International Journal of Biological Macromolecules 146 (2020) 1–8

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International Journal of Biological Macromolecules

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

Lignin assisted Pickering emulsion polymerization to microencapsulate

1-tetradecanol for thermal management
Yanbin Wang, Xiang Li, Chuanfei Shen, Zhiping Mao, Hong Xu, Yi Zhong, Xiaofeng Sui ⁎,
Xueling Feng, Bijia Wang ⁎
Key Lab of Science and Technology of Eco-textile, Ministry of Education, College of Chemistry, Chemical Engineering and Biotechnology, Donghua University, Shanghai 201620, People's Republic of
China
Innovation Center for Textile Science and Technology of DHU, Donghua University, Shanghai 201620, People's Republic of China

a r t i c l e i n f o a b s t r a c t

Article history: This work explored the use of Pickering emulsion stabilized by lignin nanoparticles (LNPs) to microencapsulate
Received 30 August 2019 1-tetradecanol (TDA) via polymerization of acrylates for thermal management. The morphology and thermal
Received in revised form 18 December 2019 performance of the resulting microcapsules were explored using scanning electron microscopy (SEM) and differ-
Accepted 19 December 2019
ential scanning calorimetry (DSC). A highest encapsulation ratio of 81.4% and melting enthalpy of 190 J/g could be
Available online 21 December 2019
achieved when the core/shell mass ratio was 2:1, and 10 wt% of the crosslinking monomer pentaerythritol
Keywords:
tetraacrylate (PETRA) was used. Results of the leakage and accelerated thermal cycling tests showed that the mi-
Lignin nanoparticles crocapsules had good thermal and chemical stability. When the microcapsules were combined with gypsum, an
Pickering emulsion effective thermal storage composite was obtained, showing good potential for thermal management in the con-
Thermal energy storage struction field.
1-tetradecanol © 2019 Elsevier B.V. All rights reserved.

1. Introduction encapsulation efficiency [13], and the shell strength of the resulted cap-
sules could be enhanced by the stabilizing particles [14].
Phase change materials (PCMs) can absorb, store and release huge Lignin as a natural biopolymer with good biodegradability and
latent thermal energy during the process of melting and solidification biocompatibility has attracted considerable attention in recent
at defined temperature ranges [1–5] making them promising candidate years [15–18]. Micro- and nano particles of lignin, recently were
for latent thermal energy storage (LTES). Among the PCMs, fatty alco- shown to be effective solid emulsifiers for Pickering emulsions
hols stand out for being renewable and eco-friendly, having high latent [19–23]. Report from Ma et al. [24] ranked lignin particles as the
enthalpy and low cost, yet are limited by their inherent flammability best emulsion stabilizer among 10 different emulsifiers. Our group
and tendency to leak above phase change temperature. The encapsula- has also previously reported that O/W Pickering emulsion stabilized
tion of fatty alcohols into micro- or nano-capsules is an effective method by lignin nanoparticles as a precursor to PLA/lignin composites that
to address the above-mentioned drawbacks. Methods including in situ are mechanically enhanced and UV-shielding [25]. To the best of
polymerization [6,7], miniemulsion polymerization [8,9], emulsion po- our knowledge, the study of using lignin particle stabilized O/W
lymerization [10] and suspension polymerization [11] have been Pickering emulsions to prepare phase change microcapsules has
employed to encapsulate fatty alcohols PCMs, which were mostly en- not been reported.
abled by styrene-maleic anhydride copolymer, a costly synthetic surfac- Herein, we put forward a facile and efficient method based on lignin
tant, as the emulsifier. assisted Pickering emulsions templating for the synthesis of microcap-
Solid particles could be used to form Pickering emulsions, which are sules (TDA/PMMA/MPCMs) (Scheme 1). The effects of crosslinking
considered more stable and more environmental friendly [12]. More- monomer and core/monomer mass ratio on the morphology and ther-
over, microencapsulation via Pickering emulsion templated polymeri- mal properties of microcapsules were investigated. The thermal stabil-
zation could reduce the loss of core material and ensure high ity, thermal cycle stability and leakage resistance were also discussed.
Finally, a heat storage construction material gypsum/microcapsules
composite (GS@TDA/PMMA/MPCMs) was prepared and its heat-
⁎ Corresponding authors at: Donghua University, People's Republic of China. shielding and heat storage properties were studied using calibrated in-
E-mail addresses: [email protected] (X. Sui), [email protected] (B. Wang). frared camera and DSC.

https://doi.org/10.1016/j.ijbiomac.2019.12.175
0141-8130/© 2019 Elsevier B.V. All rights reserved.
2 Y. Wang et al. / International Journal of Biological Macromolecules 146 (2020) 1–8

Scheme 1. Schematic illustration of preparing (a) LNPs, (b) TDA/PMMA/MPCMs via Pickering emulsion polymerization.

2. Experiment resulting emulsion was placed in a 100 mL three-neck flask with a mag-
netic stirrer, nitrogen inlet and reflux condenser, the temperature was
2.1. Materials maintained at 60 °C for 0.5 h and then heated to 75 °C for another 6 h.
After cooling down to room temperature the resultant microcapsules
Lignin alkali powder (AL) was purchased from Sigma Aldrich. Ace- latex was filtered and washed with 60 °C D.I. water for three times to re-
tone was obtained from Shanghai Lianyu Chemical Co., Ltd. Methyl move any unencapsulated TDA, residual monomers and finally left to
methacrylate (MMA) was purchased from Sinopharm Chemical Re- dry for 48 h at room temperature. For comparison, microcapsules with-
agent Co., Ltd. 1-Tetradecanol (TDA) was purchased from Shanghai out TDA were prepared by the same procedures.
Titan Technology Co., Ltd. Pentaerythritol tetraacrylate (PETRA) was
purchased from Shanghai Macklin Biochemical Co., Ltd. 2,2′-Azobis(2- 2.4. Preparation of GS@TDA/PMMA/MPCMs
methylpropionitrile) (AIBN) was purchased from Adamas Reagent Co.,
Ltd. Gypsum was purchased from Nantong Jimuwu E-commerce Co., GS@TDA/PMMA/MPCMs were prepared as follows. A
Ltd. All reagents were used as received without further purification. De- predetermined amount of TDA/PMMA/MPCMs were mixed with 10 g
ionized water (D.I. water) was used throughout the experiments unless gypsum powders and then added to appropriate D.I. water. Subse-
specified. quently, the resulting mixture was transferred into round molds and
subjected to dry for 48 h at room temperature.
2.2. Preparation of LNPs
2.5. Characterizations
LNPs were conveniently obtained using the nanoprecipitation
method [26]. The procedure to prepare LNPs is illustrated in Scheme The morphology of LNPs was characterized using TEM (JEM-2100,
1a. Specifically, 1 g AL was first dissolved in 100 mL acetone/water JEOL, Japan) at voltage of 100 kV. TEM observation was performed on
(7:3, vol/vol) mixture. After continuous stirring for 1 h (300 rpm, one dried drop of a 0.05% aqueous suspension of LNPs on a carbon
25 °C), the solution was filtered through a 1000 mesh filter screen to re- coated grid (200 mesh).
move any undissolved particles. The filtrate was diluted by adding The SEM images of microcapsules were obtained using a scanning
70 mL D.I. water with stirring. After that, the mixture was continuously electron microscope (SEM) (TM3030, Hitachi, Japan).
stirred 36 h to allow completely evaporation of acetone. The resulting The microstructure of microcapsules shells was investigated by field
mixture was an aqueous suspension of LNPs that could be used to pre- emission scanning electron microscope (FE-SEM) (S-4800, Hitachi,
pare MPCMs. Japan) to confirm the existence of LNPs.

2.3. Preparation of TDA/PMMA/MPCMs Table 1

Formulations used to prepare TDA/PMMA/MPCMs.
The formulations for the preparation of TDA/PMMA/MPCMs are Sample no. TDA (g) MMA (g) PETRA (g) Lignin/oil phase (wt%)
listed in Table 1 and a schematic illustration of the synthetic procedures
S1 2 2 – 3
is shown in Scheme 1b. The TDA/PMMA/MPCMs were prepared by the S2 2 2 0.2 3
following steps. A predetermined amount of the aqueous LNPs suspen- S3 2 2 0.4 3
sion was mixed with oil phase prepared by mixing MMA, PETRA, AIBN S4 2 2 0.6 3
and TDA at 60 °C. A stable Pickering emulsion was formed by homoge- S5 4 2 0.2 3
S6 3 1 0.1 3
nization (IKA T18 homogenizer, Germany) at 8000 rpm for 3 min. The
 Y. Wang et al. / International Journal of Biological Macromolecules 146 (2020) 1–8 3

Fig. 1. (a) Size distributions and (b) TEM images of LNPs; (c) O/W Pickering emulsion stabilized by LNPs.

The volume mean droplet diameter (D43) of LNPs was measured temperature. The DSC measurements will be performed for this samples
using a laser particle-size analyzer (LS13320, Beckman Instruments, after different heating/cooling cycles.
Inc., USA). All measurements were performed at 25 °C, and the result re- The thermal behavior of the GS@TDA/PMMA/MPCMs was studied by
corded was an average of three times. using a forward looking infra-red system (Ti450 Thermal imagers,
The optical micrographs of O/W Pickering emulsions stabilized by Fluke, USA). The samples were placed on a heating plate at a controlled
LNPs were obtained using an optical microscope (Nikon, ECLIPSE 80i, temperature (60 °C) and immediately tested.
Japan).
Fourier transform infrared spectroscopy (FT-IR) analysis was per- 3. Results and discussion
formed using a PerkinElmer Spectrum Two instrument (USA) equipped
with an attenuated total reflectance accessory spectrometer in the 3.1. LNPs and Pickering emulsions stabilized by LNPs
range of 400–4000 cm−1 with a resolution of 4 cm−1.
The thermal properties were measured using differential scanning The aggregation of alkaline lignin in water is an obstacle for prepar-
calorimetry (DSC 214 Polyma) at a heating or cooling rate of ing Pickering emulsions and other high value-added applications of lig-
10 °C min−1 after elimination of the thermal history under nitrogen at- nin. Recently, a great deal of effort has been made to address this
mosphere and the temperature ranges from −10 °C to 70 °C. problem [28–30]. Herein, a straight forward method was employed to
The leakage test was measured by heating the samples at 60 °C for prepare LNPs. The size and morphology of LNPs were observed using
60 h. The cycle stability of TDA/PMMA/MPCMs was tested using a sim- laser particle-size analyzer and TEM.
ilar method previously reported by Yi. et al. [27], the samples were first As observed in Fig. 1a, the average size of lignin particles is 160 nm
heated in an oven (60 °C) for 10 min and then cooled in air to room with a narrow polydispersity index (PDI) of 0.169. The TEM images

Fig. 2. SEM images of TDA/PMMA/MPCMs.

4 Y. Wang et al. / International Journal of Biological Macromolecules 146 (2020) 1–8

Fig. 3. Size distributions of emulsions (a) sample S1 without PETRA; (b) sample S2 with PETRA stabilized by LNPs.

are shown in Fig. 1b, indicate that the prepared LNPs have a uniform All crosslinked microcapsules (S2–S5) have concaves and core-shell
spherical shape and the particle sizes are consistent with the results of structure (Fig. 2). The emergence of concaves can be reasoned as fol-
laser particle-size analyzer. The O/W Pickering emulsion of TDA and lows: density difference between the monomer and the forming poly-
MMA is shown in Fig. 1c. It can be clearly seen the morphology of emul- mer could produce expansion space in the process of polymerization
sion droplets are spherical shape in different size with clear boundary [32–34] and TDA would shrink from liquid state to solid state [35].
and good roundness. With the increasing PETRA dosage, the surfaces of the microcapsules be-
come smooth. The reduced number of the concaves as the amount of
3.2. Effects of PETRA dosage and core/monomer mass ratio on the morphol- PETRA increased, could be understood in that the degree of cross-
ogy of the TDA/PMMA/MPCMs linking enhanced the mechanical strength of the shell material making
them more resistant to deformation [36]. The microcapsules (S5) were
The morphologies of the microcapsules are shown in Fig. 2. All the further investigated by FE-SEM to reveal the microstructure of the
microcapsules have spherical profiles with dimples. However, visible PMMA shells (Fig. 4). The FE-SEM images of outer-surface and cross-
holes and broken microcapsules could be found on the surface of S1, section of the shell clearly show the presence of nano-scale particles
in which no PETRA was added, but no holes were found for other sam- within the PMMA matrix, confirming that LNPs are embedded in the
ples, showing crosslinking is essential to obtain desirable shell strength. shells of these microcapsules.
Moreover, the size of the microcapsules in sample S1 was on average
larger than those in samples S2–S5. While the DLS results (Fig. 3) of 3.3. Effects of PETRA dosage and core/monomer mass ratio on the thermal
emulsions with and without PETRA show that size of the most of parti- properties of the TDA/PMMA/MPCMs
cles in both were distributed between 2 μm and 20 μm and the larger
particles may be due to the aggregation of solid emulsion droplets dur- The thermal energystorage/release performances of pristine TDA
ing the test condition. The microcapsules formed without PETRA were and samples S2–S5 were determined by DSC, and the results are
larger possibly due to the Ostwald ripening process during the polymer- shown in Fig. 5. For all samples tested, there is only one endothermic
ization (see attached video), which could be suppressed by incorpora- peak appeared on the DSC heating curves. However, during the cooling
tion of the crosslinking monomer PETRA and enhanced stiffness of the process, two consecutive exothermic peaks were observed (labeled as α
shell. When the mass ratio of core/monomer was increased to 3:1, and β peaks from high to low temperature). The emergence of α and β
many broken microcapsules can be found (Fig. 2S6), indicating the peaks for microcapsules and pristine TDA can be explained by the con-
amount of shell material was not enough to completely cover the currence of heterogeneous and homogeneous nucleation [37–39]. From
core. In addition, spherical particles are observed on the inner wall of Fig. 5b, it can be seen that the crystallization peaks of the microcapsules
the microcapsules (Fig. 2S3), which could be attributed to polymeriza- broadened and shifted to lower temperatures comparing with pristine
tion of remnant hydrophobic monomers and initiator trapped inside TDA, indicative of a change in crystallization mechanism of TDA after
the forming microcapsules [31]. microencapsulation [40]. This super-cooling phenomenon was

Fig. 4. FE-SEM images (a) outer-surface; (b) cross-section of TDA/PMMA/MPCMs ( S5).

 Y. Wang et al. / International Journal of Biological Macromolecules 146 (2020) 1–8 5

Fig. 5. DSC curves (a) heating curves and (b) cooling curves of TDA and TDA/PMMA/MPCMs (S2–S5).

triggered by the decrease in number of crystal nucleus located in each mass ratio increased from 1:1 to 2:1, the ΔHm increased from 164 J/g
capsule, the presence of the impurity (Fig. 2S3), the interaction between to 190 J/g, indicating more TDA was encapsulated.
shell materials and core materials, and the geometric confinement of In order to evaluate the thermal properties of TDA/PMMA/MPCMs,
the microcapsules [38,41–43]. The degree of the super-cooling of micro- encapsulation ratio (Een) [44], the energy storage efficiency (Ees) [45]
capsules prepared in this work is lower to previous reports [1,6,7,43]. and the thermal storage capability (η) parameters [46] were put for-
The crystallization enthalpy (ΔHc) and melting enthalpy (ΔHm) are ward as follows and the results were listed in Table 2.
two essential parameters to evaluate the thermal energy storage/re-
lease capability of PCMs and can be obtained by calculating the area of
the peak. The results were summarized in Table 2. Pristine TDA has con- ΔHm;micro
Een ¼  100% ð1Þ
siderably high phase change enthalpies about 230 J/g. When the core/ ΔHm;PCM
monomer mass ratio was fixed at 1:1, the enthalpies of the TDA/
PMMA/MPCMs decreased with increasing PETRA dosage. This phenom-
enon can be explained by the fact that thicker shells were formed with ΔHm;micro þ ΔHc;micro
Ees ¼  100% ð2Þ
more PETRA added and shell materials had no contribution to the en- ΔHm;PCM þ ΔHc;PCM
thalpy during the phase change process. When the core/monomer

Ees
η¼  100% ð3Þ
Een
Table 2
Thermal properties of TDA and TDA/PMMA/MPCMs (S2–S5).

Sample Melting Crystallization Een Ees η where ΔHm,micro and ΔHm,PCM are melting enthalpy of TDA/PMMA/
Tm,o Tm ΔHm Tc,α Tc,β ΔHc
(%) MPCMs and TDA, respectively; ΔHc,micro and ΔHc,PCM are crystallization
(°C) (°C) (J/g) (°C) (°C) (J/g) enthalpy of TDA/PMMA/MPCMs and TDA, respectively.
TDA 32.41 42.74 233.5 31.97 29.66 228.2 – – – As shown in Table 2 the sample S5 has the highest Een of 81.4% with a
S2 33.13 42.74 164.0 30.95 15.36 154.2 70.2 68.9 98.1 melting enthalpy 190 J/g higher than previously reported data
S3 32.84 42.89 151.4 30.50 15.35 143.6 64.8 63. 9 98.6 [1,6,39,47–50]. The actual encapsulation ratio was found to be slightly
S4 32.84 42.46 121.6 30.21 16.96 114.2 52.1 51.1 98.1
higher than the theoretical values according to the formulations listed
S5 32.82 43.48 190.0 30.80 13.75 175.8 81.4 79.2 97.4
in Table 1. The reason could be ascribed to the volatilization and incom-
Note: Tm,0, onset temperature on DSC melting curve; Tm, peak temperature on DSC melt- plete conversion of the monomers during polymerization [32,51].
ing curve; ΔHm, enthalpy on DSC heating curve; Tc,α, alpha peak temperature on DSC
cooling curve; Tc,β, beta peak temperature on DSC cooling curve; ΔHc, enthalpy on DSC
All of the as-prepared TDA/PMMA/MPCMs (S2–S5) presented a
cooling curve; Een, encapsulation ratio; Ees, energy storage efficiency; η, thermal storage thermal storage capability higher than 97%, indicating good potential
capability. to efficiently store and release latent heat.

Fig. 6. (a) Images of pristine TDA and S5 taken at different time intervals during heating at 60 °C and (b) phase change enthalpies of S5 after different heating times.
6 Y. Wang et al. / International Journal of Biological Macromolecules 146 (2020) 1–8

Fig. 7. (a) DSC curves; (b) phase change enthalpies; (c) FT-IR spectra of pristine TDA, PMMA, S4 and S5 and (d) SEM images of samples S4 and S5 after different thermal cycling times: S4
(1th and 200th) and S5 (1th, 40th and 50th).

3.4. Leakage test enthalpy, SEM and FT-IR spectra changes of microcapsules after differ-
ent cycling times were presented in Fig. 7. The DSC curves of the sam-
The leakage test was done using a similar method previously re- ples remained mostly unchanged during the accelerated thermal
ported by Zhu. et al. [38]. Fig. 6a shows the results of the leakage tests cycling tests (Fig. 7a). The melting enthalpies value only decrease
sample S5 by heating them at 60 °C for different hours. Pristine TDA, 0.65% for S4 after 200th cycles and 0.84% for S5 after 40th cycles
which was used as the control, melted in just 5 min upon heating, (Fig. 7b), suggesting both S4 and S5 have good thermal reliability. The
while S5 maintained its powdery appearance and no TDA leakage was FT-IR spectra of pristine TDA and PMMA were shown in Fig. 7c, compar-
observed over 60 h of heating. In addition, it can be inferred from ing with the spectra of TDA, PMMA, all the characteristic peaks can be
Fig. 6b, the melting enthalpies of S5 only decreased by 4.1% (from found in the FT-IR of the microcapsule samples confirming successfully
190 J/g to 182 J/g) after being heated for 60 h. encapsulation of TDA by the PMMA polymer shell [38]. The intensity
and frequency values of all peaks were consistent with the samples be-
fore and after the cycling tests, indicating good structural stability of S4
3.5. Thermal cycling stabilization and S5.
As shown by Fig. 7d, S4 still exhibited smooth and compact surface
Thermal cyclic durability is considered as a significant factor in prac- and spherical shapes even after 200th repeated heating-cooling cycles.
tical applications of PCMs. Samples S4 and S5 were selected to conduct However, broken microcapsules and core leakage were observed after
accelerated thermal cycling tests. The comparison of DSC curves, 50th repeated heating-cooling cycles for S5, which had thinner shells.

Fig. 8. (a) Optical photos of pure gypsum and GS@TDA/PMMA/MPCMs (Gypsum-S1 and Gypsum-S2 containing 10 wt% and 20 wt% MicroPCMs respectively); (b) Infrared camera images
of pure gypsum and GS@TDA/PMMA/MPCMs at different heating times and (c) the surface temperature of the gypsum and GS@TDA/PMMA/MPCMs at different heating times were
captured using a calibrated infrared camera. Pure gypsum (left), Gypsum-S1 (middle) and Gypsum-S2 (right). All samples were sized Ф25 mm × 6 mm.
 Y. Wang et al. / International Journal of Biological Macromolecules 146 (2020) 1–8 7

Fig. 9. (a) DSC curves and (b) phase change enthalpies of gypsum and GS@TDA/PMMA/MPCMs composites.

3.6. Thermal energy storage performance of GS@TDA/PMMA/MPCMs crucial roles on the morphology and thermal enthalpy of the resulting
microcapsules. When the mass ratio of core/monomer was 1:1, the
The amount of energy used in the building sector has increased al- PETRA dosage was 10% of the mass of monomer, the melting enthalpy
most 30% during the past two decades [52]. Some studies have been of the resulting microcapsules was 121 J/g. The thermal cyclic durability
conducted on reducing the building energy by adding PCMs to mortar test indicated the microcapsules had good thermal reliability and chem-
[53] or concrete [54]. So, we prepared a heat storage construction mate- ical stability even after 200th heating-cooling cycles. The melting en-
rial GS@TDA/PMMA/MPCMs to alleviate the energy consumption and thalpy of the microcapsules could reach 190 J/g and the encapsulation
studied its heat storage properties. ratio was as high as 81.4%, when the mass ratio of core/monomer was
As shown in Fig. 8a, color of the GS@TDA/PMMA/MPCMs changed 2:1, the PETRA dosage was 10 wt% of monomer and it also showed
from white to brown upon addition of microcapsules (S5). The infrared good resistance to leakage, where the change in melting enthalpy was
camera images during heating process were displayed in Fig. 8b. It is as low as 4.1% after heating at 60 °C for 60 h. The as-prepared TDA/
clearly observed that the color of the photographs changes gradually PMMA/MPCMs were combined with gypsum to construct GS@TDA/
from purple to green with prolonged time. In order to quantify the tem- PMMA/MPCMs composite that showed good thermal energy-storage
perature difference between the gypsum samples, the average surface performance. The as-prepared TDA/PMMA/MPCMs has great potential
temperature curves of the gypsum composite during the heating pro- as a LTES material for industrial manufacture.
cess were shown in Fig. 8c. The surface temperature of pure gypsum ex- Supplementary data to this article can be found online at https://doi.
hibits a rapid linear increase with longer heating time until it reaches org/10.1016/j.ijbiomac.2019.12.175.
the set temperature of 60 °C, while for the GS@TDA/PMMA/MPCMs, a
temperature hysteresis regime is observed that spans from 31 to
Author statement
50 °C. The appearance of the hysteresis region should be attributed to
the latent heat of added MPCMs. The difference of surface temperature
Yanbin Wang: Conceptualization, Methodology, Validation, Formal
of gypsum composites and pure gypsum becomes more obvious with
analysis, Investigation, Writing - Original Draft, Writing - Review &
increasing content of TDA/PMMA/MPCMs in the composites. This phe-
Editing.
nomenon can be explained by the fact that the higher loading of micro-
Xiang Li: Validation, Writing - Original Draft.
capsules leads to the more amount of latent heat absorbed during the
Chuanfei Shen: Formal analysis, Investigation.
heating process. The temperature of Gypsum-S2 was over 10 °C lower
Zhiping Mao: Methodology, Resources.
than that of pure gypsum at the same heating times indicating the
Hong Xu: Visualization.
Gypsum-S2 had greater thermal insulation performance.
Yi Zhong: Project administration.
The DSC curves and phase change enthalpies of the pure gypsum
Xiaofeng Sui: Conceptualization, Resources, Supervision.
and GS@TDA/PMMA/MPCMs composites were displayed in Fig. 9. Pure
Xueling Feng: Resources, Supervision, Funding acquisition.
gypsum has no phase change behavior during the heating or cooling
Bijia Wang: Conceptualization, Writing - Review & Editing, Funding
process due to the absence of TDA/PMMA/MPCMs, on the contrary,
acquisition.
Gypsum-S1 and Gypsum-S2 demonstrated phase change behavior
(Fig. 9a–b). Although the crystallization behavior became more com-
Acknowledgments
plex after being combined with gypsum, this doesn't affect its applica-
tion as a building material [55]. It is clearly observed that the
This work was financially supported by the Fundamental Research
enthalpies of the GS@TDA/PMMA/MPCMs increased with increasing
Funds for the Central Universities (No. 2232018A3-04).
the amount of TDA/PMMA/MPCMs. The results suggest that the micro-
capsules prepared in this work can maintain the phase change perfor-
Declaration of competing interest
mance for further practical applications after combining with gypsum.
The authors declare no competing financial interest.

4. Conclusions
References

In this work, LNPs with an average size of 160 nm were prepared [1] H. Zhang, W. Li, R. Huang, N. Wang, J. Wang, X. Zhang, Microstructure regulation of
using a nanoprecipitation method. TDA was successfully microencapsu- microencapsulated bio-based n-dodecanol as phase change materials via in situ po-
lymerization, New J. Chem. 41 (2017) 14696–14707.
lated using PMMA as shell based on the O/W Pickering emulsions stabi- [2] Z. Huang, N. Xie, Z. Luo, X. Gao, X. Fang, Y. Fang, Z. Zhang, Characterization of
lized by LNPs. The core/monomer mass ratio and the PETRA dosage play medium-temperature phase change materials for solar thermal energy storage
8 Y. Wang et al. / International Journal of Biological Macromolecules 146 (2020) 1–8

using temperature history method, Sol. Energy Mater. Sol. Cells 179 (2018) [28] H. Bian, L. Chen, R. Gleisner, H. Dai, J.Y. Zhu, Producing wood-based nanomaterials
152–160. by rapid fractionation of wood at 80 °C using a recyclable acid hydrotrope, Green
[3] A. Zhao, J. An, J. Yang, E.-H. Yang, Microencapsulated phase change materials with Chem. 19 (2017) 3370–3379.
composite titania-polyurea (TiO2-PUA) shell, Appl. Energy 215 (2018) 468–478. [29] W. Zhao, B. Simmons, S. Singh, A. Ragauskas, G. Cheng, From lignin association to
[4] J. Yang, L.-S. Tang, R.-Y. Bao, L. Bai, Z.-Y. Liu, B.-H. Xie, M.-B. Yang, W. Yang, Hybrid nano-/micro-particle preparation: extracting higher value of lignin, Green Chem.
network structure of boron nitride and graphene oxide in shape-stabilized compos- 18 (2016) 5693–5700.
ite phase change materials with enhanced thermal conductivity and light-to-electric [30] S. Salentinig, M. Schubert, Softwood lignin self-assembly for nanomaterial design,
energy conversion capability, Sol. Energy Mater. Sol. Cells 174 (2018) 56–64. Biomacromolecules 18 (2017) 2649–2653.
[5] L.-S. Tang, J. Yang, R.-Y. Bao, Z.-Y. Liu, B.-H. Xie, M.-B. Yang, W. Yang, Polyethylene [31] Y. Ma, Q. Xie, X. Wang, J. Lu, Synthesis and characterization of microencapsulated
glycol/graphene oxide aerogel shape-stabilized phase change materials for photo- phase change materials with comb-like acrylic co-polymer shell as thermal energy
to-thermal energy conversion and storage via tuning the oxidation degree of storage materials, Sol. Energy 179 (2019) 410–423.
graphene oxide, Energy Convers. Manag. 146 (2017) 253–264. [32] W. Li, G. Song, G. Tang, X. Chu, S. Ma, C. Liu, Morphology, structure and thermal sta-
[6] X. Geng, W. Li, Q. Yin, Y. Wang, N. Han, N. Wang, J. Bian, J. Wang, X. Zhang, Design bility of microencapsulated phase change material with copolymer shell, Energy 36
and fabrication of reversible thermochromic microencapsulated phase change ma- (2) (2011) 785–791.
terials for thermal energy storage and its antibacterial activity, Energy 159 (2018) [33] M. You, X. Zhang, J. Wang, X. Wang, Polyurethane foam containing microencapsu-
857–869. lated phase-change materials with styrene–divinybenzene co-polymer shells, J.
[7] Y. He, W. Li, N. Han, J. Wang, X. Zhang, Facile flexible reversible thermochromic Mater. Sci. 44 (2009) 3141–3147.
membranes based on micro/nanoencapsulated phase change materials for wearable [34] X.X. Zhang, X.M. Tao, K.L. Yick, Y.F. Fan, Expansion space and thermal stability of
temperature sensor, Appl. Energy 247 (2019) 615–629. microencapsulatedn-octadecane, J. Appl. Polym. Sci. 97 (2005) 390–396.
[8] Z.-H. Chen, F. Yu, X.-R. Zeng, Z.-G. Zhang, Preparation, characterization and thermal [35] X. Qiu, W. Li, G. Song, X. Chu, G. Tang, Fabrication and characterization of microen-
properties of nanocapsules containing phase change material n-dodecanol by capsulated n-octadecane with different crosslinked methylmethacrylate-based
miniemulsion polymerization with polymerizable emulsifier, Appl. Energy 91 polymer shells, Sol. Energy Mater. Sol. Cells 98 (2012) 283–293.
(2012) 7–12. [36] X.L. Shan, J.P. Wang, X.X. Zhang, X.C. Wang, Formaldehyde-free and thermal resis-
[9] F. Yu, Z.H. Chen, X.R. Zeng, X.N. Gao, Z.G. Zhang, Poly(methyl methacrylate) copoly- tant microcapsules containing n-octadecane, Thermochim. Acta 494 (2009)
mer nanocapsules containing phase-change material (n-dodecanol) prepared via 104–109.
miniemulsion polymerization, J. Appl. Polym. Sci. 132 (2015) 1–7. [37] X. Baoquan, L. Guoming, J. Shichun, Z. Ying, W. Dujin, Crystallization behaviors of n-
[10] M.S. Tözüm, S.A. Aksoy, C. Alkan, Microencapsulation of three-component octadecane in confined space: crossover of rotator phase from transient to metasta-
thermochromic system for reversible color change and thermal energy storage, Fi- ble induced by surface freezing, J. Phys. Chem. B 112 (2008) 13310–13315.
bers Polym 19 (2018) 660–669. [38] C. Li, H. Yu, Y. Song, H. Liang, X. Yan, Preparation and characterization of PMMA/TiO2
[11] Y. Ma, J. Zong, W. Li, L. Chen, X. Tang, N. Han, J. Wang, X. Zhang, Synthesis and char- hybrid shell microencapsulated PCMs for thermal energy storage, Energy 167
acterization of thermal energy storage microencapsulated n-dodecanol with acrylic (2019) 1031–1039.
polymer shell, Energy 87 (2015) 86–94. [39] L. Geng, S. Wang, T. Wang, R. Luo, Facile synthesis and thermal properties of
[12] Y. Zhang, J. Wu, B. Wang, X. Sui, Y. Zhong, L. Zhang, Z. Mao, H. Xu, Cellulose nanoencapsulated n-dodecanol with SiO2 shell as shape-formed thermal energy
nanofibril-reinforced biodegradable polymer composites obtained via a Pickering storage material, Energy Fuel 30 (2016) 6153–6160.
emulsion approach, Cellulose 24 (2017) 3313–3322. [40] R. Montenegro, M. Antonietti, Y. Mastai, K. Landfester, Crystallization in
[13] X. Zheng, Y. Zhang, H. Wang, Q. Du, Interconnected macroporous polymers synthe- miniemulsion droplets, J. Phys. Chem. B 107 (2003) 5088–5094.
sized from silica particle stabilized high internal phase emulsions, Macromolecules [41] S. Liang, Q. Li, Y. Zhu, K. Chen, C. Tian, J. Wang, R. Bai, Nanoencapsulation of n-
47 (2014) 6847–6855. octadecane phase change material with silica shell through interfacial hydrolysis
[14] S. Zou, Y. Hu, C. Wang, One-pot fabrication of rattle-like capsules with multicores by and polycondensation in miniemulsion, Energy 87 (2015) 654–662.
Pickering-based polymerization with nanoparticle nucleation, Macromol. Rapid [42] R. Al-Shannaq, J. Kurdi, S. Al-Muhtaseb, M. Dickinson, M. Farid, Supercooling elimi-
Commun. 35 (2014) 1414–1418. nation of phase change materials (PCMs) microcapsules, Energy 87 (2015)
[15] M. Pishnamazi, S. Casilagan, C. Clancy, S. Shirazian, J. Iqbal, D. Egan, C. Edlin, D.M. 654–662.
Croker, G.M. Walker, M.N. Collins, Microcrystalline cellulose, lactose and lignin [43] X. Geng, W. Li, Y. Wang, J. Lu, J. Wang, N. Wang, J. Li, X. Zhang, Reversible
blends: process mapping of dry granulation via roll compaction, Powder Technol. thermochromic microencapsulated phase change materials for thermal energy stor-
341 (2019) 38–50. age application in thermal protective clothing, Appl. Energy 217 (2018) 281–294.
[16] M. Pishnamazi, H. Hafizi, S. Shirazian, M. Culebras, G.M. Walker, M.N. Collins, Design [44] B. Jiang, X. Wang, D. Wu, Fabrication of microencapsulated phase change materials
of controlled release system for paracetamol based on modified lignin, Polymers 11 with TiO2/Fe3O4 hybrid shell as thermoregulatory enzyme carriers: a novel design of
(2019) 1–10. applied energy microsystem for bioapplications, Appl. Energy 201 (2017) 20–33.
[17] M. Pishnamazi, J. Iqbal, S. Shirazian, G.M. Walker, M.N. Collins, Effect of lignin on the [45] L. Chai, X. Wang, D. Wu, Development of bifunctional microencapsulated phase
release rate of acetylsalicylic acid tablets, Int. J. Biol. Macromol. 124 (2019) 354–359. change materials with crystalline titanium dioxide shell for latent-heat storage
[18] A. Beaucamp, Y. Wang, M. Culebras, M.N. Collins, Carbon fibres from renewable re- and photocatalytic effectiveness, Appl. Energy 138 (2015) 661–674.
sources: the role of the lignin molecular structure in its blendability with biobased [46] B. Li, T. Liu, L. Hu, Y. Wang, L. Gao, Fabrication and properties of microencapsulated
poly (ethylene terephthalate), Green Chem. 21 (2019) 5063–5072. paraffin@SiO2 phase change composite for thermal energy storage, ACS Sustain.
[19] W. Boerjan, J. Ralph, M. Baucher, Lignin biosynthesis, Annu. Rev. Plant Biol. 54 Chem. Eng. 1 (2013) 374–380.
(2003) 519–546. [47] F. Yu, Z.-H. Chen, X.-R. Zeng, X.-N. Gao, Z.-G. Zhang, Poly(methyl methacrylate) co-
[20] I. Spiridon, C.E. Tanase, Design, characterization and preliminary biological evalua- polymer nanocapsules containing phase-change material (n-dodecanol) prepared
tion of new lignin-PLA biocomposites, Int. J. Biol. Macromol. 114 (2018) 855–863. via miniemulsion polymerization, J. Appl. Polym. Sci. 132 (2015) 423341–423347.
[21] X. He, F. Luzi, X. Hao, W. Yang, L. Torre, Z. Xiao, Y. Xie, D. Puglia, Thermal, antioxidant [48] Z. Chen, J. Wang, F. Yu, Z. Zhang, X. Gao, Preparation and properties of graphene
and swelling behaviour of transparent polyvinyl (alcohol) films in presence of hy- oxide-modified poly(melamine-formaldehyde) microcapsules containing phase
drophobic citric acid-modified lignin nanoparticles, Int. J. Biol. Macromol. 127 change material n-dodecanol for thermal energy storage, J. Mater. Chem. A 3
(2019) 665–676. (2015) 11624–11630.
[22] M.N. Collins, M. Nechifor, F. Tanasa, M. Zanoaga, A. McLoughlin, M.A. Strozyk, M. [49] Z. Liu, Z. Chen, F. Yu, Enhanced thermal conductivity of microencapsulated phase
Culebras, C.A. Teaca, Valorization of lignin in polymer and composite systems for ad- change materials based on graphene oxide and carbon nanotube hybrid filler, Sol.
vanced engineering applications - a review, Int. J. Biol. Macromol. 131 (2019) Energy Mater. Sol. Cells 192 (2019) 72–80.
828–849. [50] F. Yu, Z.-H. Chen, X.-R. Zeng, Preparation, characterization, and thermal properties of
[23] X. Luo, C. Liu, J. Yuan, X. Zhu, S. Liu, Interfacial solid-phase chemical modification microPCMs containing n-dodecanol by using different types of styrene-maleic anhy-
with Mannich reaction and Fe(III) chelation for designing lignin-based spherical dride as emulsifier, Colloid Polym. Sci. 287 (2009) 549–560.
nanoparticle adsorbents for highly efficient removal of low concentration phos- [51] Y. Zhang, X. Zheng, H. Wang, Q. Du, Encapsulated phase change materials stabilized
phate from water, ACS Sustain. Chem. Eng. 5 (2017) 6539–6547. by modified graphene oxide, J. Mater. Chem. A 2 (2014) 5304–5314.
[24] Y. Ma, Z. Li, H. Wang, H. Li, Synthesis and optimization of polyurethane microcap- [52] E.Y. Tuncel, B.Y. Pekmezci, A sustainable cold bonded lightweight PCM aggregate
sules containing [BMIm]PF6 ionic liquid lubricant, J. Colloid Interface Sci. 534 production: its effects on concrete properties, Constr. Build. Mater. 181 (2018)
(2019) 469–479. 199–216.
[25] X. Li, N. Hegyesi, Y. Zhang, Z. Mao, X. Feng, B. Wang, B. Pukánszky, X. Sui, Poly(lactic [53] S. Kim, S. Paek, S.-G. Jeong, J.-H. Lee, S. Kim, Thermal performance enhancement of
acid)/lignin blends prepared with the Pickering emulsion template method, Eur. mortar mixed with octadecane/xGnP SSPCM to save building energy consumption,
Polym. J. 110 (2019) 378–384. Sol. Energy Mater. Sol. Cells 122 (2014) 257–263.
[26] Y. Qian, X. Zhong, Y. Li, X. Qiu, Fabrication of uniform lignin colloidal spheres for de- [54] U. Stritih, V.V. Tyagi, R. Stropnik, H. Paksoy, F. Haghighat, M.M. Joybari, Integration of
veloping natural broad-spectrum sunscreens with high sun protection factor, Ind. passive PCM technologies for net-zero energy buildings, Sustain. Cities and Soc. 41
Crop. Prod. 101 (2017) 54–60. (2018) 286–295.
[27] H. Yi, W. Zhan, Y. Zhao, X. Zhang, F. Jia, W. Wang, Z. Ai, S. Song, Design of MtNS/SA [55] A. Safari, R. Saidur, F.A. Sulaiman, Y. Xu, J. Dong, A review on supercooling of phase
microencapsulated phase change materials for enhancement of thermal energy change materials in thermal energy storage systems, Renew. Sust. Energ. Rev. 70
storage performances: effect of shell thickness, Sol. Energy Mater. Sol. Cells 200 (2017) 905–919.
(2019) 1–8.