Céline Montanari1, Yuanyuan Li1, Hui Chen1, Max Yan2, Lars A Berglund1. 1. Department of Fiber and Polymer Technology, Wallenberg Wood Science Center , KTH Royal Institute of Technology , Teknikringen 56 , 100 44 Stockholm , Sweden. 2. Department of Applied Physics , KTH Royal Institute of Technology , Isafjordsgatan 22 , 164 40 Kista , Sweden.
Abstract
Functional load-bearing materials based on phase-change materials (PCMs) are under rapid development for thermal energy storage (TES) applications. Mesoporous structures are ideal carriers for PCMs and guarantee shape stability during the thermal cycle. In this study, we introduce transparent wood (TW) as a TES system. A shape-stabilized PCM based on polyethylene glycol is encapsulated into a delignified wood substrate, and the TW obtained is fully characterized, also in terms of nano- and mesoscale structures. Transparent wood for thermal energy storage (TW-TES) combines large latent heat (∼76 J g-1) with switchable optical transparency. During the heating process, optical transmittance increases by 6% and reaches 68% for 1.5 mm thick TW-TES. Characterization of the thermal energy regulation performance shows that the prepared TW-TES composite is superior to normal glass because of the combination of good heat-storage and thermal insulation properties. This makes TW-TES composites interesting candidates for applications in energy-saving buildings.
Functional load-bearing materials based on phase-change materials (PCMs) are under rapid development for thermal energy storage (TES) applications. Mesoporous structures are ideal carriers for PCMs and guarantee shape stability during the thermal cycle. In this study, we introduce transparent wood (TW) as a TES system. A shape-stabilized PCM based on polyethylene glycol is encapsulated into a delignified wood substrate, and the TW obtained is fully characterized, also in terms of nano- and mesoscale structures. Transparent wood for thermal energy storage (TW-TES) combines large latent heat (∼76 J g-1) with switchable optical transparency. During the heating process, optical transmittance increases by 6% and reaches 68% for 1.5 mm thick TW-TES. Characterization of the thermal energy regulation performance shows that the prepared TW-TES composite is superior to normal glass because of the combination of good heat-storage and thermal insulation properties. This makes TW-TES composites interesting candidates for applications in energy-saving buildings.
Entities:
Keywords:
biocomposite; encapsulation; energy storage; phase-change material; wood
The global energy consumption in the building
sector exceeds 30%, and technologies for reduced energy consumption
and CO2 emission are therefore under development.[1] Transparent wood (TW) composites are of interest
in energy-saving buildings because of low thermal conductivity (0.15
W m–1 K–1),[2,3] high
optical transmittance (92% for 1.5 mm thick),[4] and haze (80% for 1 mm thick),[5] as well
as favorable mechanical properties.[6−8] To prepare TW, a wood
template is first chemically treated for removing lignin, which is
the major light-absorbing component in wood. In a second step, light
scattering is reduced by infiltrating the pore space with a polymer
component matching the wood refractive index.[9] In comparison to glass, which is generally used for light-transmitting
building structures, the TW shows better thermal insulation and could
reduce heat loss. Furthermore, the TW exhibits a combination of high
optical transmittance and haze, which offers uniform indoor lighting
while preserving privacy. Most of the reported studies on TW for energy-saving
applications focus on the excellent thermal insulating properties
of this material.[2,10] Thermal energy storage (TES)
has emerged as a key technology to harvest and store solar energy.
Latent heat storage systems based on phase-change materials (PCMs)
are among the most efficient in reducing energy consumption because
of their large latent heat capacity over a narrow temperature range.[11−13] PCMs act as temperature regulators that can store and release thermal
energy in order to shift the heating and cooling loads over time and
thus reduce heat energy loss. In particular, organic PCMs store latent
heat energy during a reversible solid–liquid phase-change process
that occurs at the melting temperature of the material.[14,15]The present study focuses on the incorporation of polyethylene
glycol (PEG) in the TW. PEG is nontoxic and biodegradable, with a
large latent heat and a tunable solid–liquid transition temperature
that can be varied by tuning PEG molecular weight.[16,17] However, solid–liquid PCMs such as PEG suffer from leakage
issues during melting, which limits their long-term thermal reliability.
In order to address leakage issues, PEG can be entrapped by a surrounding
polymer matrix, such as polymethyl methacrylate (PMMA).[18−21] Porous supporting materials can be used to encapsulate the PCM,[22] such as silica and cellulosic networks.[23,24] Here, wood is investigated as a PCM substrate. Wood is an abundant
and renewable material, which has a unique hierarchical structure
with organized cells formed during tree growth[25−27] Wood cells
have structurally advantageous microscale pores for chemical modification
and polymer impregnation. The diameter could be 10–50 μm,
with length at the scale of millimeters. Because delignified wood
(DW) has a unique mesoporous cell wall structure, a high specific
area, and a high adsorption capacity,[6] it
is an attractive supporting material for PCM encapsulation. Therefore,
in this study, the PCM was encapsulated into a DW scaffold. Very few
studies report the use of wood scaffold as a porous supporting material
for PCM.[28−30] Excellent TES properties are reported in the present
study, associated with high optical transmittance and haze. A multifunctional
TW material was prepared via a two-step procedure, which involves
wood delignification followed by encapsulation of the PEG/PMMApolymer
blend into the porous DW scaffold. A schematic representation of the
preparation procedure of the multifunctional TW, labeled as a transparent
wood for thermal energy storage (TW-TES), is shown in Figure . TW-TES can store thermal
energy even for small temperature variations and combines excellent
latent heat storage properties with low thermal conductivity, tunable
optical transmittance, and robust mechanical performance. These properties
make the multifunctional TW-TES composite a potential candidate for
heat-transfer control in building applications, such as light-transmitting
structures with reduced heat energy consumption and improved thermal
comfort indoors. The objectives are to investigate the TW-TES concept
and its potential. Also, the mesoscale structures are investigated
so that the role of PCM distribution in TW-TES can be assessed.
Figure 1
Schematic representation
of the two-step preparation of TW-TES applications. First, wood is
delignified to remove absorbing lignin, and subsequently, the PEG/MMA
blend is infiltrated and polymerized into the wood fibers and vessels.
Schematic representation
of the two-step preparation of TW-TES applications. First, wood is
delignified to remove absorbing lignin, and subsequently, the PEG/MMA
blend is infiltrated and polymerized into the wood fibers and vessels.
Experimental Section
Materials
Silver birch wood (Betula pendula, purchased from Glimakra of Sweden AB) with an oven-dried density
of 620 kg/m3 was used as a raw material. Specimens with
dimensions of 2 cm × 2 cm × 0.5 mm and 2 cm × 2 cm
× 1.5 mm were prepared. More specimens were prepared for mechanical
testing with dimensions of 5 mm × 60 mm × 1.5 mm. Sodium
chlorite (NaClO2, Alfa Aesar), 2,2′-azobis(2-methylpropionitrile)
(AIBN, Sigma-Aldrich), and PEG (Sigma-Aldrich) with a molecular weight
of 1000 g mol–1 were used as received. Methyl methacrylate
(MMA, Sigma-Aldrich) was passed through a column of neutral aluminum
oxide (Sigma-Aldrich) prior to use to remove the inhibitor.
Delignification
of the Wood Samples
The delignification process was performed
using NaClO2 (1 wt %) in an acetate buffer solution (pH
4.6) at 80 °C. The reaction was ended once the wood samples became
white. The DW samples were then thoroughly washed several times with
deionized water and sequentially dehydrated with ethanol and acetone.
Preparation of TW-TES Composites
PEG 1000 was heated at
45 °C until complete dissolution. MMA (30 wt %) was added to
the molten PEG (70 wt %) solution and kept under stirring at 45 °C
for 10 min. The initiator, AINB (0.3 wt % based on MMA), was then
added to the PEG/MMA solution, and the blend was continuously stirred
at 45 °C for 10 min. The maximum PEG/PMMA ratio without any leakage
during phase transition was 70/30 (w/w). The DW sample was then immersed
in the blend solution for infiltration. Infiltration was performed
under vacuum at room temperature for about 15 min; it was repeated
three times. The blend solution containing the DW samples was heated
at 40 °C for a few minutes between each infiltration to delay
PEG crystallization. The infiltrated DW template was finally sandwiched
between two glass slides, packaged with aluminum foil, and polymerized
in an oven at 70 °C for 4 h. The final TW-TES composites prepared
have thicknesses of 0.5 and 1.5 mm and possess a thin layer of PEG/PMMA
at their surfaces. The density of the final composite was determined
by measuring their dimensions and weight. The DW volume fraction was
determined and is presented in Table S1.
Characterization
The cross-sectional morphologies of TW-TES
composites were characterized by field emission scanning electron
microscopy (Hitachi SEM S-4800, Japan). A differential scanning calorimeter
(Mettler Toledo DSC1, Switzerland) was used to analyze the thermal
properties of neat PEG, PEG/PMMApolymer blend, and TW-TES composite
under nitrogen with a flow rate of 50 mL min–1.
The samples were heated from 0 to 60 °C with a heating rate of
2 °C min–1. The latent heat was determined
by numerical integration of the area of the thermal transition peak.
The thermal reliability of the TW-TES composite was investigated by
performing 20 heating–cooling cycles. The data were recorded
from the second scan. The thermal stability of the TW-TES composite
was studied by thermogravimetric analysis (TGA) using a Mettler Toledo
TGA/DSC1 (Switzerland) with a heating rate of 10 °C min–1 from room temperature to 600 °C under nitrogen atmosphere.
A light flash apparatus (LFA 467 HyperFlash Netzsch, Germany) was
employed to determine cross-plane thermal diffusivities (α)
on square samples (20 × 20 × 1.5 mm). The measurements were
performed at 45 °C in order to avoid the PCM phase transition.
The sample surfaces were graphitized using a graphite spray before
the measurements. Thermal conductivity, κ, was then calculated
from the equation κ = ραC, where ρ is the density and C is the specific heat capacity of the
material. The chemical structure of native wood (NW), DW, neat PEG,
neat PMMA, and TW-TES composite was evaluated by Fourier transform
infrared spectrometry (FTIR) using a PerkinElmer spectrum 100 FT-IR
equipped with a MKII Golden Gate, single-reflection accessory unit
with a diamond ATR crystal (Graseby Specac Ltd., UK). The spectra
were recorded at room temperature in the range of 4000–600
cm–1. Tensile tests and three-point bending tests
were performed using an Instron 5944 (USA) instrument equipped with
a 500 N load cell. The tests were carried out with a 10% min–1 strain rate and span of 30 mm. All samples were preconditioned
for 24 h and tested in a room at a temperature of 22 ± 1 °C
and 50 ± 2% relative humidity. The optical measurements were
performed using an integrating sphere in the visible and NIR wavelength
region (400–1000 nm). A Quartz tungsten halogen light source
(model 66181 from Oriel Instruments) with strong, stable output mainly
in the visible and NIR region was used. The visible transmittance
and haze were measured according to ASTM D1003 “Standard Method
for Haze and Luminous Transmittance of Transparent Plastics”[31] by placing the sample at the entrance port of
the integrating sphere and following the same procedure as previously
reported in another study.[6] Thermal images
were captured using an infrared camera (FLIR A655sc).
Results
and Discussion
Morphological and Chemical Analysis
A TW composite is prepared with encapsulated PCM for TES applications.
Silver birch was used as a starting material. Wood tissues comprise
elongated tubular cells preferably aligned in the longitudinal direction
of the stem. In silver birch species, close-ended libriform fibers
provide mechanical support, whereas water conduction is supplied by
open-ended vessels. Birch fibers and vessels have a mean diameter
of 18 and 82 μm, respectively. At the ultrastructural level,
the cell wall structure of the wood cells consists of layers with
oriented cellulose microfibrils bonded by a mixed hemicelluloses-lignin
matrix. Figure a shows
the SEM image of the cell wall structure of birch wood. The delignification
process adds nanoscale porosity in the middle lamella (lignin-rich
region) and in the cell wall,[6] while preserving
the anisotropic structure of wood (Figures b and S1). PEG
with a molecular weight of 1000 g mol–1 was chosen
as the PCM owing to its excellent energy storage capacity at a suitable
working temperature range; in addition, PEG is highly miscible with
wood.[32−34] In order to guarantee high-energy density and avoid
PEG leakage during the phase transition, PEG (70 wt %) was mixed with
MMA monomer (30 wt %) and AIBN as an initiator, the blend was infiltrated
in the DW scaffold, and then MMA polymerized, so that a polymer blend
termed PEG/PMMA was formed. The DW scaffold is used as a supporting
structure for encapsulation of the PEG/PMMApolymer blend. TW-TES
composites with thicknesses of 0.5 and 1.5 mm were prepared. The morphology
of the TW-TES composite was investigated using SEM and is presented
in Figure c. Upon
infiltration, the wood microstructure is preserved and the PEG/PMMA
blend is homogeneously distributed at the scale of 20 μm so
that the cell lumen is completely filled by the polymer phase. PEG/PMMA
is of immiscible two-phase polymer blend.[19,20] No interface gaps were apparent between PEG/PMMA and the wood cell
wall. This indicates favorable interfacial interaction between PEG/PMMApolymer blend and the wood cell wall (Figure d). This may be attributed to the good miscibility
between the hydrophilic PEG phase and the wood cell wall. Figure e shows the interior
of TW-TES wood cell wall where polymer domains are apparent, indicating
the successful impregnation of the wood cells.
Figure 2
SEM micrographs showing
(a) original birch wood and (b) delignified birch wood. SEM images
of TW-TES (c) shows the successful impregnation of DW with PEG/PMMA
and (d) shows the integrity between wood cell wall and PEG/PMMA matrix.
(e) SEM micrograph of the interior of TW-TES wood cell wall. (f) FTIR
spectra of NW, DW, TW-TES, neat PMMA, and neat PEG.
SEM micrographs showing
(a) original birch wood and (b) delignified birch wood. SEM images
of TW-TES (c) shows the successful impregnation of DW with PEG/PMMA
and (d) shows the integrity between wood cell wall and PEG/PMMA matrix.
(e) SEM micrograph of the interior of TW-TES wood cell wall. (f) FTIR
spectra of NW, DW, TW-TES, neat PMMA, and neat PEG.In order to assess if the PEG phase is located
in the cell wall, a DW piece was soaked in a 30 wt % PEG 1000 aqueous
solution and the cell wall morphology was evaluated. Figure S2 shows a high-resolution SEM image of the wood cell
wall after PEG infiltration. After PEG infiltration, PEG-rich domains
could be identified and no pores were detected at this scale in contrast
with DW before infiltration (Figure S1).
The similarities between the SEM micrographs of the cell wall interior
shown in Figures e
and S2 provide support for PEG diffusion
into the wood cell wall. Figure e indicates that the PEG-rich domain inside the cell
wall is at the scale of 100–200 nm particles.The chemical
interactions between the PCM and the DW template in TW-TES composites
were analyzed by the FTIR analysis. FTIR spectra of NW, DW, neat PMMA,
neat PEG, and TW-TES composite are presented (Figure f). In comparison with NW, the peak at 1505
cm–1 attributed to aromatic skeleton vibrations
from lignin is lacking from the DW spectrum.[35] This confirms successful removal of lignin by delignification. In
addition, all of the major characteristic absorption peaks of DW,
PEG, and PMMA are present in the TW-TES composite. The absorption
peak of PMMA ascribed to C=O stretching (1725 cm–1) is present. Moreover, shift in the O–H stretching vibration
peak in the TW-TES (3419 cm–1) spectrum compared
with that of DW (3350 cm–1) and PEG (3468 cm–1) indicates hydrogen-bonding interactions between
PEG and DW. The PEG absorption peak at 947 cm–1,
attributed to −CH2 vibrations,[36] is shifted in TW-TES, also suggesting intermolecular interaction
between PEG and DW. Thus, the DW template can effectively prevent
leakage because of capillary forces and intermolecular interactions
with the small-scale PCM domains. No new absorption peak is apparent
in the TW-TES spectrum, so that only intermolecular interactions are
expected between PEG and PMMA and between PEG and the DW template.
The stabilization of PEG in PMMA and DW template does not significantly
alter the chemical structure of PEG, and the thermal properties of
PEG are possibly preserved.
Thermal Properties
The TES properties
are important for the application of TW-TES in energy-saving buildings.
Thermal storage cycles include two steps: absorption of latent heat
by the crystalline polymer (PEG) upon heating above the melting temperature
(Tm) and latent heat release during cooling
until the crystallization temperature (Tc). The melting and cooling curves of neat PEG, PEG/PMMA blend, and
TW-TES composite are presented in Figure a,b, respectively. TW-TES shows excellent
thermal properties with latent heat of melting and crystallization
of about 76 and 74 J g–1, respectively. The melting
process of TW-TES occurs over a temperature range between ∼27
and ∼40 °C, with a Tm of 38
°C. When heated above Tm, the TW-TES
composite consists of molten PEG encapsulated into the wood template
and surrounded by PMMA. At this stage, the TW-TES stores latent heat
of the liquid PCM. Cooling until the crystallization point (Tc = 29 °C) will initiate the crystallization
of PEG and hence release the stored latent heat. The differential
scanning calorimetry (DSC) curves show that TW-TES exhibits endothermic
and exothermic behavior similar to the PEG/PMMA blend. Neat PEG exhibits
a shoulder on the leading edge of the endothermic peak associated
with the melting point of crystallites. The presence of a shoulder
is a consequence of heterogeneous melting and is attributed to variations
in crystal thicknesses.[17,37] Further support is
given in Table , which
summarizes the latent heat of melting (ΔHm) and crystallization (ΔHc) and characteristic temperatures (Tm and Tc) of neat PEG, PEG/PMMA, and TW-TES
composite. The theoretical data were defined as follow: ΔHTh = X·ΔHPEG, where ΔHTh is the theoretical latent heat, ΔHPEG is the latent heat of neat PEG, and X is the mass
fraction of PEG. The enthalpy values of PEG/PMMA blend and TW-TES
composite are proportional to the PEG fraction and are shown in Table . The experimental
results for TW-TES were close to predicted data based on PEG/PMMA
behavior. This can be attributed to the preserved thermal performance
of PEG in TW-TES, and it indicates that the domain size of PEG is
sufficiently large so that PEG preserves its melting and crystallization
behavior. If PEG was completely soluble in the wood cell wall, the
melting and crystallization behavior could have been altered in a
negative manner because of the lower PEG crystallinity.
Figure 3
(a) DSC scans
of neat PEG, PEG/PMMA blend, and TW-TES obtained while heating from
0 to 60 °C followed by (b) cooling process. (c) DSC curves of
TW-TES before and after thermal cycling, indicating good thermal reliability
after 20 cycles. (d) TG/DTG curves of DW, neat PEG, neat PMMA and
TW-TES.
Table 1
Thermal Properties
of Neat PEG, Neat PEG/PMMA Blend, and TW-TES Composite During the
Melting and Crystallization Processes
Tm [°C]a
ΔHm [J g–1]b
ΔHmTh [J g–1]c
Tc [°C]d
ΔHc [J g–1]e
ΔHcTh [J g–1]f
neat PEG
37.8 ± 0.3
159.0 ± 2.1
29.5 ± 0.7
161.5 ± 2.5
PEG/PMMA (70/30 w/w)
36.9 ± 0.2
103.0 ± 2.5
111.3
25.5 ± 1.2
101.1 ± 0.2
113.1
TW-TES composite
38.3 ± 0.3
76.3 ± 3.4
77.3
28.6 ± 1.3
74.2 ± 3.1
78.5
Melting temperature.
Latent heat of melting.
Theoretical latent heat of melting.
Crystallization temperature.
Latent heat of crystallization.
Theoretical latent heat of
crystallization. The values in the tables are given as mean ±
standard deviations.
(a) DSC scans
of neat PEG, PEG/PMMA blend, and TW-TES obtained while heating from
0 to 60 °C followed by (b) cooling process. (c) DSC curves of
TW-TES before and after thermal cycling, indicating good thermal reliability
after 20 cycles. (d) TG/DTG curves of DW, neat PEG, neat PMMA and
TW-TES.Melting temperature.Latent heat of melting.Theoretical latent heat of melting.Crystallization temperature.Latent heat of crystallization.Theoretical latent heat of
crystallization. The values in the tables are given as mean ±
standard deviations.The
phase-change phenomenon is critical to TW-TES performance, and it
was therefore investigated if PEG could crystallize in the wood cell
wall. A DW template was soaked in 30 wt % aqueous PEG solution in
order to selectively infiltrate the wood cell walls, while keeping
the lumen pore space free of polymer. The DSC analysis was performed
on the DW template with PEG infiltrated cell walls (Figure S3). Latent heat of melting and crystallization of,
respectively, 39 and 38 J g–1 were achieved when
PEG was located in the wood cell wall only. It is concluded that crystallization
of PEG does not only take place in the microscale lumen space but
also in the wood cell wall. This provides further information with
respect to PEG distribution and supports that the wood cell wall contains
PEG-rich domains. The PCM penetrates throughout the whole wood template,
ensuring high heat storage efficiency in TW-TES.The thermal
reliability of the TW-TES composite was evaluated by performing 20
heating–cooling cycles. Data are presented in Figure c. After 20 cycles, the phase-change
temperatures, Tm and Tc, remain comparable with those at the initial state.
After cycling, the latent heat of crystallization ΔHc showed a minor increase of 0.55% because of enhanced
nucleation of PEG crystallites after several heating–cooling
cycles. The latent heat of melting, ΔHm, did not show any variations. TW-TES exhibits excellent thermal
reliability after 20 thermal cycles.The thermal stability was
evaluated using TGA in nitrogen, and the TG curves of neat PEG and
TW-TES are shown in Figure d. From 30 to 150 °C, TW-TES exhibits only 1.0% weight
loss attributed to residual moisture evaporation, which is much lower
than that for the DW template (5.3%). TW-TES exhibits a two-step degradation
starting from ∼290 °C, including the degradation of DW
template and the degradation of PMMA and PEG compounds. The thermo-oxidative
stability was also studied in oxygen (Figure S4). Under these conditions, thermal oxidation of TW-TES starts from
∼190 °C. The degradation of TW-TES is initiated by the
production of formic esters originating from the degradation of PEG.[38] Overall, these results show that TW-TES is thermally
stable below ∼290 °C in the absence of oxygen (nitrogen
environment), and below ∼190 °C in an oxidative environment
(oxygen).Thermal insulating materials are essential in limiting
heat loss and thus reducing energy consumption in buildings. A light
flash test was employed in order to preliminary evaluate the thermal
conductivity of TW-TES composites. TW-TES has efficient thermal insulation
properties with a low cross-plane thermal conductivity of 0.30 W m–1 K–1, compared with 1.36 W m–1 K–1 for normal glass (Table S2). The combination of heat storage and
thermal insulation properties is favorable.
Optical Function and Mechanical
Properties
Wood optical transparency is obtained by first
partially removing the lignin component and then introducing a material
matching closely the wood refractive index in order to reduce the
light scattering sources located at the air/wood interfaces in the
lumen area and inside the cell wall.[38] In
our study, optical transmittance was obtained by infiltrating the
PEG/PMMA blend in the porous DW structure.TW-TES shows good
optical properties with switchable optical transmittance during the
phase-change process. The optical properties of TW-TES were determined
using an integrating sphere at temperatures below and above Tm to assess the variations in optical properties
with temperature (Figure a,b). The optical transmittance of TW-TES increases by 6%
at λ = 550 nm after the phase change (T > Tm) as PEG crystals melt in the composite. As
the temperature is lowered below Tm, the
optical transmittance of TW-TES is reduced because of the crystallization
of PEG. The change in transmittance can be visually observed as the
TW-TES composite changes from opaque to transparent when undergoing
the phase transitions (Figure c). Above Tm, 1.5 mm thick TW-TES
shows a transmittance of 68%. Lower thickness results in higher optical
transmittance because a shorter light pathway lowers light attenuation.[39] The TW-TES specimen with a thickness of 0.5
mm results in transmittance up to 84% above Tm. It should be noted that the PEG/PMMA blend has a transmittance
of 86% above Tm. The difference in transmittance
is probably caused by the refractive index mismatch between holocellulose
(1.53), PEG (1.46), and PMMA (1.49).[38,40] Haze is the
percentage of transmitted light that is scattered at large angles
from the direction of light propagation.[41] The haze of 1.5 mm thick TW-TES (77% at λ = 550 nm) did not
significantly vary with temperature. As the haze was measured by subtracting
the transmitted light at small scattering angles, the visual difference
might be due to transmitted light which is scattered to larger angles.
A relative decrease in haze of 3% was observed for the thinner specimens
when heated above Tm. This can be attributed
to a reduction in scattering centers, such as voids, upon melting
of PEG crystals. The visual change in transparency of TW-TES with
increased temperature can be advantageous for applications such as
temperature sensors for the environment and light-transmitting structures
with homogeneous lighting.
Figure 4
Optical (a) transmittance and (b) haze of TW-TES
at below and above the melting temperature (Tm) of PCM in the visible spectrum range. (c) Images showing
the visible change from opaque to transparent with increase in temperature
for 0.5 and 1.5 mm thick TW-TES specimens. The transmittance is tunable
by varying the temperature. (d) Tensile test curves and table showing
the strength and elastic modulus of NW and TW-TES. Note: the values
in the tables are given as mean ± standard deviations.
Optical (a) transmittance and (b) haze of TW-TES
at below and above the melting temperature (Tm) of PCM in the visible spectrum range. (c) Images showing
the visible change from opaque to transparent with increase in temperature
for 0.5 and 1.5 mm thick TW-TES specimens. The transmittance is tunable
by varying the temperature. (d) Tensile test curves and table showing
the strength and elastic modulus of NW and TW-TES. Note: the values
in the tables are given as mean ± standard deviations.The mechanical properties were
evaluated below Tm using three-point bending
and tensile tests. The reduced stress–strain curves of TW-TES
from flexural tests for longitudinal properties are shown in Figure S5. TW-TES shows a flexural strength of
74.5 ± 10.2 MPa and a strain to failure as high as 3.2 ±
0.6%. Glass shows brittle nature with a low strain to failure (0.2
± 0.1%), whereas TW-TES is much more ductile (3.2%). Overall,
the work to fracture of TW-TES (1.9 MJ m–3, area
under stress–strain curve) is about 10 times higher than that
for glass (0.2 MJ m–3) because of more favorable
mechanisms of failure in TW-TES composites. Tensile test results for
NW and TW-TES are shown in Figure d. TW-TES shows high elastic modulus (14.9 ± 1.3
GPa) compared with polymers, and this is similar to NW (14.5 ±
3.4 GPa). TW-TES shows a strength of 70.5 ± 6.6 MPa, which is
lower than that for NW (129.6 ± 10.4 MPa). The lower strength
of the TW-TES composite could be attributed to the presence of residual
nanoporosity in the cell wall because of delignification. In addition,
PEG impregnation reduces mechanical strength because molar mass and
PEG glass-transition temperature are low, so that stress transfer
between cellulose fibrils in the cell wall is compromised.[33] In general, TW-TES shows satisfactory mechanical
strength and modulus for load-bearing applications. An important reason
is the relatively low porosity of birch wood, which means that the
content of wood cell wall material is high.In order to demonstrate
the TES performance of TW-TES in real applications, an infrared camera
was used to record temperature changes in TW-TES during heating. Specimens
at room temperature were placed on a heating plate set at a temperature
of 60 °C, and the time for each specimen to reach the heating
plate temperature was recorded. Figure shows thermal images of TW-TES and glass specimens
when placed in contact with a surface heated at 60 °C. The samples
were transferred simultaneously from room temperature to the heated
surface (Figure a).
After 20 s, the glass specimen reached the temperature of the heated
surface (Figure b),
indicating the fast temperature equilibration. In contrast, TW-TES
required 210 s of heating in order to reach the equilibrium temperature
(Figure c), showing
the heat storage capacity and thermal energy regulating property of
TW-TES. The equilibration temperature of TW-TES was compared with
TW without PCM, prepared as previously reported.[6] The results are shown in the Supporting Information (Video S1). The results show that temperature
equilibrium of the specimens is first reached by glass, followed closely
by TW without PCM, and finally by TW-TES. Compared with TW without
PCM, TW-TES shows great efficiency in terms of TES. These differences
between glass and TW-TES are attributed to the lower thermal conductivity
of TW-TES and to the ability of the TW-TES composite to absorb and
store thermal energy. TW-TES is a candidate as heat-storage and light-transmitting
material for applications in energy-saving buildings.
Figure 5
Thermal images for thermal
evolution of TW-TES and glass with respect to time when placed from
room temperature to a surface heated at 60 °C. (a) Start of the
experiment, (b) after 20 s, the glass specimen has reached the temperature
of the heated surface and (c) TW-TES reaches it after 210 s.
Thermal images for thermal
evolution of TW-TES and glass with respect to time when placed from
room temperature to a surface heated at 60 °C. (a) Start of the
experiment, (b) after 20 s, the glass specimen has reached the temperature
of the heated surface and (c) TW-TES reaches it after 210 s.
Conclusions
This
study presents a novel concept of multifunctional TW-TES that combines
mechanical properties, TES, and optical transmittance. A mesoporousDW template was used as a supporting, nonleaking substrate material
for encapsulation of the PCM. The TW-TES composite was obtained by
impregnation with a liquid PEG/MMA blend, followed by MMA polymerization.
The final impregnated polymer component was a 70/30 (w/w) physical
blend of PEG/PMMA.The TES properties of the TW-TES composite
were highly favorable and proportional to the 49 wt % PEG content.
The TES function was combined with high mechanical properties. In
addition, the materials showed tunable optical transmittance when
the external temperature was increased because the PEG phase was melting.
With increasing thickness, the optical transmittance is reduced because
of increasing light attenuation. This can be a limitation for applications
of higher thickness TW-TES as light-transmitting materials. The optical
transmittance of TW-TES can be enhanced by reducing the wood volume
fraction by using higher porosity wood species, so that the number
of wood/polymer interfaces is lowered.Dissolution experiments
suggest that the PEG phase was continuous in the wood lumen pore space.
The morphological analysis of TW-TES composites also indicates that
a PEG-rich phase was present in the wood cell wall, in the form of
100–200 nm mesoscale domains. The PEG distribution is critical
to the mechanical, optical, and TES properties of the material.The design of TW-TES materials requires optimization of mechanical
properties with respect to TES capacity. The PEG content could be
increased by the selection of higher porosity wood species, but then
the mechanical performance would be reduced.The thermal properties
of the TW-TES composite can be further tailored, for instance, by
tuning the melting temperature of PEG. The present concept of multifunctional
TW materials can expand the applications of wood-based materials to
new areas including temperature sensors, heat storage, and light-transmitting
structural materials.
Authors: Martin Höglund; Jonas Garemark; Mathias Nero; Tom Willhammar; Sergei Popov; Lars A Berglund Journal: Chem Mater Date: 2021-05-04 Impact factor: 9.811
Authors: Hui Chen; Adil Baitenov; Yuanyuan Li; Elena Vasileva; Sergei Popov; Ilya Sychugov; Max Yan; Lars Berglund Journal: ACS Appl Mater Interfaces Date: 2019-09-13 Impact factor: 9.229
Authors: Tainise Lourençon; Michael Altgen; Timo Pääkkönen; Valentina Guccini; Paavo Penttilä; Eero Kontturi; Lauri Rautkari Journal: ACS Omega Date: 2022-02-16