Biocomposite foams consisting of microencapsulated phase change materials for enhanced climatic regulation with reduced carbon dioxide emissions in buildings

Construction and Building Materials 448 (2024) 138214
Contents lists available at ScienceDirect
Construction and Building Materials

journal homepage: www.elsevier.com/locate/conbuildmat
Biocomposite foams consisting of microencapsulated phase change

materials for enhanced climatic regulation with reduced carbon dioxide
emissions in buildings
Osman Gencel a,* , Ercan Aydoğmuş b , Onur Güler c, Abid Ustaoğlu d , Ahmet Sarı c,e,
Gökhan Hekimoğlu c, Serkan Subaşı f, Muhammed Maraşlı g
a
Civil Engineering Department, Faculty of Engineering, Architecture and Design, Bartin University, Bartin 74100, Türkiye
b
Department of Chemical Engineering, Faculty of Engineering, Fırat University, Elazığ 23119, Türkiye
c
Department of Metallurgical and Material Engineering, Karadeniz Technical University, Trabzon 61080, Türkiye
d
Department of Mechanical Engineering, Faculty of Engineering, Architecture and Design, Bartin University, Bartin 74100, Türkiye
e
Interdisciplinary Research Center of Renewable Energy and Power Systems (IRC-REPS), King Fahd University of Petroleum & Minerals, Dhahran 31261, Saudi Arabi
f
Department of Civil Engineering, Faculty of Technology, Düzce University, Düzce, Türkiye
g
Fibrobeton Inc., Istanbul 34810, Türkiye
A R T I C L E I N F O A B S T R A C T
Keywords: Using polyurethane foam (PUF) matrix-based phase change material-enhanced composites is crucial for
Biocomposite improving energy efficiency, enhancing thermal regulation, and reducing environmental impact in buildings.
Polyurethane foam Integrating bio-components into PUF production and using these bio-composite foams (BPUFs) as the matrix
Microencapsulated phase change material,
offers environmentally friendly and structurally advanced solutions. Microencapsulated phase change material
renewable energy
Energy and energy efficiency
(MPCM) further enhances these foams, creating innovative, high-performance, eco-friendly composites for
Carbon emission reduction building applications. In this context, the biocomponent castor oil (CO) to be used in BPUF production has been
modified with epoxy. BPUF-MPCM biocomposites with different compositions were produced using MPCM in the
range of 0–90 wt% and modified castor oil (MCO) in the range of 0.75–7.50 wt% in BPUF production. The
addition of 90 wt% MPCM content in BPUF-MPCM biocomposites has facilitated the attainment of a melting
enthalpy value of 176.8 J/g (at 25.4 ◦ C) while providing a solidification enthalpy value of 175.7 J/g (at 20.8 ◦ C).
The advancements in the microstructure of BPUF-MPCM composites contribute to physical improvements, such
as a more homogeneous cell structure and enhancements in thermal transformation properties, thereby
contributing to their thermoregulatory characteristics. BPUF-MPCM 90 wt% composites have achieved 100 %
energy savings and zero CO2 emission values by varying material thicknesses across all climate conditions.
Materials with environmentally friendly characteristics play a crucial

1. Introduction role in addressing global sustainability challenges. The significance of
these materials lies in their ability to reduce the environmental footprint
In recent years, the significance of utilizing materials with enhanced of various industries. Additionally, their adoption leads to substantial
thermal properties in buildings has increasingly gained importance, savings in natural resource consumption, such as water and energy, with
primarily due to their significant contributions to energy saving and CO2 potential efficiency gains of up to 40 % [7]. Moreover, their biode
reduction [1–3]. This trend is especially noticeable in the construction gradability and recyclability offer long-term benefits by minimizing
industry, where energy consumption and building carbon emissions waste generation and promoting circular economy principles. Thus,
significantly impact the overall environment. By incorporating prioritizing eco-friendly materials not only aligns with environmental
high-performance materials into building design and construction pro objectives but also presents economic advantages and fosters sustainable
cesses, there is a clear potential to achieve substantial reductions in development on a global scale [8,9].
energy consumption. Potential savings can reach up to 30 %, leading to Bio-based polyurethane foams (BPUFs) offer a compelling solution at
lower CO2 emissions and a more sustainable built environment [4–6]. the intersection of environmental sustainability and superior insulation
* Corresponding author.
E-mail address: [email protected] (O. Gencel).
https://doi.org/10.1016/j.conbuildmat.2024.138214
Received 12 July 2024; Received in revised form 30 August 2024; Accepted 2 September 2024
Available online 9 September 2024
0950-0618/© 2024 Elsevier Ltd. All rights are reserved, including those for text and data mining, AI training, and similar technologies.
O. Gencel et al. Construction and Building Materials 448 (2024) 138214
Nomenclature NHCOO Carbamate

BPUF-MPCM-1 Bio-based polyurethane composites without
Abbreviations microencapsulated phase change material
PCM Phase change materials BPUF-MPCM-1, PCM30 Bio-based polyurethane composites with
MPCM Microencapsulated phase change materials 30 %wt. microencapsulated phase change material
PU Polyurethane BPUF-MPCM-1, PCM60 Bio-based polyurethane composites with
PUF Polyurethane foam 60 %wt. microencapsulated phase change material
BPUF Bio-based polyurethane foam BPUF-MPCM-1, PCM90 Bio-based polyurethane composites with
ThC Thermocouple 90 %wt. microencapsulated phase change material
CO Castor oil
MCO Modified castor oil Symbols
MDI 2,4′-methylene diphenyl diisocyanate d50 Size at which 50 % of the particles are smaller and 50 % are
CPP Commercial polyether polyol larger
SEM Scanning electron microscopy d20 Size at which 20 % of the particles are smaller and 80 % are
FT-IR Fourier-transform infrared spectroscopy larger
DSC The differential scanning calorimetry d90 Size at which 90 % of the particles are smaller and 10 % are
ThC1, ThC2, ThC9, ThC10 Thermocouples for the lower surface larger
temperature of samples T Temperature (◦ C)
ThC3, ThC4, ThC11, ThC12 Thermocouples for the upper surface of T Time (o′clock)
samples TPCM-Tref Temperature difference (◦ C)
ThC5, ThC6, ThC13, ThC14 Thermocouples for the near-surface ΔT Temperature difference curves
temperature of samples Tamb Ambient temperature
ThC7, ThC8, ThC15, ThC16 Thermocouples for the room center Λ Enthalpy efficiency
temperature of cabins ΔHm, composite Melting latent heat of the composite
NCO Isocyanate ΔHm, mpcm Melting latent heat of the pure MPCM
performance, particularly in building applications [10–12]. These foams need for active heating and cooling systems, lowering energy con
are derived from renewable biomass sources, reducing reliance on finite sumption, and enhancing building comfort levels. Therefore, adding
fossil fuel reserves and mitigating environmental impact. Their excep PCMs to PUFs has emerged as a frequently researched topic for their
tional thermal insulation properties contribute significantly to utilization as building construction materials [22]. Aydın and Okutan
energy-saving efforts in buildings, with potential heating and cooling [23] determined that the heat storage capacities of PUF composites
energy consumption reductions [13,14]. By minimizing thermal losses enhanced with approximately 22 wt% of tetradecyl tetradecanoate
through walls, roofs, and floors, BPUFs enhance indoor comfort and PCM, increased by 34 wt% due to the PCM. Gama et al. [24] found that
substantially decrease CO2 emissions, with potential reductions of up to adding just 10 wt% PCM not only improved the thermal energy storage
40 % compared to conventional insulation materials. Moreover, their properties but also increased the thermal conductivity and compressive
versatility and ease of installation make them ideal for various con strength value by more than three times compared to unmodified PUFs.
struction applications, further amplifying their importance in promoting This was due to the alteration of cell morphology and dimensions. Chen
sustainable building practices [14,15]. While the main components of et al. [25] demonstrated that the PCM of PEG at a ratio of 60 wt% within
PUFs are typically polyols and polyisocyanates derived from petro the PUF did not exhibit any leakage problems, and even after 1000
chemical sources, the necessity to explore alternative solutions has heating-cooling cycles, the composites showed almost no change in
arisen due to the limited availability and environmental impacts of these enthalpy value. However, although it is reported that the thermal
sources [16]. In this context, a sustainable approach called properties are enhanced when PCM additives are incorporated into the
bio-compositing has emerged as a significant strategy to enhance the PUF structure, it is known that the PCM addition rate is limited due to
sustainability of PUFs. Bio compositing involves incorporating envi the leakage problem. In this context, the review study conducted by
ronmentally friendly components into the structure of PUs. One such Ikutegbe and Farid [26] reports that encapsulated PCMs added to PUFs
component is castor oil (CO), which enhances the structural properties provide a significantly high PCM contribution without experiencing
of PUFs while reducing their environmental footprint. CO is an leakage issues. This demonstrates that a higher PCM ratio produces
eco-friendly option due to its renewable nature and biodegradability. more latent heat storage capacity. Microencapsulated phase change
Therefore, incorporating bio-components like CO into the composition materials (MPCMs) are advanced thermal energy storage materials
of PUFs contributes to sustainable construction practices by minimizing consisting of microcapsules containing a PCM core encapsulated within
environmental impacts [17–19]. Modifying CO with epoxy during the a protective shell [27,28]. This microencapsulation imparts several ad
production of BPUFs impacts pore formation. The modification process vantages, including enhanced stability, reduced leakage, and improved
influences the kinetics of foam formation and the stability of the foam compatibility with matrix materials [29,30]. Additionally, MPCMs offer
structure. This creates a more homogeneous pore structure and en greater flexibility in application, enabling their incorporation into a
hances the mechanical properties of the foam. Additionally, the modi wide range of materials, including polymers, textiles, and building
fied CO (MCO) acts as a catalyst in foam formation, promoting the construction materials, without altering their physical properties. This
formation of smaller and more uniform pores. Consequently, epoxy advanced encapsulation technique enhances the efficiency and effec
contributes to achieving a more stable and homogeneous pore structure tiveness of thermal energy storage systems, making MPCMs a preferred
in BPUFs [20,21]. choice for applications requiring precise temperature control and energy
Adding phase change materials (PCMs) to PUFs enhances thermal efficiency [31–33]. Qu et al. [34] investigated the latent heat storage
regulation properties. When incorporated into the foam matrix, PCMs properties of MPCM-added PUF composites and found that the enthalpy
absorb and release thermal energy during phase transitions, stabilizing values increased proportionally with the increase in the MPCM ratio.
indoor temperatures. This improves energy efficiency by reducing the This indicates that the MPCM particles are compatible with the matrix
2
PUF. Xiang et al. [35] determined that the PUF composites exhibited a cross-linking degree of the segments in their composition. These prop
latent heat enthalpy value exceeding 50 J/g when the MEPCMs consti erties can also be affected by external factors such as temperature and
tuted 50 wt% of the composites. During surface temperature tests con time, which allow such biocomposites to have a wide range of uses. In
ducted on MPCM-added PUF composites, Naikwadi et al. [36] observed this study, we have emphasized the environmental effectiveness of BPUF
that the temperature of the unmodified PUF composites reached their materials, the superiority of biocomposites obtained by adding MPCM
peak value after 90 minutes as the temperature increased, however, in materials during the production of BPUF materials with plant-based
PUF composites with 40 wt% MPCM addition, this time was approxi additives, and the need for energy efficiency and carbon emission tests
mately 210 minutes, indicating that the addition of MPCM delayed the for the use of these materials in new generation building applications.
heating of the composites under increasing temperature conditions due
to their latent heat storage property. Furthermore, the moisture resis 2. Materials and methods
tance of PU composites including MPCM can be enhanced with the
content of MPCM. The importance of moisture resistance, especially 2.1. Raw materials and chemicals used in experimental studies
when used in construction and building materials, and the necessity of
minimizing moisture effects to ensure long-term durability in structures In this study, Nextek 24D brand MPCMs sourced from Microtek
are clearly stated in the literature [37]. When it comes to similar ap Laboratories, Inc. were utilized. This is a commercial MPCM in a dry
plications of MPCM-added BPUFs, these applications are lacking in the powder form. It contains at least 97 % solids. The shell of the MPCMs is
literature. Even though they are not in foam form, there are still very few composed of melamine-formaldehyde. This shell prevents leakage of the
studies on the impregnation of MPCMs into porous bio-structures. core, which consists of branched-chain hydrocarbon mixtures, during
Öztürk et al. [38] have produced composites with a thermal conduc phase transitions. The melting point of the PCM within the MPCM is
tivity of 0.1041 W/mK and an enthalpy value of 51.1 J/g by incorpo approximately 24 ◦ C. While the MPCM particles have a melting enthalpy
rating MPCMs into porous wood fiber composites to enhance value of approximately 200 J/g, the particle size distribution ranges
thermoregulation properties for building applications. Cieślikiewicz from about 1–45 µm. The acetic acid, hydrogen peroxide, methyl thio
et al. [39] developed a composite of hemp shives and magnesia binder glycolate, and perchloric acid with analytic grade were used in the
with MPCM to enhance the thermal mass of building materials. The fabrication of MCO and procured from Merck. In this research, 2,4′-
MPCM effectively delayed the building material’s temperature response methylene diphenyl diisocyanate (MDI) and commercial polyether
to thermal stress until the phase change process was complete. polyol (CPP) are used to produce BPUFs as main components. The vis
Considering the advantages of those BPUF composites produced with cosity of the castor oil used in this study at room temperature is 426
MCO and the thermal energy storage properties conferred by the addi mPa⋅s and its density is 947 kg/m3. Its melting point is known to be − 10
tion of MPCMs, there is a notable gap in the literature regarding studies ◦
C and its flash point is 230 ◦ C. Standard quality, 100 % pure castor oil is
focusing on these new composites where BPUFs serve as the matrix and preferred in this study. In addition, the viscosity of the commercial
MPCMs are utilized as additives. This study will be the first to include polyether polyol used at room temperature is 432 mPa⋅s and its density
MPCM additives to BPUF composites with MCO additives in the litera is 1063 kg/m3. The viscosity of commercial MDI at room temperature is
ture, although studies on MPCM additives to PUF composites or PCM known to be 760 mPa⋅s and its density is 1158 kg/m3. The gelation time
additives to BPUF composites are found in the literature. Combining of the mixture obtained during production is 5 min. Touch drying time is
MCO-enhanced BPUFs with MPCMs represents a novel material given as 30 min and average Shore A hardness is 72.
composition showcasing exceptional building material properties. Given
the recent trend of frequent preference for these materials in construc 2.2. Synthesis of MCO and chemical reaction mechanism of BPUF
tion, attributed to their environmental and structural advantages, the
synergy between them holds significant promise. BPUFs-MPCM com 500 g of castor oil is added to bora silicate glass reactor. 250 g of
posites offer a multifaceted approach to addressing sustainability con 30 % hydrogen peroxide and 50 g of 85 % formic acid are slowly added
cerns in the built environment. By harnessing the environmentally to the existing reactor. The mixture is subjected to reaction for 7 hours at
friendly attributes of MCO and the thermal regulation capabilities of 57–59 ◦ C with continuous stirring. After the chemical reaction is com
MPCMs, these composites contribute to both energy savings and CO2 plete, the mixture is cooled, and 50 mL of pure water is added. Sodium
emissions reduction. The integration of MPCMs enhances the thermal bicarbonate is added to the mixture to neutralize it and continuously
performance of BPUFs, enabling them to efficiently store and release stirred it. The neutralization is completed by checking the pH. The
thermal energy, thereby reducing the need for active heating and mixture is separated with ethyl acetate, the organic phase is separated
cooling systems. This not only promotes indoor comfort but also results with a separating funnel and the volatile components are removed with
in substantial reductions in energy consumption and associated carbon a vacuum rotary evaporator. The epoxidized CO obtained is placed in a
emissions. Thus, the unique combination of BPUFs-MPCM composites separate reactor and added to 250 mL of methyl alcohol (99.5 %). 1 %
emerges as a promising solution for sustainable building materials, potassium hydroxide (KOH) solution, which acts as a catalyst in the
exemplifying innovation at the intersection of environmental con opening of the epoxy rings, is added to the reactor. The mixture is
sciousness and performance efficiency. Furthermore, BPUF-MPCMs are subjected to reaction for 5 hours at 54–56 ◦ C with continuous stirring.
flexible polymers with properties such as high flexibility, abrasion After the reaction is complete, the mixture is cooled and neutralized. The
resistance, and durability. This biocomposite is formed as a result of the resulting mixture is separated with ethyl acetate to separate the organic
reaction of polyester or polyether-based polyols with diisocyanates. phase, and the impurities are removed by vacuum. Hydroxylated CO is
BPUF-MPCM can be used in various processing methods such as injec modified by physical and chemical processes as stated above. Within the
tion molding, extrusion, and 3D printing thanks to its thermoplastic technique employed to MCO with epoxy, the inherent unsaturated
properties. In addition, BPUF-MPCM are polymers that attract attention double bonds within the fatty acid chains are commonly unsealed,
with their viscoelastic behavior. Such materials exhibit the properties of initiating oxygen binding to create epoxide groups. This procedure en
both viscous liquids and elastic solids; that is, they both deform under an tails the interaction of the unoccupied locations with an epoxy sub
applied force and partially or completely return to their original shape stance, culminating in incorporating an oxygen atom and creating an
when this force is removed. BPUF-MPCM are materials with high energy epoxide ring with three members. The final phase in acquiring polyols
absorption and damping capabilities thanks to these properties. For this from vegetable oils is the hydroxylation procedure. Once optimal pa
reason, they are widely used in applications such as sponges, cushions, rameters are reached, this stage is executed under acidic circumstances,
beds, and shock-absorbing materials. The viscoelastic property of BPUF- facilitated by primary alcohols and water. When water or acids are
MPCM varies depending on the chemical structure, chain length, and present, the epoxide ring undergoes an opening, rendering the oxygen
3
atom accessible for protonation. Afterward, the oxygen atom in the within an oven. Fig. 1 presents the workflow diagram of the fabrication
hydroxyl group accepts a proton, creating a hydroxyl group with a of BPUF-MPCM composites. The compositions and mixing ratios of each
negative charge. This gives the MCO molecule hydroxyl groups attached component used in the production of BPUF are expressed in Table 1,
to the atoms previously making up the epoxy groups. These hydroxyl along with the codes of the fabricated samples.
groups make the MCO more reactive and polar, allowing it to be used in
various polyol, resin, and polymer manufacturing applications. The
2.4. Characterization processes
addition of -OH groups increase the versatility of the modified oil in
different formulations, particularly in the production of epoxy resins.
The examination of particle size distribution was meticulously con
MDI is transformed chemically to create PU by mixing MCO with com
ducted on the MEPCM sample using the Mastersizer3000 (Malvern
mercial polyether polyol. Polyether polyol, which has hydroxyl (-OH)
Panalytical Co.) instrument, which employs laser diffraction technology.
groups, is added to the MCO. The polyol hydroxyl groups then partici
By systematically analyzing the distribution of particle sizes, valuable
pate in a polyaddition process with the remaining epoxy or hydroxyl
insights were gained into the composition and behavior of the MEPCM
groups in the modified CO. MDI is then introduced to the polyol-MCO.
material. The bulk density values of BPUF and BPUF-MPCM composites
The reaction between MDI and the polyether polyol facilitates the pro
were calculated after being poured into molds with dimensions of
duction of a PUF, where a foaming agent plays a critical role. The
20×10×5 mm3 and removed from the mold. Weight measurements
foaming agent, typically water or a volatile organic compound, reacts
were obtained using a precision balance with a sensitivity of 0.001 g,
with the isocyanate groups to release gas, forming the cellular structure
and the dimensions used in volume calculations were determined using
of the foam. This process significantly influences the density, mechani
a precise digital caliper. The density values were calculated in kg/m3
cal properties, and thermal insulation performance of the resulting bio-
following the mass and volume calculations. To assess the tensile
based polyurethane foam (BPUF) [40]. The careful control of the
properties of specimens incorporating BPUF composites, tensile testing
foaming agent and reaction conditions ensures the desired foam char
follows the guidelines outlined in the ASTM D638–22 standard [41],
acteristics are achieved, making the BPUF suitable for various applica
utilizing a UTEST Material Test Equipment model universal tensile
tions. Then, the isocyanate groups within MDI react with the remaining
testing device) with a 1 kN capacity. To determine the tensile strength,
hydroxyl groups, producing a prepolymer. Subsequently, this prepol
three samples with the same composition were subjected to tensile tests
ymer is elongated through interaction with additional polyether polyol,
at room temperature with a crosshead speed of 1.0 mm/min. The
facilitating the formation of urethane linkages and the extension of the
average tensile strength values obtained from these tests were used to
polymer chain. The elongated PU-based BCF is subsequently fortified
ensure accuracy and reliability by accounting for any material proper
through crosslinking, achieved by further interaction with MDI. This
ties variations. Tensile strength values are determined by calculating the
cross-linking significantly enhances the strength and resilience of the
average of the results obtained from the tensile tests. Utilizing a TCi
PU-based BCF network. The sample (mixture) obtained in this study is
thermal conductivity analyzer device, the thermal conductivity coeffi
prepared as a homogeneous liquid at room temperature. MDI used as a
cient of the samples is determined. The measurement entails drilling a
crosslinker, is added to the mixture within half a minute at the last stage,
hole, 2.5 mm in diameter and 2.5 cm in depth, from the midpoint of the
mixed at 2000 rpm, and then cast into standard molds. In this mixture,
samples (5×5×5 cm3) extracted from the molds.
where physical interactions and chemical reactions occur together, the
The thermal decomposition behavior of BPUF was examined using
curing process of the samples occurs quickly. First, gelation reactions
the Coats-Redfern method, and the activation energy was calculated.
and then swelling reactions happen. The gelling time is on average
This method evaluates the thermal decomposition data of BPUF with the
5 minutes and the rising time continues until the 6th and 13th minutes.
help of kinetic equations. Activation energy is calculated with the help
The resulting sample is waited for 24 hours to cure for physical testing
of equations adapted to mathematical models, such as diffusion equa
and chemical analysis fully.
tions. In this study, the thermal decomposition behavior of BPUF from
room temperature to 625 ◦ C with a temperature increase ratio of 10 ◦ C/
2.3. Production and proportions of BPUF composites
Table 1
At the beginning, an appropriate amount of MPCM was blended The experimental study plan in MPCM added samples.
mechanically with polyol and MCO for 5 minutes at 1000 rpm. The MDI Samples CPP (wt%) MCO (wt%) MDI (wt%) MPCM (wt%)
was combined with the blend and thoroughly stirred in a beaker by a
BPUF-MPCM− 1 42.50 7.50 50 0
mechanical mixer for 1 minute at a speed of 1000 revolutions per BPUF-MPCM− 2 29.75 5.25 35 30
minute. Following this, the resulting amalgamation was transferred into BPUF-MPCM− 3 17.00 3.00 20 60
a mold and left to sit at ambient temperature for 24 hours, facilitating BPUF-MPCM− 4 4.25 0.75 5 90
complete expansion and further solidification in a vacuum environment
Fig. 1. BPUF-MPCM production steps.
4
min is examined in an inert environment (nitrogen gas). It is seen that temperatures of the cabinets containing the samples were recorded with
BPUF has the highest coefficient of determination (R2˃0.9894) accord thermocouples ThC7, ThC8, ThC15, and ThC16. Thermocouples placed
ing to the three-dimensional diffusion equation, with a conversion ratio on the lower and upper surfaces of the samples provide critical data on
between 0.10 and 0.90. the thermal gradients across the thickness of the samples. This helps in
Samples with a diameter of 5 cm were utilized to determine the understanding how effectively the material insulates and how temper
hardness values using the Shore A test method. The final hardness values ature variations affect its performance. Thermocouples located near the
were recorded by averaging at least 5 measurements on each surface. surfaces measure the temperature variations close to the surface, which
Hardness measurements for BPUF and BPUF composite samples were is essential for evaluating the thermal resistance and insulation prop
conducted per the ASTM D 2240 standard [42]. The investigation delved erties of the material under realistic conditions. Thermocouples
into the chemical compositions of BPUF composites and scrutinized the recording central temperatures in the test cabinets help monitor the
physicochemical bonds between BPUFs and MPCM, employing a Fourier overall thermal environment within the cabinet, ensuring that temper
Transform Infrared Spectrophotometer (FTIR) apparatus with the Per ature conditions are consistent and accurately reflect the influence of the
kinElmer brand. This analysis ensued across the spectrum spanning sample’s thermal performance. These strategic placements allow for a
4000–450 cm− 1. The differential scanning calorimetry (DSC) analysis comprehensive assessment of the thermal behavior of the materials,
was employed to examine the properties of the MPCM and the produced helping to evaluate both the insulation efficiency and the thermal sta
composites. The DSC analysis was performed using a HITACHI 7020 bility of the samples in various conditions. Fig. 2 clearly depicts the
model instrument. The temperature increased and decreased at a rate of entire experimental system. An Eco MS-410 brand pyranometer was
3 ◦ C per minute, from 5 ◦ C to 40 ◦ C. The procedure occurred in a ni used to determine the total intensity of sunlight reaching the surfaces. A
trogen gas environment with a flow rate of 30 mL per minute. For the midi logger of the Graphtec GL-240 model was used to record all the
characterization of microstructural properties such as voids, porosity, data. These tests were conducted on the roof of the Faculty of Engi
and cell structure within MPCM-modified BPUF composite, the TESCAN neering, Architecture, and Design building affiliated with Bartın Uni
MAIA3 XMU model scanning electron microscope (SEM) was employed. versity, located in the Western Black Sea region of Türkiye, at
For the determination of crystal structures of MPCM and BPUF compo coordinates 41.6◦ N, 32.3◦ E, on April 6, 2024, and April 7, 2024, with
nents, as well as potential crystalline phases, a Rigaku SmartLab X-ray exposure to sunlight throughout the day.
diffractometer equipped with a Cu tube operating at a wavelength of
1.54184 Å and a voltage of 40 kV was utilized. Determining carbon 3. Results and discussions
dioxide output for every kilogram of fuel consumed resulting from the
full combustion of a hydrocarbon fuel containing carbon, hydrogen, 3.1. Particle size distribution results of MPCM
nitrogen, and sulfur required the utilization of relevant formulas in
preceding investigations [43,44]. Furthermore, the yearly aggregate Fig. 3 presents the particle size distribution of the MPCM particles
heat requirement and carbon emission figures were computed, with used in the study. The cumulative distribution curve is evaluated as an
comprehensive discussion in a prior study delving deeply into the spe important parameter obtained from the particle size distribution. The
cific Turkish cities and climates where these computations were con most critical parameter in the particle size distribution is the median,
ducted [45]. It was considered that materials were used for a 400 m2 d50. d50 indicates that 50 % of the MPCM particles used in the study are
wall for energy saving and CO2 emission calculations. smaller than the d50 value, while the other 50 % are larger than the d50
value. Accordingly, the d50 value determined in the study is 4.22 µm.
2.5. Thermoregulation tests Thus, it is understood that the average particle size of MPCM particles is
4.22 µm, with 50 % smaller than 4.22 µm and the other 50 % larger.
Samples of BPUFs with MPCMs were produced in dimensions of Additionally, it was observed that the d20 value is 1.66 µm, indicating
20×20×5 cm3 and placed inside test cabins to determine their behavior that 20 % of the MPCM particles have a particle size below 1.66 µm.
against temperature changes under real environmental conditions. Another important particle size parameter is d90, indicating that 90 % of
Thus, it was elucidated how the cabins containing composite blocks of the MPCM particles have a size smaller than 32.97 µm. Finally, the d100
BPUF-MPCM with varying MPCM ratios changed different locations value shows the particle size value that none of the MPCM particles
within the cabins depending on ambient temperature. Consequently, the exceed. Accordingly, all MPCM particles used have a particle size value
heat storage and release properties of the MPCM content in the cabins lower than 46.87 µm. The incorporation of larger-sized MPCM particles
with BPUF-MPCM composites were thoroughly investigated as the into polyurethane foams negatively impacts their distribution within the
ambient temperature changed. Cube-shaped cabins (39×39×39 cm3) matrix, leading to increased agglomeration. his adverse effect is pri
made of fibreboard material were utilized for these tests. Each cabin marily due to the difficulty in achieving a uniform dispersion of larger
containing a different sample had identical characteristics. EPS foam MPCM particles, which results in the formation of clusters within the
material with a thickness of 50 mm was used on the rear side of each BPUF matrix. These clusters create localized weaknesses and irregular
wall of all cabins. Each test sample was placed in the void remaining at ities in the foam structure, leading to reduced mechanical strength,
the bottom of the cabins. The dimensions of each sample were 20 cm in decreased durability, and potentially compromised thermal insulation
length, 20 cm in width, and 5 cm in height, respectively. After placing properties. Consequently, the overall performance of the BPUF is
the test samples inside the cabins, the top covers of the cabins were negatively impacted, highlighting the importance of optimizing particle
closed. The top covers of the cabins have a square-shaped double-glazed size to achieve the desired balance between thermal management and
window with dimensions of 14 cm in length and width, positioned at the mechanical integrity. This issue has been highlighted in a study by Ana
center, allowing solar radiation to enter the cabin easily. K-type ther et al. [46], where the incorporation of MPCM into polyurethane foams
mocouples were used to record temperature differences on all cabin and was investigated.
sample surfaces. Four thermocouples were used in each cabin containing
a different sample, and these thermocouples were responsible for 3.2. Bulk density results of samples
detecting temperature changes at various locations. Thermocouples
ThC1, ThC2, ThC9, and ThC10 measured temperatures from the lower Fig. 4 shows the samples whose bulk densities have been determined
surfaces of the samples, while ThC3, ThC4, ThC11, and ThC12 were versus the MPCM ratio in the BPUF structure in the study. Increasing the
responsible for measuring temperatures from the upper surfaces. Tem MPCM ratio results in a significant increase in the bulk density of BPUF
peratures near the surfaces of the samples were measured using ther composites. In BPUF-MPCM-1 samples where MPCM is not applied, the
mocouples ThC5, ThC6, ThC13, and ThC14, whereas the central bulk density is 38.5 kg/m3. This value increases to 50.3, 67.4, and
5
Fig. 2. Thermoregulation test cabins with the samples and thermocouple positions.
Fig. 3. Particle size distribution results of MPCM. Fig. 4. Effect of MPCM ratios on bulk density of the samples.
85.6 kg/m3 for BPUF-MPCM-2, BPUF-MPCM-3, and BPUF-MPCM-4 physical properties of polyurethane foam composites. These findings
samples, respectively, with MPCM ratios of 30 %, 60 %, and 90 %. align with similar results observed in previous studies regarding the
This finding indicates that the physical properties of the composites vary effects of PCM materials added to polyurethane foam materials, as
significantly depending on the amount of MPCM added. With the rise in supported by Amaral et al. [47,48]. Density is a pivotal factor influ
MPCM content, there’s a notable increase in the density of the com encing crucial characteristics of composite materials, including me
posites. This increase can be attributed to the distribution of MPCM chanical strength and thermal conductivity. Therefore, carefully
particles within the composite matrix and their interactions at the adjusting the MPCM ratio is crucial to achieving the desired composite
microstructure level. MPCM particles fill the voids and porosity within performance.
the polyurethane foam matrix, thus increasing the overall volume of the
composite. Additionally, the inherently higher density of MPCM parti
3.3. Shore A hardness results of samples
cles contributes to the increase in the composite’s overall density. This
result highlights the significant impact of MPCM addition on the
Fig. 5 exhibits how varying the MPCM addition ratio affects the
6
values (Fig. 7) of the samples reveals a dramatic decrease in contrast to

the hardness results with the increase in the MPCM ratio. Since the
measurement of hardness values is based on the resistance force against
the applied penetrative load on the surface, the cellular structure of
composites has shown a positive effect on this response. Although
MPCM addition may result in a more uniform cell structure, its impact
on tensile strength is significant. The disruption in the polymer matrix
compromises the interfacial bonding between polymer chains, leading
to decreased tensile strength. Moreover, the increased porosity from
higher MPCM content serves as stress concentration points, facilitating
crack initiation and propagation, further diminishing overall tensile
strength. The uneven distribution of MPCM particles within the polymer
matrix also exacerbates mechanical property inconsistencies, hastening
material failure under tensile strength. However, this decrease is notably
dramatic with a 90 wt% MPCM addition, primarily due to a substantial
reduction in polymer chain entanglement effect, significantly compro
mising the polymer structure. The increase in the MPCM ratio results in
Fig. 5. Effect of MPCM ratios on Shore A hardness of the samples. increased cell ruptures within the structure of BPUF-MPCM composites.
Tensile testing leads to an easier separation of already ruptured cell
hardness of BPUF composites. An elevation in the MPCM ratio corre walls upon applying the testing force. This results in a reduction of
sponds to a significant uptick in hardness values. For instance, whereas tensile strength as the foam becomes more susceptible to cracking and
sample BPUF-MPCM-1 exhibits a hardness of 66.5 Shore A, this figure deformation under stress. On the other hand, the incorporation of rigid
spikes to 82.4 Shore A for sample BPUF-MPCM-4, featuring a 90 % or brittle MPCM particles leads to decreased flexibility and elongation at
MPCM addition. The augmentation in MPCM addition induces alter the break because the presence of MPCMs within the foam creates weak
ations in the cell structure of polyurethane composites. These modifi points due to their incompatibility with the polymer matrix. The foam
cations encompass changes in cell size, distribution, and morphology. becomes less capable of absorbing energy and deforming plastically,
Increasing MPCM content influences cell nucleation and growth during which is crucial for maintaining tensile strain capacity. Consequently,
the foaming process. Furthermore, MPCM particles may serve as the tensile strength and tensile strain capacity values of the BPUF-
nucleating agents, fostering the development of smaller and more uni MPCM-4 samples have decreased to 158.4 kPa and 39.5 %, respec
form cells. Changes in cell structure due to increased MPCM content tively. In contrast, these values were measured as 241.5 kPa and 87.6 %
directly impact the hardness of the composites. Typically, smaller and in MPCM-free BPUF-MPCM-1 samples. The frequent highlighting of the
more uniform cells lead to a denser and sturdier foam structure, trans adverse impact of adding MPCM additive to polyurethane foams on the
lating into elevated hardness values. This is due to increased cell density cell walls in the microstructure is a common observation in the literature
and uniformity, making the foam more resilient against deformation and [24,50,51]. Although mechanical properties are compromised, it is
resulting in greater hardness. These findings align with similar outcomes acceptable for building applications. Furthermore, MPCMs enhance the
reported in the literature. Fan et al. [49] observed that both a reduction thermal regulation capacity of BPUF composites by absorbing and
in cell size and an augmentation in cell number played roles in elevating releasing heat during phase changes. This provides better insulation and
hardness properties. This rise in performance can be attributed to the energy management properties, making them ideal for applications
increased density of cell walls and struts per unit area within the BPUF, requiring thermal stability. While the inclusion of MPCMs improves the
which fortifies the foam structure during loading. Additionally, the thermal regulation capacity, it typically comes at the expense of me
incorporation of fillers into the cell walls and struts enhances the chanical strength. The trade-off occurs because the structural compro
hardness of the foams. mises made to enhance thermal properties (such as the introduction of
weak points and density changes) simultaneously reduce the material’s
mechanical performance. The key is to optimize the MPCM content to
3.4. Tensile strength and tensile strain capacity results of samples achieve a desirable balance between improved thermal properties and
acceptable mechanical strength. This involves careful consideration of
Examining the tensile strength (Fig. 6) and tensile strain capacity
Fig. 6. Effect of MPCM ratios on tensile strength of the samples. Fig. 7. Effect of MPCM ratios on the tensile strain capacity of the samples.
7
the particle size, loading percentage, and distribution of MPCMs within

the foam matrix.
3.5. Thermal conductivity results
Fig. 8 illustrates the effect of increasing the MPCM ratio on the

thermal conductivity of BPUF composites. As the MPCM ratio increases,
there is a noticeable increase in the thermal conductivity values. At the
same time, the thermal conductivity value determined for BPUF-MPCM-
1 samples is 0.0265 W/m⋅K, a 90 wt% MPCM addition has increased the
thermal conductivity value of BPUF-MPCM-4 composites to 0.0418 W/
m⋅K. One of the significant reasons for using polyurethane foams as
insulation materials is reported in the literature [22] to be their low
thermal conductivity (0.02–0.05 W/m⋅K), which is influenced by the
cell distribution and structure within the foam. Many studies have re
ported that the number of closed cells and cell size directly influence
thermal conductivity [52–55]. Increasing the number of closed cells
Fig. 9. Effect of MPCM ratios on the activation energy of the samples.
leads to lower thermal conductivity because it restricts airflow.
Conversely, a decrease in cell size increases the number of cell walls,
complicating the direction of electron flow and thereby reducing ther energy barrier that must be overcome for the curing reaction. The effi
mal conductivity. The increase in the thermal conductivity coefficient ciency and effectiveness of various curing processes and formulations
according to the MPCM ratio is related to the closed pore ratio and used in producing polyurethane composites are assessed by determining
matrix density. The MPCM ratio and the closeness of the solid particles the activation energy. Higher activation energies indicate more complex
to each other also increase the thermal conductivity coefficient. In curing reactions or slower reaction rates, whereas lower activation en
BPUF-MPCM samples, a decrease in the MPCM ratio leads to a reduction ergies suggest simpler reactions or faster curing kinetics. As seen in this
in both the number of pores and the homogeneity of pore distribution, study, with the increase in the MPCM content, the activation energy
which in turn affects the thermal conductivity. Considering the micro required for the curing process of BPUF composites also increases. The
structure according to the SEM images provided in the following section activation energy necessary for BPUF composites without MPCM addi
(Fig. 13), there are no significant large holes although the BPUFs with tive is nearly half that needed for BPUF-MPCM-4 composites with 90 %
added MPCMs exhibit some broken cells due to increased viscosity This MPCM content. The rise in activation energy suggests that the curing
suggests that the microstructure is relatively stable, with microcapsules reaction becomes more intricate with the incorporation of MPCM. This
being well-distributed within the foam matrix. However, the presence of could imply additional steps or more energy-intensive processes
MPCMs within the cell walls alters the path through which heat is required for curing the composite material. The presence of MPCM
conducted, facilitating more direct paths for heat flow, thus slightly probably leads to interactions with the polyurethane matrix during the
increasing thermal conductivity. The increase in thermal conductivity curing process. These interactions alter the kinetics of the curing reac
aligns with previous literature [22,24,50], where similar changes have tion, requiring higher energy inputs to overcome potential barriers. Cao
been observed in PU foams containing PCM. This suggests that the et al. also found that the addition of PCM alters the thermal dynamics of
observed changes are consistent with the known effects of microen the system and leads to a higher requirement for activation energy in
capsulation on foam structure and thermal behavior. phase change processes [56].
3.6. Activation energy results of samples 3.7. FTIR spectra results of samples
The increase in the ratio of MPCM to BPUF structure is seen to cause Fig. 10 shows the FTIR spectra of MPCM, BPUF-MPCM-1, and BPUF-
changes in the activation energy values, as shown in Fig. 9. Calculating MPCM-4 composites. Peaks corresponding to MPCM and BPUF struc
activation energies for BPUF composites provides valuable insights into tures are identified in all BPUF-MPCM composites. Accordingly, only the
the kinetics of their curing process. Specifically, it sheds light on the carbonyl stretching peaks specific to the BPUF structure are observed in
the BPUF-MPCM composites. The presence of carbonyl stretching peaks
particular to the BPUF structure in the BPUF-MPCM composites can be
attributed to the chemical composition of the materials and the in
teractions between them during the composite formation process. BPUF,
a polyurethane foam, contains carbonyl groups in its chemical structure,
typically associated with urethane bonds. These carbonyl groups give
rise to characteristic peaks in the FTIR spectrum. When MPCM is added
to BPUF to form composites, the carbonyl stretching peaks of BPUF
remain present because the chemical structure of BPUF is retained
within the composite. On the other hand, MPCM does not contain
carbonyl groups in its chemical structure. Therefore, while peaks cor
responding to MPCM and BPUF structures are observed in the BPUF-
MPCM composites, only the carbonyl stretching peaks specific to the
BPUF structure are detected. On the other hand, the vibrations occur due
to the stretching and bending motions of the carbon-oxygen-carbon (C-
O-C) bonds, typically found in ether linkages or polymer chains con
taining ether groups. In polymeric materials like BPUFs, these bonds are
often present in the backbone structure or as part of crosslinking agents.
Fig. 8. Effect of MPCM ratios on the thermal conductivity of the samples. -CH group stretching vibrations arise from stretching carbon-hydrogen
8
Fig. 10. FTIR spectra of MPCM, BPUF-MPCM-1, and BPUF-MPCM-4.
(-CH) bonds in various organic compounds. In polymeric materials, such

as BPUFs or MPCMs, -CH groups are commonly found in the polymer
chains or side groups. The vibrations occur due to the stretching of
hydroxyl (-OH) bonds, characteristic functional groups of alcohols,
phenols, and other compounds containing hydroxyl groups. In poly
meric materials, -OH groups may be present as pendant groups, in chain
extenders, or as part of additives. These observations suggest that the
chemical bonds and functional groups associated with -C-O-C- bonds,
-CH groups, and -OH bonds exhibit consistent characteristics across all
samples. The presence of hydroxyl groups connected to hydrogen bonds
is seen in the wavelength range of approximately 3350–3550 cm− 1. The
peak indicating the presence of isocyanate and amine groups is in the
wavelength range of 3200–3400 cm− 1. The carbonyl peak (C– –O)
stretching band is in the 1700–1750 cm− 1 wavelength range. This peak
indicates isocyanate (NCO) and carbamate (NHCOO) groups. The peak
indicating the presence of the amine group is seen in the wavelength
range of 1150–1300 cm− 1. Bands originating from groups with different
C-H bonds, such as methyl, methylene, and aromatic rings, are in the
1400–1500 cm− 1 wavelength range. Bonds indicating polyester and
polyether (C-O-C) bonds are also seen in the wavelength range of
1100–1200 cm− 1. The similarity in the detected wavelengths suggests
that the samples’ molecular structures and chemical compositions, Fig. 11. DSC curves of MPCM, BPUF-MPCM-2, BPUF-MPCM-3 and BPUF-
particularly about these functional groups, remain relatively unchanged MPCM-4 with 500th cycle test.
despite composition or processing conditions variations. This consis
tency is important for understanding the stability and uniformity of the Furthermore, the corresponding enthalpy values for these melting and
samples and provides valuable insights into their structural properties. solidification temperatures were calculated to be 199.2 J/g and
198.4 J/g, respectively. Regarding the properties of BPUF-MPCM com
posites, no significant change was observed in the melting and solidifi
3.8. DSC Results cation temperatures with increasing MPCM content. However, the
enthalpy values for melting and solidification of BPUF-MPCM compos
Fig. 11 presents the DSC curves comparing the thermal trans ites increased significantly with increasing MPCM content. In this
formation properties of MPCM and BPUF-MPCM composites, i.e., their context, the enthalpy values measured for the melting and solidification
phase change characteristics, as seen in Table 2. It was determined that of BPUF-MPCM-2 composites were 59.1 J/g and 58.5 J/g, respectively,
MPCM particles melted at 25.4 ◦ C and solidified at 20.9 ◦ C.
9
Table 2 including 90 %. Additionally, in the literature, MPCM additions as high

Melting and solidification data show the phase change properties of the as 90 % have yet to be achieved in PUF composites. These findings
composites. suggest that the enthalpy values obtained in this study are notably
Sample Melting Solidification Melting Solidification higher than those reported in the literature for MPCM-added PUF
Enthalpy Enthalpy (J/g) Point Point (◦ C) composites. Despite significantly lower MPCM content, the BPUF-MPCM
(J/g) (◦ C) composites in this study showed higher enthalpy values indicating the
MPCM 199.2 198.4 25.4 20.9 effectiveness of the formulation and manufacturing process. Moreover,
BPUF- 59.1 58.5 25.6 21.1 the absence of MPCM additions as high as 90 % in the literature further
MPCM− 2
emphasizes the novelty and significance of the results obtained in this
BPUF- 118.2 117.4 25.5 21.0
MPCM− 3 study.
BPUF- 177.3 176.4 25.3 20.7
MPCM− 4 3.9. XRD results
BPUF- 176.8 175.7 25.4 20.8
MPCM− 4
(500th
The XRD patterns demonstrating the crystallographic phase analysis
cycle) results of the tested BPUF and its composites with MPCM are presented
in Fig. 12. The main peak at 18.9◦ , showing a broad and amorphous
structure, characterizes the pristine BPUF materials described by BPUF-
while these values were determined to be 177.3 J/g and 176.4 J/g for MPCM-1. The crystal structure of PU and the peak and degree it forms
BPUF-MCPM-4 composites. are similar in the literature [50,60]. It is observed that the crystal
Besides, the enthalpy efficiency (λ) of these composites was deter structure of BPUF-MPCM-2 composites with a 30 % MPCM addition is
mined using the following equation: nearly identical to that of the BPUF materials. Due to the low MPCM
λ = [(ΔHm, composite) /(ΔHm, mpcm)] ×100 (1) ratio, the crystal structure of MPCM is not prominently visible in these
composites. However, in BPUF-MPCM-3 and BPUF-MPCM-4 composites,
In this calculation, ΔHm, composite represents the melting latent heat of the effect of MPCM addition is evident in the XRD patterns. These
the composite, and ΔHm, mpcm denotes the melting latent heat of the pure composites exhibit characteristic peaks at 7.6◦ , 19.4◦ , 20.8◦ , 23.4◦ ,
MPCM. Based on this equation, the λ value for the BPUF-MPCM-2, BPUF- 24.7◦ , 34.6◦ , 39.6◦ , and 44.5◦ , representing MPCM. It is noted that with
MPCM-3, and BPUF-MCPM-4 composites were found to be 29.66 %, an increase in the MPCM ratio, the intensities of the peaks representing
59.33 % and 89.00 %, respectively. These values closely align with the MPCM increase. These observations suggest that the fabrication of
impregnation ratio of MPCM within the BPUFs, indicating effective composite BPUF materials incorporating MPCM has been achieved
material integration. They suggest that the MPCM is almost fully effectively, with no discernible damage to the crystal structure of
impregnated within the BPUFs, pointing to a successful synthesis MPCM. This preservation of crystal structure holds significance in
process.
After 500 cycles of melting-solidification tests, latent heat values for
BPUF-MCPM-4 composites were recorded as 176.8 J/g and 175.7 J/g.
These results contribute to understanding how adding MPCM affects the
thermal behavior of BPUF composites. While the melting and solidifi
cation temperatures remain relatively stable, the increase in enthalpy
indicates enhanced energy storage capacity within the composites.
Furthermore, the results of repeated tests demonstrate that the com
posite maintains its structural and thermal properties even after
repeated thermal cycling. This is critical for its intended application in
building materials, as they are exposed to daily and seasonal climate
fluctuations.
Table 3 compares the thermal transition values obtained from
MPCM-added PUF composites in the literature and those of BPUF-MPCM
composites tested in this study. The table presents the melting and so
lidification temperatures, and the melting and solidification enthalpy
values of composites obtained by providing different ratios and types of
MPCM addition to PUF materials. The MPCM ratios contained in the
compared composites are significantly lower than those in this study.
Therefore, the lower enthalpy values compared to those in this study can
be considered a normal occurrence. Even theoretically, no MPCM-
containing PUF composite can achieve an enthalpy value exceeding
175 J/g, as obtained in this study, regardless of the MPCM content, Fig. 12. Crystallography peaks of the samples.
Table 3
The comparison of phase transition properties exhibited by MPCM-added PUF composites in the literature with those tested in this study for BPUF-MPCM composites.
Samples Melting Enthalpy (J/g) Solidification Enthalpy (J/g) Melting Point (◦ C) Solidification Point (◦ C) Reference
PUF-MPCM50 56.3 53.1 32.1 23.0 [35]

PUF-MPCM20 14.92 14.26 57.63 50.62 [50]
PUF-MPCM27 24 24 28 18 [57]
PUF-MPCM12 8.6 8.6 33.1 17.3 [34]
PUF-MPCM40 39.91 39.59 35.81 29.93 [58]
PUF-MPCM40 31.74 31.19 29.71 23.10 [36]
PUF-MPCM30 55.46 54.10 4.05 − 4.21 [59]
BPUF-MPCM90 177.3 176.4 25.3 20.7 Current work
10
preserving the phase change properties essential for the materials’ The morphological forms of the samples significantly influence the
functionality. observed outcomes. Specifically, the structural characteristics, such as
cell size, cell wall thickness, and overall pore distribution, play a critical
3.10. SEM analysis role in determining the material’s properties. For instance, variations in
cell size and density can directly affect thermal conductivity, with larger
The porosity and pore morphology of the BPUF-MPCM-1 bio pores or more interconnected cell structures typically leading to higher
composites, which do not contain MPCM, and BPUF-MPCM-4 bio thermal conductivity. Similarly, the mechanical properties, such as
composites, which contain 90 % MPCM, are evident from the SEM hardness and tensile strength, are influenced by the cellular structure;
images provided in Fig. 13. For BPUF-MPCM-4 composites, the presence thicker and more robust cell walls generally enhance mechanical
of MPCM manifests itself as spherical-shaped structures within the strength, while thinner walls may lead to increased deformation and
microstructure, while in BPUF-MPCM-1 composites, there are quite flat reduced strength. In terms of thermal energy storage, the distribution
and smooth pore surfaces. The foaming in the microstructure of BPUF and integration of MPCMs within the foam matrix affect how efficiently
foams has significantly changed depending on the MPCM ratio. In this the material can store and release thermal energy. Well-distributed
context, it has been determined that the pores formed due to foaming in microcapsules facilitate better thermal performance and stability.
BPUF-MPCM-1 composites are considerably larger and fewer than those Thus, the morphologic forms of the samples directly impact their ther
in BPUF-MPCM-4 composites. Additionally, according to the magnified mal and mechanical behavior, explaining the variations observed in the
images (the ones on the right), the pore walls in BPUF-MPCM-4 samples experimental results. All these critical morphological and microstruc
are thinner. Besides being thinner, many pores can be seen even within tural effects have been reported by different researchers in the literature
the walls, as shown in the further magnified SEM image within the right- [35,50,51,64,65].
side SEM image of BPUF-MPCM-4. The inclusion of MPCM introduces
numerous nucleation sites within the polymer matrix. These nucleation 3.11. Thermoregulation results
sites facilitate the formation of gas bubbles during the foaming process
[61]. With more nucleation sites available, there is an increase in the The first step in conducting thermoregulation tests was to determine
number of pores formed, leading to a higher porosity in the the instantaneous changes in solar radiation at specific time intervals
BPUF-MPCM-4 composites compared to BPUF-MPCM-1. MPCM parti during the periods when the tests were performed. Accordingly, Fig. 14
cles act as stabilizing agents for the foams’ cell walls. During expansion, illustrates how solar radiation values changed at certain time intervals
MPCM particles help stabilize the gas-liquid interface which leads to from April 5, 2024, to April 7, 2024, when the tests were conducted. The
thinner and more evenly distributed cell boundaries. This stabilization tests commenced around 19:00 on April 5, 2024, and concluded around
effect prevents the coalescence of bubbles, thus producing a larger 17:00 on April 7, 2024. Since the tests started after the end of the day, no
number of smaller pores rather than fewer larger ones [62]. On the other solar radiation value was detected until the beginning of the next day,
hand, adding MPCM may alter the surface tension of the polymer matrix. April 6, 2024. Subsequently, on April 6, 2024, around 12:38 PM, the
Reduced surface tension results in the creation of finer and more global radiation value peaked at approximately 868 W/m2. The absence
consistent pores. This is because the energy required to form smaller of significant fluctuations in the graphs on this date indicated that
bubbles is reduced, allowing for a more homogeneous distribution of daylight was almost continuously effective, and the sky was clear
pore sizes [63]. It should be noted that the phase change materials throughout the mentioned day. The sudden drops observed in the global
within the microcapsules can absorb and release heat during the foam and direct radiation curves between 11:15 AM and 11:45 AM on the
ing process, which can influence the kinetics of bubble formation and following day, April 7, 2024, indicated cloud cover during this period.
growth. Absorbing heat can reduce bubble expansion and result in However, this condition quickly reverted to a sunny and clear sky.
smaller pores, whereas releasing heat can promote more bubble for Therefore, the global radiation value rose again after this period,
mation and increase overall porosity. reaching its peak (872 W/m2) around 12:20 PM. Accordingly, it was
Fig. 13. Pore morphology of the BPUF-MPCM-1 and BPUF-MPCM-4.
11
2024), the ambient temperature varied between 19 ◦ C and 3 ◦ C. During

this time frame, the temperature on the bottom surface of the reference
sample in the cabin fluctuated between 25 ◦ C and 9 ◦ C. In contrast, these
temperature values increased significantly with increased MPCM con
tent. In the PCM90 sample cabin, the bottom surface temperature of the
sample ranged between 32 ◦ C and 9 ◦ C. Around 06:00, the bottom
surface temperatures of all samples in the cabins began to equalize, and
the response to solar radiation started to change throughout the day. As
observed, when the ambient temperature began to rise due to solar ra
diation around 06:00 on April 6, 2024, the bottom surface temperature
of the sample in the reference cabin began to increase suddenly. How
ever, the bottom surface temperature values in the cabins containing
MPCM samples increased relatively slowly. It was observed that the
peak temperature of the bottom surface of the sample in the reference
Fig. 14. Measuring global, direct, and diffuse solar radiation under actual
environmental conditions on April 5–7, 2024.
cabin coincided with the peak temperature of the ambient temperature
around 13:27 on April 6, 2024. In contrast, the peak temperature hour
for MPCM-containing samples was significantly delayed. For example,
determined that predominantly sunny weather conditions prevailed
in the PCM90 sample cabin, the peak temperature hour for the bottom
throughout the daytime hours on the days when the tests were
surface temperature of the sample was around 16:35. Additionally,
conducted.
among all samples, PCM90 samples provided the lowest temperature
Fig. 15 exhibits the temperature changes in different locations within
corresponding to the time when the ambient temperature peaked.
the test cabins containing both reference and test samples concerning
Accordingly, the peak temperature values for reference, PCM30,
changes in ambient temperature during the intervals when the tests
PCM60, and PCM90 samples were approximately 44.7 ◦ C, 40.6 ◦ C, 40.3
were conducted. In Fig. 15a, temperature variations recorded on the ◦
C, and 39.8 ◦ C, respectively. As the ambient temperature began to
bottom surfaces of the samples placed inside the test cabins are
decrease, it was observed that the bottom surface temperature of the
observed. It can be seen that during night-time hours, the bottom surface
reference sample began to decrease abruptly from around 16:36 on April
temperatures of the samples in both the reference (BPUF-MPCM-1) and
6, 2024, while for MPCM-containing test samples, a slower temperature
PCM30, PCM60, and PCM90 test cabins (BPUF-MPCM-2, BPUF-MPCM-
decrease was achieved. The slowest temperature decrease was observed
3, and BPUF-MPCM-4, respectively) are higher than the ambient tem
in PCM90-containing samples. With the onset of the day on April 7,
perature. This can be attributed to the insulation of the inner walls of
2024, similar effects to the previous day emerged for all locations
each cabin. The critical point is determining which material provides a
(Fig. 16a). Similar effects were observed for all locations. Figs. 15b, 15c,
more temperate environment during relatively cool ambient tempera
and 15d illustrate how the temperature changes on the top surfaces of
tures at night. On April 5, 2024, between 19:00 and 06:00 (April 6,
the samples, the inner side surfaces of the cabins, and the center of the
Fig. 15. Measurement of the temperature of lower-surface (a), upper-surface (b), near-surface (c), and room center (d) in the experimental cabins on April 5–7, 2024.
12
Fig. 16. Measuring the temperature differences between the cabins, including test and reference samples for lower-surface (a), upper-surface (b), near-surface (c),
and room center, on April 5–7, 2024.
cabins varied concerning ambient temperature. According to the graph cold environments as it undergoes the reverse phase change from liquid
showing top surface temperature changes, on April 6, 2024, when the to solid, slowing the cooling process within the cabins and maintaining
ambient temperature peaked, the reference sample provided nearly 70 higher temperature values. This behavior is characteristic of phase
◦
C temperature, while the PCM90 sample provided only 62.8 ◦ C. The change materials like MPCM, which are crucial in regulating tempera
effect of MPCM contribution became more pronounced on the following ture fluctuations and enhancing thermal comfort in various applications.
day when solar radiation was higher, and the PCM90 sample showed Many newly published studies emphasize the thermoregulation tests
only 61.5 ◦ C temperature despite the ambient temperature peaking. In conducted in cabins using building application materials with PCM ad
contrast, the reference sample provided a temperature of 70 ◦ C under ditives, providing information on the suitability of these tests for
similar conditions. PCM90 samples again exhibited the slowest cooling revealing the PCM effect in real-life conditions [66–68]. In the present
due to the cooling of the ambient temperature at night, providing rela study, the incorporation of MPCM into BPUF leads to a significant
tively high-temperature values. The inner side surface temperature enhancement in thermal stability and insulation properties. Specifically,
changes in the cabins showed that as the ambient temperature rose, the the use of MPCMs with a high latent heat capacity result in a reduction of
highest temperature values were obtained in cabins containing refer peak temperature fluctuations by more than 10 % compared to tradi
ence samples. In contrast, cabins containing PCM90 had the lowest tional BPUF in all locations of the test cabins. This stabilization of
temperature values on the inner side surfaces. The same trend was temperature reduces the need for active heating and cooling systems,
observed in the center temperature values of the cabins. Especially thereby contributing to energy savings.
around 13:45 on April 7, 2024, when the ambient temperature reached To better illustrate this phenomenon, graphs depicting the temper
its highest level, the center of the cabins containing PCM90 samples ature differences obtained at the mentioned locations in cabins con
resisted heating and had the lowest temperature. For instance, under taining both reference and MPCM-containing composites throughout
these conditions, while the center temperature of the cabin containing the testing process have been plotted (Fig. 16). Fig. 16a presents the
the reference sample exceeded 71 ◦ C, the center temperature of the curve of the temperature difference between the lower surfaces in cabins
cabin containing the PCM90 sample remained around 63 ◦ C. Cabins containing reference and test samples. In contrast, Fig. 16b shows that of
containing composites with PCM90 material heat up more slowly in hot upper surfaces, Fig. 16c shows that of near surfaces, and Fig. 16d shows
environments, providing lower temperatures, and cool down more that of room-center temperatures. As observed, on the first day of
slowly in cold environments, resulting in higher temperature values. The testing, when cooler ambient temperatures occurred at night, having a
results demonstrate the latent heat storage capability of MPCM in BPUF- 90 % MPCM content resulted in the lower surface temperature in the
MPCM-4 composites. This phenomenon occurs due to the intrinsic reference cabin being 7.83 ◦ C warmer. However, on the following day,
properties of PCM90 material, which has a higher heat storage capacity due to the peak ambient temperature, the lower surface temperature in
than other materials. When exposed to a hot environment, PCM90 ab the reference cabin was 21.37 ◦ C cooler (Fig. 16a). Similar trends were
sorbs heat energy from its surroundings, causing a slower increase in exhibited in the temperature differences between the upper surfaces of
temperature within the cabins. This is because PCM90 undergoes a samples in both reference and test cabins. As shown in Fig. 16b, corre
phase change from solid to liquid as it absorbs heat, effectively storing sponding to the minimum ambient temperature, PCM90 samples pro
the excess thermal energy. Conversely, PCM90 releases heat energy in duced upper surface temperatures that were 2.57 ◦ C warmer compared
13
to the upper surface temperature in the reference sample cabin on April 3.12. Temperature changes on composite surface results
6, 2024. Conversely, with the ambient temperature reaching its
maximum the following day, PCM90 samples provided upper surface Fig. 18 compares the change in surface temperatures during the
temperatures that were 10.14 ◦ C cooler. Regarding the differences cooling process after heating for BPUF-MPCM-1, which does not contain
observed in near-surface temperatures in cabins where the samples were MPCM and serves as the reference sample, and BPUF-MPCM-2, BPUF-
located, as depicted in Fig. 16c, the 90 wt% MPCM content resulted in MPCM-3, and BPUF-MPCM-4 composites containing 30 wt%, 60 wt%,
near-surface temperatures being 2.04 ◦ C warmer in cool ambient con and 90 wt% MPCM, respectively. Inspired by studies [71,72] examining
ditions and 8.73 ◦ C cooler in warm ambient conditions. The differences samples heated above the melting point of PCM, thermal cameras were
in room center temperature values are presented in Fig. 16d, according used to investigate how PCM additives delay cooling by releasing stored
to whether the samples contained a reference or MPCM. When the heat when reaching the phase change temperature during the cooling
ambient temperature peaked, the 90 % MPCM content provided a room process. Firstly, it was determined that the one with the highest surface
8.64 ◦ C cooler than the reference sample. In contrast, it provided a room temperature (31.7 ◦ C) after heating for the same duration was
that was 2.02 ◦ C warmer in cooler ambient temperatures. BPUF-MPCM-1 among the four samples. It was found that as the MPCM
Fig. 17 presents a thermal camera map illustrating how surface ratio increased in the samples, the achieved surface temperature
temperatures varied in cabins containing reference BPUF materials and decreased. The melting point of MPCM in the composite samples being
BPUF-MPCM composites with different MPCM ratios in an outdoor 25 ◦ C to 26 ◦ C indicates that during heating, the ambient temperature
environment. While the surface temperature values of the cabin con exceeds this temperature range, causing the MPCM to melt. Thus, it is
taining the reference BPUF-MPCM-1 sample reached up to 42 ◦ C, this
temperature decreased to 41.7 ◦ C for the BPUF-MPCM-2 sample with
increasing MPCM content. The cabin containing the BPUF-MPCM-3
sample exhibited a maximum surface temperature of 40.4 ◦ C. Howev
er, the best results were achieved with the BPUF-MPCM-4 sample, which
contained 90 wt% MPCM. This sample kept the cabin surface tempera
ture at just 40.3 ◦ C throughout the study. These results indicate that
adding MPCM to BPUF composites effectively reduces heat buildup on
cabin surfaces in outdoor environments. As MPCM content increases,
surface temperatures decrease, demonstrating the material’s ability to
regulate thermal conditions. The significant decrease in surface tem
perature observed with the BPUF-MPCM-4 sample underscores the
enhanced heat storage and release capabilities conferred by higher
MPCM content. Such analyses are commonly used in the literature to test
the thermal management of PCM-containing building materials, thereby
revealing PCM’s latent heat storage property [69,70]. It can be observed
that there is a temperature difference between the enclosures containing
the BPUF-MPCM-1 reference material and the BPUF-MPCM-4 composite
material. Notably, despite the BPUF material with MPCM being posi
tioned at the bottom surface of the enclosure, the external surfaces of the
enclosure show a temperature reduction of up to 2 ◦ C. This indicates that
the addition of MPCM to the BPUF material contributes to improved
thermal regulation, effectively lowering the surface temperatures even
when subjected to similar external conditions. Consequently, the ther
mal camera results demonstrate the potential of BPUF-MPCM compos
ites, particularly those with a higher MPCM ratio, in providing more
comfortable indoor environments by minimizing heat transfer from
outdoor surfaces.
Fig. 17. Thermal camera image for surface temperatures of the experimental Fig. 18. Comparing the surface temperatures of BPUF and BPUF-MPCM com
cabins in thermoregulation tests. posites during the cooling process.
14
understood that the MPCM in the composite melts, revealing its heat emphasizes the importance of MPCM-based composite materials,
storage property, and as the MPCM ratio increases, the surface tem particularly in applications that offer greater resilience and balanced
perature values decrease. In this context, the surface temperature values heat control against sudden drops in ambient temperature.
determined after the initial heating for BPUF-MPCM-2, BPUF-MPCM-3,
and BPUF-MPCM-4 samples were measured as 31.1 ◦ C, 27.5 ◦ C, and 25.8 3.13. Energy saving and CO2 emission
◦
C, respectively. By the way, it was discussed in previous sections that
the thermal conductivity values of the composites increase with the In buildings located in regions with diverse climatic conditions
increasing MPCM content. Despite the increase in thermal conductivity (Region 1, Region 2, Region 3, and Region 4 in this study), the total
values, the temperature in the samples during heating remains lower energy required for heating was calculated based on the thickness of the
compared to the reference sample with lower thermal conductivity. This insulation materials. The calculations for total heat need and CO2
indicates a critical implication of the MPCM’s latent heat storage emissions, which highlight the energy-saving feature, were conducted in
property. When the cooling process is initiated, similar observations are the same manner as detailed in the previous study [70]. These calcula
made from the changes in surface temperature. The cooling rate in tions consider traditional EPS foam and the novel developed
samples without MPCM is higher than that of samples containing BPUF-MPCM-4 biocomposites from this study as insulation materials.
MPCM, even though their thermal conductivity values are lower. Traditional EPS foam is a widely used insulating material known for its
Considering that the solidification temperature of MPCM is approxi low thermal conductivity and lightweight properties. It is commonly
mately 20 ◦ C to 21 ◦ C, it can be said that at the 20th minute of cooling, used in various applications due to its cost-effectiveness and efficient
the MPCM within the BPUF-MPCM-4 sample contains 90 wt% MPCM insulation performance. However, its production process involves sig
starts to solidify and release the stored heat upon melting. This phe nificant energy consumption and generates substantial CO2 emissions,
nomenon is observed around the 40th minute of cooling in composites contributing to environmental concerns. Understanding these aspects is
with lower MPCM ratios. The heat release starting at the 20th minute in crucial for evaluating the energy-saving and emission-reduction benefits
the BPUF-MPCM-4 sample results in a slighter decrease in temperature of alternative materials such as MPCM composites as in this study. On
in the sample. For example, while the surface temperature decreases to the other hand, the temperature conditions for the four different regions
18.6 ◦ C between the 40th and 60th minutes in the reference are consistent with those used in our previous study [70]. The same
BPUF-MPCM-1 sample and BPUF-MPCM-2 samples, it is observed at the climatic zones and temperature parameters have been applied for
60th minute in the BPUF-MPCM-3 sample and at the 100th minute in the comparative consistency. The obtained results on the total heat need are
BPUF-MPCM-4 sample. It is evident from this that the high MPCM ratio seen in Fig. 19. When considering that the thermal conductivity values
significantly delays the cooling of the samples. At the final minute of of insulation materials typically range from 0.02 to 0.05 W/m⋅K, it is
cooling, the surface temperature in the reference BPUF-MPCM-1 sample observed that the thermal conductivity values of all the compared ma
is measured as 14.8 ◦ C, whereas it is 18.6 ◦ C in the BPUF-MPCM-4 terials fall within this range. The energy requirement for buildings in
composites. Therefore, it should be noted that BPUF-MPCM-4 compos Region 1, which has the highest ambient temperature among the four
ites allow for a milder environment in the event of a sudden drop in mentioned regions, is shown in Fig. 19a. It has been determined that
ambient temperature. These results highlight that samples with higher heating is required in this region even if the thickness of EPS insulation
MPCM ratios cool more slowly, demonstrating that MPCM is effective in material and BPUF-MPCM-1 composites is 0.1 m. Accordingly, when
maintaining a more stable temperature during the cooling process. This EPS insulation material with a thickness of 0.1 m is used, the total
Fig. 19. Total heat need of a sample building located in four different climate regions using common insulation material EPS compared to BPUF-MPCMs; (a) Region
1, (b) Region 2, (c) Region 3 and (d) Region 4.
15
energy requirement is approximately 23.45 kWh/m2. In contrast, this BPUF-MPCM-1 insulation materials still results in an energy require
value decreases to 21.31 kWh/m2 when the same BPUF-MPCM-1 ma ment of around 100 kWh/m2. Furthermore, even with cold climate
terial is used. Furthermore, it is understood that the increasing MPCM conditions, when the MPCM ratio is further increased, and
ratio leads to a gradual decrease in the required energy demand. Using BPUF-MPCM-2 and BPUF-MPCM-3 composites are used as insulation
BPUF-MPCM-2, BPUF-MPCM-3, and BPUF-MPCM-4 composites as materials, the energy requirement ranges between 25 and 60 kWh/m2.
insulation materials have shown that energy savings can be achieved by When used at a thickness of 0.08 m in a building located in Region 4,
eliminating the energy requirement based on material thickness. It has BPUF-MPCM-4 composites have eliminated the total energy require
been observed that when BPUF-MPCM-2 composite with a thickness of ment. This suggests that even in climates colder than Region 4, there is
0.092 m, BPUF-MPCM-3 composite with a thickness of 0.044 m, and still potential to nullify the total energy requirement by increasing the
BPUF-MPCM-4 composite with a thickness of 0.028 m are used, the total thickness of BPUF-MPCM-4 composite material. It is evident that uti
energy requirement is reduced to near-zero. It is evident that the use of lizing BPUF composites with a 90 wt% MPCM addition is key to
BPUF-MPCM-4 composites with a thickness of 0.028 m was obtained achieving significant energy savings.
with a 90 wt% MPCM ratio eliminates the energy requirement. In other It was determined that the most effective material in achieving en
words, as the MPCM ratio decreases, the thickness of the insulation ergy savings and completely nullifying the total energy requirement is
material to be used increases. Region 2, where higher energy demand is the BPUF-MPCM-4 composite. Accordingly, the change in CO2 emissions
anticipated due to climate change compared to Region 1, is projected to resulting from the use of insulation materials in four different regions,
require insulation material with a thickness greater than 0.1 m EPS and BPUF-MPCM-4 materials, with varying thicknesses, and the use
(Fig. 19b). However, it is expected that more than BPUF-MPCM-1 and of other fuel types for heating, is presented in Fig. 20. Fig. 20a shows the
BPUF-MPCM-2 will be necessary for this purpose. Using BPUF-MPCM-3 change in CO2 emissions from using insulation materials in a building in
with a thickness of 0.092 m and BPUF-MPCM-4 with a thickness of Region 1, the hottest region. It is evident that among coal, electric, fuel
0.055 m eliminates the energy requirement in a building in Region 2. oil, LPG, and NG fuels, NG exhibits the lowest CO2 emission value, while
Once again, the increase in the MPCM ratio has reduced the required coal has the highest. Accordingly, when EPS is used as the insulation
thickness of the insulation material, playing a role in addressing the material, the CO2 emission value varies between 5 and 14 kg/m2.year in
energy demand. Fig. 19c demonstrates that the total energy necessary case the thickness is 0.1 m. The year depends on the type of fuel used.
demand reaches levels similar to those of Region 3, which has similar Even using EPS at a thickness of 0.1 m only achieves a reduction in these
climatic conditions to that of Region 2. Despite increasing the thickness values. On the other hand, using BPUF-MPCM-4 composite material
of the insulation materials, the gradually horizontal trend of the energy revolutionizes insulation by reducing CO2 emissions to 0 even at a
requirement curve indicates that the MPCM content is insufficient. thickness of 0.028 m, regardless of the type of fuel used. In Region 2,
However, it has been possible to achieve thicknesses of BPUF-MPCM-3 where the climate conditions are slightly cooler, the CO2 emission value
and BPUF-MPCM-4 materials that can eliminate the energy require can still be nullified by increasing the material thickness to approxi
ment, with MPCM ratios of 60 wt% and 90 wt%, respectively. In a mately 0.055 (Fig. 20b). However, EPS usage still needs to be improved,
building application in Region 4, which experiences the coldest climate and CO2 emissions increase compared to Region 1 due to increased heat
conditions, as shown in Fig. 19d, using 0.1 m thick EPS and demand. In Region 3, the rise in heating demand has made EPS
Fig. 20. Carbon emission amounts of a sample building located in four different climate regions using common insulation material EPS compared to BPUF-MPCMs;
(a) Region 1, (b) Region 2, (c) Region 3, and (d) Region 4.
16
insulation material less effective, leading to a further increase in fuel fully explore performance across seasonal and climatic changes. Testing
demand and CO2 emission values ranging from 14 to 41 kg/m2 in varied climate conditions would enhance understanding. Further
(Fig. 20c). Conversely, in this region, the utilization of BPUF-MPCM-4 investigation into how the materials manage thermal energy over
composite material with a thickness of 0.062 m ensures the nullifica extended periods and varying daily temperatures is required.
tion of CO2 emissions regardless of the type of fuel used. In the coldest
climate region (Region 4), BPUF-MPCM-4 composites with a thickness of 4. Conclusions
approximately 0.08 m have eliminated fuel requirements for all fuel
types, thus allowing for the nullification of CO2 emission values BPUF-MPCM composites were successfully developed by incorpo
(Fig. 20d). On the other hand, using EPS in this region has resulted in rating MPCM at different ratios, notably achieving a high percentage
CO2 emission values ranging from only 20–55 kg/m2.year depending on (90 wt%) during the production of epoxy-modified CO-added BPUF
the type of fuel used, regardless of the fuel type in thickness of 0.1 m. In composites. Following that, an in-depth examination was conducted on
summary, using EPS as insulation material only reduces CO2 emissions the physical, mechanical, and thermal attributes of these innovative
to a specific level, regardless of the thickness of the material or climate BPUF-MPCM composites, showcasing improved thermoregulatory ca
conditions. In contrast, using BPUF-MPCM-4 composites as insulation pabilities. Moreover, the impact of these composites on energy saving
allows for eliminating fuel requirements across all types of fuel with and CO2 emissions was assessed. The summary of the results is given
increasing thickness, depending on climate conditions. This approach below:
effectively nullifies CO2 emissions.
The practical applications of BPUF-MPCM composites are diverse 1. Adding MPCM results in more than a twofold increase in bulk density
and impactful across several sectors. Energy-efficient building insulation values and contributes to forming a homogeneous cell structure.
is one of the primary applications, where these composites reduce the 2. Hardness values have increased from 66.5 to 82.4 Shore A with the
need for mechanical heating and cooling systems, leading to lower en rise in MPCM content. The rise in MPCM content has led to further
ergy consumption and operational costs. In the realm of sustainable thinning of the cell walls and enhanced rupturing during tensile
construction, BPUF-MPCM composites are ideal for projects aiming to testing, consequently decreasing tensile strength and tensile strain
minimize environmental impact, contributing to near-zero CO2 emis capacity values.
sions and aligning with green building standards like LEED or BREEAM. 3. The attainment of enthalpy values exceeding 175 J/g indicates
Furthermore, these composites are well-suited for climate-responsive enhanced latent heat storage capability. The increase in MPCM
building design, offering effective temperature regulation in both hot content has increased the activation energy required to cure BPUF
and cold climates, which enhances indoor comfort and overall building composites.
performance. They are also beneficial for retrofitting existing buildings, 4. Phase and chemical bond analyses have demonstrated that, apart
significantly reducing energy bills and improving thermal comfort from the components inherent to BPUF and MPCM content, no
without requiring extensive structural modifications. Incorporating additional component exists in the structure. The presence of char
BPUF-MPCM composites into smart building technologies allows for acteristic peaks for both BPUF and MPCM in the XRD pattern of the
dynamic temperature management, optimizing energy use when inte composite, along with the absence of additional peaks, indicates
grated with smart thermostats and building management systems. These successful integration and purity, suggesting desirable properties.
composites are also suitable for building envelope solutions, including 5. When 90 wt% MPCM composites were integrated into the cabin, and
walls, roofs, and floors, providing an efficient barrier to heat flow and they provided an interior environment temperature of more than 8
enhancing overall building insulation. In green roof and wall systems, ◦
C coolers under maximum ambient temperature conditions.
BPUF-MPCM composites improve the thermal performance of green Regarding delayed cooling, 90 wt% MPCM enabled the samples to
roofs and walls, contributing to energy savings and urban heat island cool by only approximately 7 ◦ C after 100 minutes of cooling,
mitigation. Collectively, these applications highlight the significant whereas samples without MPCM cooled by about 17 ◦ C.
benefits of BPUF-MPCM composites, advancing energy-efficient, sus 6. While the use of EPS insulation material, regardless of its thickness,
tainable, and climate-responsive building solutions. fails to achieve near-zero energy saving and CO2 emission values, the
In this study, ensuring uniform distribution of MPCM within the utilization of BPUF-MPCM composites has resulted in near-zero en
BPUF matrix was challenging. Variations in the distribution could affect ergy saving and CO2 emission values across all climate conditions. In
thermal performance. To mitigate this, the mixing process was opti summary, integrating MPCM into BPUFs presents promising pros
mized, and rigorous quality control measures were employed to ensure pects for sustainable building applications.
consistency. Maintaining the integrity of the MPCMs during processing 7. The significance of BPUF-MPCM composites in meeting region-
was difficult. This was addressed by carefully monitoring processing specific climate requirements is paramount. This study has demon
conditions and using protective measures to prevent leakage or degra strated the performance of BPUF-MPCM composites in climates with
dation of the encapsulation. Achieving precise measurements of thermal diverse weather conditions. Significant energy savings were
properties required meticulous calibration of the equipment. Regular observed in warmer climates like the Mediterranean and Aegean
calibration checks were performed, and multiple replicates were used to regions. At the same time, these benefits showed less impact in the
ensure the accuracy of the results. Fluctuations in laboratory tempera regions surrounding the Black Sea, in Central Anatolia, and across
ture and humidity could potentially influence the data. These variables Eastern Anatolia.
were controlled by conducting experiments in a controlled environment
and employing consistent procedures across all tests. Variability in raw CRediT authorship contribution statement
materials could introduce inconsistencies. This was addressed by using
standardized materials and performing multiple tests to average out any Onur Güler: Writing – review & editing, Writing – original draft,
discrepancies. Variations in processing parameters were minimized Visualization, Formal analysis. Abid Ustaoğlu: Writing – review &
through careful control and monitoring throughout the experimental editing, Writing – original draft, Visualization, Investigation, Formal
process. Furthermore, the study has some limitations that could impact analysis. Ahmet Sarı: Writing – review & editing, Writing – original
the practical implications of the research. The effectiveness of BPUF- draft, Methodology. Gökhan Hekimoğlu: Writing – review & editing,
MPCM composites as insulation materials was not directly evaluated. Writing – original draft, Investigation. Serkan Subaşı: Writing – review
Future research should assess their impact on building insulation and & editing, Writing – original draft, Visualization, Methodology.
energy efficiency. A more detailed analysis of how different levels of Muhammed Maraşlı: Resources, Investigation. Osman Gencel:
solar exposure affect material performance is needed. The study did not Writing – review & editing, Writing – original draft, Supervision,
17
Conceptualization. Ercan Aydoğmuş: Writing – review & editing, [18] D. Gurgel, D. Bresolin, C. Sayer, L. Cardozo Filho, P.H. Hermes de Araújo, Flexible
polyurethane foams produced from industrial residues and castor oil, Ind. Crops
Writing – original draft, Resources, Investigation.
Prod. 164 (2021) 113377, https://doi.org/10.1016/J.INDCROP.2021.113377.
[19] B.P. de Oliveira, L.C.S. Balieiro, L.S. Maia, N.C. Zanini, E.J.O. Teixeira, M.O.T. da
Declaration of Competing Interest Conceição, S.F. Medeiros, D.R. Mulinari, Eco-friendly polyurethane foams based on
castor polyol reinforced with açaí residues for building insulation, J. Mater. Cycles
Waste Manag 24 (2022) 553–568, https://doi.org/10.1007/S10163-021-01341-1/
The authors declare that they have no known competing financial TABLES/7.
interests or personal relationships that could have appeared to influence [20] I. OmraniHigh performance biobased pour-in-place rigid polyurethane foams from
the work reported in this paper. facile prepared castor oil-based polyol: Good compatibility with pentane series
blowing agent 58 Https://Doi. Org. /10. 1177/0021955X211062632 , 2021, ,
449–466, 10.1177/0021955X211062632.
Data availability [21] X. Huang, X. Yang, H. Liu, S. Shang, Z. Cai, K. Wu, Bio-based thermosetting epoxy
foams from epoxidized soybean oil and rosin with enhanced properties, Ind. Crops
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Data will be made available on request. [22] C. Amaral, R. Vicente, V.M. Ferreira, T. Silva, Polyurethane foams with
microencapsulated phase change material: comparative analysis of thermal
Acknowledgment conductivity characterization approaches, Energy Build. 153 (2017) 392–402,
https://doi.org/10.1016/J.ENBUILD.2017.08.019.
[23] A.A. Aydin, H. Okutan, Polyurethane rigid foam composites incorporated with
The support provided by Fibrobeton Inc. is acknowledged. fatty acid ester-based phase change material, Energy Convers. Manag 68 (2013)
74–81, https://doi.org/10.1016/J.ENCONMAN.2012.12.015.
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Construction and Building Materials 448 (2024) 138214

Contents lists available at ScienceDirect

Construction and Building Materials

Biocomposite foams consisting of microencapsulated phase change

Materials with environmentally friendly characteristics play a crucial

Nomenclature NHCOO Carbamate

Fig. 1. BPUF-MPCM production steps.

values (Fig. 7) of the samples reveals a dramatic decrease in contrast to

the particle size, loading percentage, and distribution of MPCMs within

3.5. Thermal conductivity results

Fig. 8 illustrates the effect of increasing the MPCM ratio on the

Fig. 10. FTIR spectra of MPCM, BPUF-MPCM-1, and BPUF-MPCM-4.

(-CH) bonds in various organic compounds. In polymeric materials, such

Table 2 including 90 %. Additionally, in the literature, MPCM additions as high

PUF-MPCM50 56.3 53.1 32.1 23.0 [35]

Fig. 13. Pore morphology of the BPUF-MPCM-1 and BPUF-MPCM-4.

2024), the ambient temperature varied between 19 ◦ C and 3 ◦ C. During

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