption capacity of
plants, than the IC fertilizer, and consequently suffered higher loss. As a
result, less N fertilizer was left in the soil system of urea group for future
use, resulting in weaker and weaker growth promoting ability as time
went by. To present a more intuitive effect, representative digital
H.-M. Ye, et al. Chemical Engineering Journal 381 (2020) 122704

Fig. 6. SEM micromorphology of polyester/urea ICs before and after urea release. (A)–(F) are the original B-polyester/urea and T-polyester/urea ICs, and (A′)–(F′)
are the corresponding samples after being completely released.

Fig. 7. Schematic of the slow-release mechanism of polyester/urea IC fertilizer.

Fig. 8. Dependence of number-average molecular weight (Mn) on time of PBS

component in IC fertilizer when soaked in water at 25 °C.

7
H.-M. Ye, et al.
Fig. 9. (A) The schematic diagram of pot trial system and (B) the growth indexes of three groups of maize seedling after five weeks. (C) and (D) are the digital photos
of seedlings after growing for two and five weeks, respectively. (I), (II), and (III) indicate the control, urea and IC groups, respectively.
photos of two- and five-week-old maize seedlings are shown in Fig. 9C
and D. The IC fertilizer was more conducive to plant growth and could
contribute more to the crop productivity than neat urea.
4. Conclusions
Herein, a new and facile strategy was used to produce environment-
friendly slow-release urea fertilizers via forming ICs with degradable
polyesters. Compared with neat urea, the IC fertilizers displayed much
lower, adjustable release rate. Detailed evaluation revealed that many
factors including granular size, compactness (i.e., processing approach),
and polyester species could be conveniently used to regulate and op-
timize the slow-release performance. Specifically, the PPS/urea IC
granules produced by twin-screw extruder with a size of 3 mm dis-
played a release period of 14 days in gently-stirred water. And, the
correlation between crystallizability of polyester chains and slow-re-
lease performance of IC fertilizers was uncovered. The weaker crystal-
lizability helped achieving a slower release rate. The release profiles
suggested that the urea component in IC fertilizers mainly exhibited a
second-order dissolution behavior first and, subsequently, a zero-order
behavior at the late stage. DSC and micromorphology confirmed the
formation of highly porous structure and polyester sheath on the re-
maining IC during release, then a sophisticated slow-release model was
proposed.
This is the first attempt to show ICs as a kind of promising slow-
release fertilizer. Many advantages of IC fertilizer have been demon-
strated; the degradation of polyester component and the promotion of
maize growth using IC fertilizer have also been verified in the lab. We
are further working on this track to optimize the design and develop
better and sustainable slow-release IC-type fertilizers.
Acknowledgments
H.M.Y. thanks the funding support from National Natural Science
Foundation of China (21674128) and China Scholarship Council
(201806445004). G.H. gratefully acknowledges the Science Foundation
of China University of Petroleum, Beijing (ZX20180416).
8
Chemical Engineering Journal 381 (2020) 122704
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.cej.2019.122704.
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