Non-isothermal Differential Scanning Calorimetry Research Articles

A Bio-Based Polybenzoxazine Derived from Diphenolic Acid with Intrinsic Flame Retardancy, High Glass Transition Temperature and Dielectric Properties.

A bio-based benzoxazine monomer, diphenolic methyl ester hexafluoro diamino benzoxazine (DPME-HFBz), was successfully synthesized from diphenolic acid (DPA), and the chemical structure was successfully verified. The curing kinetics were studied via non-isothermal differential scanning calorimetry (DSC). The activation energies of DPME-HFBz were calculated by Kissinger and Ozawa methods to be 136.15 and 139.92 kJ/mol, respectively, and the reaction order was calculated to be first order. Owing to the large number of hydrogen bonds after polymerization, poly(DPME-HFBz) presented an ultra-high glass transition temperature of 312 °C and a high initial decomposition temperature (350 °C under air and 345 °C under nitrogen). Because of the excellent charring ability (50.2% residue under nitrogen), the LOI value of poly(DPME-HFBz) was as high as 38%. Poly(DPME-HFBz) also exhibited a very low heat release capacity (HRC) of 90 J/(g·K). In addition, poly(DPME-HFBz) had a dielectric constant (Dk) of 1.88 at 1.5 MHz, which was much lower than the Dk of the reported low-dielectric polymers. This work provides an efficient and sustainable strategy for the synthesis of benzoxazine thermosetting materials with excellent comprehensive properties.

Study of Heavy Oil In-situ Combustion with Copper Biocatalysts: Kinetics and Thermodynamic Aspects of High-Temperature Oxidation Reactions

In-situ combustion is considered an efficient thermally enhanced oil recovery method. However, the combustion front stabilization remains a challenge for the scientific community. The present study examines the efficacy of copper tall oil (Cu-TO) and copper sunflower oil (Cu-SFO) on heavy oil high-temperature oxidation reactions, which are believed to solve this challenge. We applied non-isothermal differential scanning calorimetry (DSC) analyses combined with an isoconversional kinetic approach in order to calculate kinetic parameters, thermodynamic functions, and the effective rate constant of these reactions. The obtained results demonstrated that both catalysts are able to reduce the activation energies and shift oxidation regions to lower temperatures, with Cu-SFO showing superior performance. Kinetic predictions further supported these findings and revealed that the selected catalysts contributed significantly to decreasing oxidation times across all conversion ranges. Additionally, thermodynamic analyses indicated that Cu-SFO facilitated a more ordered and energetically favorable oxidation process, as demonstrated by increasingly negative entropy values and consistently lower Gibbs free energy. The research highlights the Cu-SFO catalyst exceptional ability to accelerate the transition from low-temperature to high-temperature oxidation while maintaining high catalytic activity. Taken together all these results, this research work contributes to provide comprehensive insights from the kinetic and thermodynamic analysis that reveal unique catalytic effects and reaction mechanisms, presenting an approach to stabilize combustion front and improve heavy oil recovery efficiency, addressing a critical challenge in the field of in-situ combustion.

New insight into the thermal stability of the amorphous tetraphenyl-diamine (TPD) – A combined calorimetry/in-situ Raman microscopy study

Non-isothermal differential scanning calorimetry (DSC) was used to study the influences of particle size daver and heating rate q+ on the crystal growth and decomposition kinetics of amorphous N,N’-bis(3-methylphenyl)-N,N’-bis(phenyl)-benzidine (TPD). The macroscopic crystallization kinetics was found to be strongly dependent on q+. At high q+, the crystal growth proceeded dominantly from the mechanical defects acting as primary growth centers, with the corresponding activation energy being ∼70–80 kJ mol−1. At low q+, the crystalline phase was primarily formed from heterogeneous nuclei, with the activation energy for the growth process being ∼980 kJ mol−1. The prolonged nucleation led to extensive passivation of the surface mechanical defects with respect to their function as direct crystal-growth-accelerating centers. Temperature-resolved in-situ Raman microscopy has confirmed the conclusions derived from the DSC data and helped to identify the residual low-q+ defects-originating crystal growth as proceeding from volume-located micro-cracks. The X-ray diffraction analysis confirmed that TPD crystallizes into an identical phase under all circumstances. The thermal decomposition of TPD was found to proceed in a single step, by simple nth-order reaction kinetics with the activation energy of ∼120 kJ mol−1.

Development of a Cure Model for Unsaturated Polyester Resin Systems Based on Processing Conditions.

Unsaturated polyester resin (UPR) systems are extensively used in composite materials for applications in the transportation, marine, and infrastructure sectors. There are continually evolving formulations of UPRs that need to be evaluated and optimized for processing. Differential Scanning Calorimetry (DSC) provides valuable insight into the non-isothermal and isothermal behavior of UPRs within a prescribed temperature range. In the present work, non-isothermal DSC tests were carried out between temperatures of 0.0 °C and 250 °C, through different heating and cooling ramp rates. The isothermal DSC tests were carried out between 0.0 and 170 °C. The instantaneous rate of cure of the tested temperatures were measured. The application of an autocatalytic model in a calculator was used to simulate curing behaviors under different processing conditions. As the temperature increased from 10 °C up to 170 °C, the rate of cure reduced, and the heat of reaction increased. The simulated cure behavior from the DSC data showed that the degree of cure (α) maximum value of 71.25% was achieved at the highest heating temperature of 85 °C. For the low heating temperature, i.e., 5 °C, the maximum degree of cure (α) did not exceed 12% because there was not enough heat to activate the catalyst to crosslink further.

A Study of Hydroxyl-Terminated Block Copolyether-Based Binder Curing Kinetics.

In order to determine the curing reaction model and corresponding parameters of hydroxyl-terminated block copolyether (HTPE) and provide a theoretical reference for its practical application, the non-isothermal differential scanning calorimetry (DSC) method was used to analyze the curing processes of three curing systems with HTPE and N-100 (an aliphatic polyisocyanate curing agent), isophorone diisocyanate (IPDI), and a mixture of N-100 and IPDI as curing agents. The results show that the curing activation energy of N-100 and HTPE was about 69.37 kJ/mol, slightly lower than the curing activation energy of IPDI and HTPE (75.60 kJ/mol), and the curing activation energy of the mixed curing agent and HTPE was 69.79 kJ/mol. The curing process of HTPE conformed to the autocatalytic reaction model. The non-catalytic reaction order (n) of N-100 and HTPE was about 1.2, and the autocatalytic order (m) was about 0.3, both lower than those of IPDI and HTPE. The reaction kinetics parameters of the N-100 and IPDI mixed curing agent with HTPE were close to those of N-100 and HTPE. The verification results indicate a high degree of overlap between the experimental data and the calculated data.

Pyrolysis of high-density polyethylene: Degradation behaviors, kinetics, and product characteristics

Pyrolysis is a promising technology for converting plastic waste into valuable raw materials while offering a potential solution to the global plastic pollution crisis. In this study, the thermal pyrolysis of high-density polyethylene (HDPE) is investigated in a drop tube reactor under nearly isothermal conditions. The impact of reaction temperature and gas/volatile residence time on carbon conversion and product distribution is examined across a range of 500–900 °C and 3.6–32.2 s, respectively. Non-condensable gas products detected by online mass spectrometry are H2, CH4, C2H4, C2H6, C3H6, and C3H8. At elevated temperatures and prolonged residence time, H2 yield reaches as high as 8.6 wt% of the initial HDPE mass due to intensified cracking reactions of C2–C3 hydrocarbons and long-chain aliphatic compounds. Consequently, pyrolysis tars consist mainly of polycyclic aromatic hydrocarbons (PAHs) with 5–7 rings, accompanied by visible coke deposition within the reactor. HDPE decomposition to volatiles is an endothermic process and it is complete at a temperature between 492 °C and 525 °C, depending on the heating rate employed, from non-isothermal thermogravimetric analysis and differential scanning calorimetry (TGA-DSC) measurements. The thermal degradation of HDPE pellets follows the two-dimensional nucleation growth model for conversion levels up to 0.8 with an apparent activation energy of 259–270 kJ/mol and a pre-exponential factor of 4.83 × 1017–1.37 × 1019 min−1, determined from various isoconversional methods such as Flynn-Wall-Ozawa (FWO), Kissinger-Akahira-Sunose (KAS), and Starink, along with Criado's master plots. These findings provide valuable insights into optimizing process parameters and refining reactor design for pyrolysis, which can be integrated with gasification and reforming processes to enhance hydrogen production on a larger scale.

Curing analysis of rubber film on a Hand-Shaped former in the manufacturing of rubber gloves through novel OpenFOAM solver

Vulcanization, or curing, is a crucial aspect of rubber- or polymer-product manufacturing. Determining the optimal curing time for rubbery components is a significant challenge in the rubber industry. This study focuses on enhancing a computational fluid dynamics code used for simulating the conjugate heat transfer of nitrile-butadiene rubber (NBR) glove curing. Non-isothermal differential scanning calorimetry was employed to analyze the NBR glove-curing process, utilizing constant heating rates ranging from 2.5 to 20 °C/min. Activation-energy calculations employing four isoconversional methods and multivariate nonlinear regression played a pivotal role in determining the most appropriate curing-kinetics model. The multivariate nonlinear regression yielded well-fitted outcomes with a residual sum of squares ranking from 0.44 × 10−3 to 1.60 × 10−3, indicating the suitability of the novel curing-kinetics model for the NBR curing process. After obtaining the appropriate model, adjustments were made to the novel conjugate heat-transfer solver in OpenFOAM to forecast the degree of curing during the heating process. Experimental results from a hot-air counter-flow NBR film in the tray affirmed the accuracy of the solver, demonstrating an impressive R2 value of 0.98. Consequently, the novel solver was applied to simulate the curing process of the NBR film coating on a hand-shaped former surface, offering a visual representation of the degree of curing distribution on the NBR glove. The non-uniform curing and weak curing surface of the NBR glove were revealed, which can be used for estimating the optimal conditions for the curing process or designing an appropriate curing oven for rubber glove manufacturing in the future.

Comparative study of the kinetic behaviors and properties of aromatic and aliphatic bismaleimides

In this paper, three aromatic bismaleimides (BMI-70, BMI-DE and BMI-80) and two aliphatic bismaleimides (BMI-DDA and BMI-C36) were synthesized. The structures were characterized using nuclear magnetic resonance (NMR) spectra and Fourier transform infrared (FT-IR) spectra. Their polymerization behaviors were discussed by non-isothermal differential scanning calorimetry (DSC). The thermal and dielectric properties of the poly(bismaleimide) were investigated using thermogravimetric analysis (TGA), dynamic thermo-mechanical analysis (DMA), and an impedance analyzer. The results indicate that the aliphatic bismaleimides exhibit lower apparent activation energies and dielectric properties, with BMI-DDA displaying an average activation energy of 105.5 kJ mol−1 and the dielectric constant of P(BMI-C36) is 2.558 @ 10 MHz. The aromatic polybismaleimides possessed better thermal stability, among which, the 5 % thermal decomposition temperature (Td,5) of P(BMI-70) was 513.5 °C, and the residual carbon rate at 800 °C was 44.6 %. In additional, water absorption was studied and their saturated water absorption was less than 4 %.

Effect of high copper content in Cux(As2Se3)100-x glass on properties relevant for engineering of thermally induced processes

ABSTRACT Kinetic analysis of thermally induced processes was carried out in Cux(As2Se3)100-x glass with high copper content, x = 20 and 25 at.%. Non-isothermal differential scanning calorimetry at different heating rates was used to analyze the glass-transition and crystallization processes. It was shown that the glass-transition temperature increases with the increase in the copper content and that the examined glasses during the glass transition process do not show large configurational changes in the structure. Apparent activation energy of crystallization was determined using Kissinger method. In the composition with 25 at.% of copper the crystallization of three structural units was detected: CuAsSe2, Cu3AsSe4 and Cu2Se. Analysis of the crystallization mechanism and determination of parameters that depend on the morphology of nucleation and growth showed that volume nucleation and three-dimensional growth occur with a constant number of nucleation centers. Isoconversional analysis showed that the activation energy does not change significantly during the crystallization process.

Polymerization behaviors and properties of benzoxazine resins based-on meta-substituted anilines

The molecular structure of benzoxazine is closely related to its polymerization activity and the properties of its polymer. In this work, benzoxazines were successfully synthesized from phenol, paraformaldehyde and meta-substituted anilines. Their polymerization behaviors were discussed by non-isothermal differential scanning calorimetry (DSC). Moreover, the thermal properties of corresponding polybenzoxazines were evaluated using DSC and thermogravimetric analysis. The results showed that the electron-withdrawing substituent increased the polymerization temperature while the electron-donating substituent lowered the polymerization temperature. The glass transition temperature decreased for polybenzoxazine with electron-donating substituent but elevated for polybenzoxazine with electron-withdrawing substituent. Besides, the thermal stability and thermal degradation mechanism of polybenzoxazine were significantly affected by the substituent. This work supplied further insight in the structure-property relationship of benzoxazine resin.

Non-isothermal kinetics of the organocatalytic ring-opening polymerization of ε-caprolactone with metal-free α‑hydroxy acids: Eco-friendly and facile synthesis process

Metal-free and green α‑hydroxy acids (AHA) such as l-malic (MA), DL-mandelic acid (MDL), and citric acid (CA) were successfully and effectively utilized as an effective initiator for the solvent-free ring-opening polymerization (ROP) of ε-caprolactone (ε-CL). The performance of AHAs in the polymerization of ε-CL was completely and powerfully investigated via the non-isothermal differential scanning calorimetry (DSC). The proceed of ROP of ε-CL with AHAs could be real-time monitored by the obtained polymerization exotherms at different heating rates. The polymerization exotherms obtained from the ROP of ε-CL with CA occurred at a lower temperature range than MA, and MDA, respectively. From the kinetics study, the average activation energy (Ea) values for the ROP of ε-CL with CA (38.0 ± 1.8 kJ mol−1) were lower than MA (45.2 ± 3.6 kJ mol−1) and MDA (48.8 ± 6.2 kJ mol−1). Using the first-order model fitting, the values of pre-exponential factor (lnA0) for the ROP of ε-CL with CA, MA, and MDA were 7.0 ± 0.3, 8.5 ± 0.2, and 8.9 ± 0.3, respectively. The effectiveness of AHAs in the synthesis of PCL was clarified by conducting a larger-scale (4.0000 g) polymerization using conventional heating and microwave (MW) irradiation methods. From conventional heating, the green AHAs produced PCL with the number average molecular weight (Mn) and dispersity (Đ) values in the range of 5.18 × 103 - 1.43 × 104 g mol−1 and 1.14–2.02, respectively. The irradiation by MW could enhance the synthesis of PCL by reducing the synthesis time. By using the MW power of 450 W and irradiation time of 30 min, the PLC was obtained from the ROP of ε-CL with MA and MDA initiators, and the Mn of the obtained PCL from MW heating was 4.28 × 103 - 8.45 × 103 g mol−1. The mechanism for the ROP of ε-CL with all AHAs was proposed through the activated monomer mechanism.

Simulation of thermal hazards risk in octogen based on non-isothermal DSC data

To evaluate the possible thermal risks associated with the storage of octogen (HMX), non-isothermal differential scanning calorimetry (DSC) experiments were conducted in order to ascertain the kinetic model and parameters governing its thermal decomposition. DSC measurements indicate that HMX underwent a crystal transformation prior to thermal decomposition. A kinetic model for the autocatalytic thermal decomposition process was developed through the analysis of its primary exothermic peaks. Subsequently, numerical simulations were performed using the aforementioned kinetic model to assess the potential thermal explosion hazard of HMX under two distinct storage conditions. The comparison was made between the models of HMX autocatalytic decomposition temperature and thermal explosion critical temperature under two distinct storage conditions. The prediction of the influence of ambient temperature on the critical temperature of thermal explosion is conducted simultaneously. Finally, the thermal hazard parameters of HMX under different package quality are given.

Carbohydrate Core-Shell Electrosprayed Microcapsules for Enhanced Oxidative Stability of Vitamin A Palmitate.

Vitamin A is an essential micronutrient that is readily oxidized. In this study, the encapsulation of vitamin A palmitate (AP) within a core-shell carbohydrate matrix by co-axial electrospray and its oxidative stability was evaluated. The electrosprayed core-shell microcapsules consisted of a shell of octenyl succinic anhydride (OSA) modified corn starch, maltose (Hi-Cap), and a core of ethyl cellulose-AP (average diameter of about 3.7 µm). The effect of different compounds (digestion-resistant maltodextrin, soy protein hydrolysate, casein protein hydrolysate, and lecithin) added to the base core-shell matrix formulation on the oxidative stability of AP was investigated. The oxidative stability of AP was evaluated using isothermal and non-isothermal differential scanning calorimetry (DSC), and Raman and Attenuated Total Reflectance-Fourier Transform Infrared (ATR-FTIR) spectroscopy methods. The core-shell carbohydrate matrix minimizes the amount of AP present at the microparticle surface, thus protecting AP from oxidation. Furthermore, the most effective oxidation protection was achieved when casein protein hydrolysate was added to the core of the microcapsule due to hydrophobic and hydrogen bond interactions with AP and by the resistant maltodextrin in the shell, which acted as a filler. The utilization of ethanol as a solvent for the dispersion of the core compounds increased the hydrophobicity of the hydrolyzed proteins and contributed to the enhancement of their antioxidant ability. Both the carbohydrate core-shell microcapsule prepared by co-axial electrospray and the addition of oxidation protection compounds enhance the oxidative stability of the encapsulated AP.

The effect of cross-linking system and reinforcement on the cross-linking reaction of peroxide vulcanized ethylene-propylene-diene terpolymer (EPDM) matrix

In this work, the effect of using of dicumyl-peroxide (DCP) (2, 5 & 8 phr) and co-agent triallyl-cyanurate (TAC) (2, 4 & 6 phr) as cross-linking system as well as multi-walled carbon nanotubes (MWCNTs) (5, 8 και 10 phr) as a filler, for ethylene-propylene-diene terpolymer (EPDM) was investigated. Differential scanning calorimetry (DSC) was employed in order to study the progress of the cross-linking reaction, based on the exothermic vulcanization peaks of isothermal (at 160, 170, 180, 190 °C) and non-isothermal experiments (with heating rates 5, 10, 25, 50 °C min−1). The autocatalytic model was successfully applied to the results of isothermal experiments and the activation energy (Ea) of the reaction was calculated, based on the Arrhenius equation. The Ozawa-Kissinger equations were also applied to the data obtained from the non-isothermal study. From the results obtained from isothermal DSC experiments, an increase was observed in the reaction rates accompanied with a decrease in Ea with the increase of DCP content, whereas a proportional relationship between TAC content and the enthalpy and Ea of the reaction was recorded. The incorporation of MWCNT’s in EPDM increased its Ea. From the non-isothermal DSC experiments, a significant increase in the enthalpy and Ea of the cross-linking reaction was observed at higher DCP content, whereas TAC content did not show any notable effect on the reaction. Based on the results of this research, it is concluded that the increase of peroxide content facilitates the vulcanization of EPDM, whereas inhibition was observed by the incorporation of MWCNT’s.

Activities of cellulose acetate and microcrystalline cellulose on the thermal and morphomechanical performances of a biobased hybrid composite made polybutylene succinate

Microcrystalline cellulose (MCC–30 wt%) was extruded with a blend of polybutylene succinate (PBS) and cellulose acetate (CADS=2.5–20 wt%) to produce two grades of binary (PBS/CA, PBS/MCC) and ternary (PBS/CA/MCC) specimens by injection into a mold previously thermostated at 22 °C and 78 °C. The structure-property relationships of neat PBS (n-PBS) and PBS-based blends were investigated by Fourier transform infrared (FTIR) spectroscopy, diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, scanning electron microscopy (SEM), rheology, differential scanning calorimetry (DSC), thermogravimetry, and mechanical (tensile, bending) tests. FTIR/DRIFT outcomes revealed physical interactions between the ingredients through hydrogen bonds. Rheology and SEM evidenced the presence of entanglements and micro-voids absent in n-PBS. Non-isothermal DSC showed that 22 °C-molded formulations displayed crystalline degrees higher than 78 °C-specimens, except for PBS/MCC. DSC-isothermal analysis showed a hindrance effect of CA on PBS/CA crystallinity and a nucleating impact of MCC on PBS/MCC. Tensile and bending moduli increased for both material grades while the elongation at break decreased. Entanglements and micro-voids had detrimental effects on stress levels because the maximum tensile strength decreased when each or both biofillers were added to PBS. These structural configurations were beneficial for bending strengths since all blends' stiffness relatively increased regardless of material grade.

Cure behavior and mechanism of cyanate ester with aromatic amines at room temperature

Herein, the catalytic effects of aromatic amines with different structures on the room temperature curing of bisphenol E cyanate (BECy) have been studied using differential scanning calorimetry (DSC) and Fourier transform infrared (FT-IR) spectroscopy. Our results revealed that the mixed amine comprised of aniline and N,N-dimethyl-p-phenylenediamine (AN/NNDPA) bearing primary amino groups in its structure was a highly effective catalyst for the room temperature curing of cyanate esters. When the cyanate ester and mixed amine were combined at a molar ratio of 100:5 and cured at room temperature for 5 days, the curing degree of BECy resin reached 79.7%. The room temperature curing mechanism of the BECy-AN/NNDPA system was investigated using pyrolysis gas chromatography-mass spectrometry (PY GC-MS). Our results showed that the formation reactions of the intermediate structure and cyclotrimerization reactions occurred during the room-temperature curing process. The activation energies of BECy and different aromatic amine systems at different heating rates were determined using non-isothermal DSC. The results further demonstrated the catalytic effect of AN/NNDPA on the cyanate ester curing reaction. BECy-AN/NNDPA cured at room temperature has suitable heat resistance and a 5% weight loss temperature (Td5) of 361°C.

Catalytic effect of high thermal conductive SiC on the kinetics and thermodynamics of vulcanization reaction of SBR/BR-filled nano-SiC

Nano-silicon carbide (SiC) as a high thermal conductive material with an intrinsic thermal conductivity of ~ 490 W/m K was used to improve the cure characteristics, kinetics, and thermodynamics of curing reaction of styrene-butadiene rubber/butadiene rubber (SBR/BR) compounds. The considerations were carried out by non-isothermal differential scanning calorimetry (DSC). Results revealed that the presence of SiC shifted the peak and end temperatures of the curing peak to lower temperatures. The calculated activation energy of the curing reaction based on the Kissinger approach showed a descent from 409.8 to 93.8 kJ/mol by adding SiC from 0 to 7.5 phr (part per hundred rubber). Moreover, the obtained Gibbs free energy variation and equilibrium constant of the curing reaction proved that the reaction was absolutely forced and irreversible, which can be increasingly characterized as a one-way process. According to the results, SiC accelerated the curing reaction because of the increment of heat transfer into the compound. This phenomenon caused the increment of enthalpy variation of the vulcanization reaction, particularly at the SiC content of 5 phr. The achieved kinetic parameters via fitting an autocatalytic model based on the Sestàk–Berggren model by the Màlek method to describe the kinetics of the curing reaction indicated that the SiC filler had a catalytic effect on the curing reaction of SBR/BR-SiC, particularly after 2.5 phr of the filler.

Curing Kinetics and Mechanical Properties of Epoxy-Cyanate Ester Composite Films for Microelectronic Applications.

In general, although abundant literature studies are available on epoxy resin systems, a complete description of the curing kinetics in epoxy-cyanate ester composites relevant to the microelectronics industry is still lacking. Herein, curing behaviors of Ajinomoto build-up films, which are epoxy/silica composites, were studied by the non-isothermal differential scanning calorimetry method, and then, three non-isothermal curing kinetics models and model-free curing methods were used to analyze curing behaviors. In addition, a copper layer was also deposited onto the surface of the build-up film, and its interfacial adhesion property was also analyzed at different pre-curing conditions. The results showed that the curing reaction of the build-up film contains two curing reaction processes, and the first curing process is suited for the autocatalytic curing model, while the other curing process is suited for the Kamal curing kinetics model. Three model-free curing methods were used to calculate the activating energy at different degrees of curing, which indicated that the activating energy is variable during the whole curing process. The interfacial adhesion strength between the build-up film and copper layer decreased with the increase in the degree of curing, which is attributed to the contribution of mechanical anchoring. This work will offer guidance in curing behaviors for improving interfacial bonding force and controlling warpage behavior for chip substrates in the future.

Towards Improved Cold-Start Capability of PEFCs: Patterned Gas Diffusion Layers

Polymer electrolyte fuel cells (PEFCs) are electrochemical energy converters with high efficiency and zero pollutant emissions. The unassisted cold-start of PEFCs at -30 °C is one of the major challenges for automotive applications due to the freezing of supercooled water generated by the cathodic oxygen reduction reaction (ORR). Once triggered by the nucleus in cathode gas diffusion layers (GDLs), ice propagates through the active area, leading to oxidant gas blockage and cold-start failure1.The cold-start capability of PEFCs can be improved by preventing ice propagation, especially in GDLs. In our previous work2,3, after the GDLs were segmented by polytetrafluoroethylene (PTFE) into two regions, the PEFC kept operating for another 30 minutes after the first freezing event in one region. Nevertheless, the PTFE barrier limited the active area as well as the heat and electric conductivity of PEFCs. In contrast, patterned GDLs allow water cluster separation without the abovementioned limitations. The improvement of water management and cell performance under technical operating conditions was demonstrated4. Yet, the cold-start capability with patterned GDL needs to be further investigated.This work studies the effect of patterned GDLs on the water-ice phase transition and cold-start capability of PEFCs. First, non-isothermal differential scanning calorimetry (DSC) measurements were conducted to determine the onset freezing temperature distribution of supercooled water in patterned GDLs, taking into account various properties such as coating load and pattern size. It was observed that independent freezing events occurred in patterned GDLs in all cycles, as several freezing/exothermic peaks can be seen in Figure 1b. In contrast, ice propagated immediately in untreated GDL, as only one freezing peak was observed in all cycles (Figure 1d). By computing the integral of the heat flux curve, we obtained the corresponding cumulative icing ratio over 60 cycles, as presented in Figures 1a and 1c. The effective prevention of ice propagation is only observed in patterned GDLs. Second, to assess the cold-start capability, statistical isothermal cold-start measurements were conducted using a 4.4 cm2 differential cell, with the cell temperature held at -7.5 °C, -10 °C, -15 °C, and 20 °C. In summary, nonconcurrent freezing events in patterned GDLs indicate that the use of patterned GDLs significantly improved the cold-start capability of PEFCs under isothermal subfreezing conditions.The findings of this work enhance the understanding of the cold-start dependence on the GDL and contribute to the development of unassisted freeze-start technology for PEFCs and the expansion of PEFCs applications. Figure 1

Thermal properties investigation of paraffin wax/titania nanocomposites as phase change materials

The use of phase change materials (PCMs) for thermal storage, thermal management, and thermal insulation has been widespread for many years. Thermal storage systems (TES) based on PCMs can be improved and optimized by adding nanoparticles (NPs) to them. Throughout this study, PCM nanocomposites (NCs) based on paraffin wax (PW) loaded by anatase titania (TiO2) NPs were fabricated and characterized to examine their thermal performance as phase change materials. The as-synthesized TiO2 NPs were obtained by hydrolysis technique and showed a well-defined spherical shape with a diameter in the nanoscale range and a crystallite size ~ 22.75 nm. Throughout the used concentrations of TiO2 NPs, 0, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, and 0.5%, the morphological feature for the PW/TiO2 NCs revealed a good dispersion of NPs in PW. The non-isothermal differential scanning calorimetry (DSC) measurements at a constant heating rate of 10 °C min−1 were used in order to get the melting point (Tm), latent heat of fusion (LH), and latent heat rate (LHR) as a function of TiO2 NP concentrations for the investigated PW/TiO2 NCs. Both LH and LHR values for PW/TiO2 NCs are higher than those obtained for a pure PW sample. The significant enhancement in LH and LHR values for PW/TiO2 NCs was found to be 21.2% and 134.3% in comparison with the pure PW sample, respectively. The thermal stability of the investigated PW/TiO2 NCs was examined using thermal gravimetric (TG) scans. It is found that the thermal stability varies with TiO2 NP concentrations with a non-monotonic trend. At concentrations up to 0.25 mass%, the thermal stability improved. For concentrations over 0.25 mass%, the degradation process became rapid.