Increase In Transition Temperature Research Articles

Dimerized Nonfused Electron Acceptor Based on a Thieno[3,4-c]pyrrole-4,6-dione Core for Organic Solar Cells.

In this work, the first dimerized nonfused electron acceptor (NFEA), based on thieno[3,4-c]pyrrole-4,6-dione as the core, has been designed and synthesized. The dimerized acceptor and its single counterpart exhibit similar energy levels but different absorption spectra due to their distinct aggregation behavior. The dimerized acceptor-based organic solar cells (OSCs) demonstrate a higher power conversion efficiency of 11.05%, accompanied by enhanced thermal stability. This improvement is attributed to the enhancement of the short-circuit current density and fill factor, along with an increase in the glass transition temperature. Characterizations of exciton dynamics and film morphology reveal that a dimerized acceptor-based device possesses an enhanced exciton dissociation efficiency and a well-established charge transport pathway, explaining its improved photovoltaic performance. All these results indicate that the dimerized NFEA as a promising candidate can achieve efficiency-stability-cost balance in OSCs.

Correlation of thermal and electrical properties of silver germanophosphate glasses with their structural analysis by Raman and NMR spectroscopy

In present study glasses of the system Ag2O-GeO2-P2O5 were studied in the compositional series (50−x)Ag2O-xGeO2-50P2O5 with x = 0−40 mol%. Ag2O substitution by GeO2 results in a significant increase of both glass transition temperature, Tg, and crystallization temperature, Tc, up to 628 °C (Tg) and 851 °C (Tc) at x = 40 mol% GeO2. The glass structure was investigated from the analysis of 31P MAS NMR and Raman spectra. Both methods show transformation of phosphate glass network formed mainly by Q2 units to germanate-phosphate network formed by Q1xGe and Q21Ge phosphate units and germanate units. Raman spectra, in addition, reveal evolution of P‒O‒P linkages to P‒O‒Ge and Ge‒O‒Ge linkages through the glass series. DC conductivity trend upon GeO2 addition showed non-monotonic behaviour, which is related to structural changes in the glass-network.

Nanocellulose Grades with Different Morphologies and Surface Modification as Additives for Waterborne Epoxy Coatings.

While adding different micro- and nanocellulose types into epoxy coating formulations with waterborne phenalkamine crosslinker, effects on processing conditions and coating performance were systematically investigated. The variations in viscosity, thermal and thermomechanical properties, mechanical behavior, abrasive wear, water contact angles, and coating morphologies were evaluated. The selected additives include microcrystalline cellulose (MCC) at 1 to 10 wt.% and cellulose nanocrystals (CNC), cellulose nanofibers (CNF), cellulose microfibers (CMF), and hydrophobically modified cellulose microfibers (mCMF) at 0.1 to 1.5 wt.%. The viscosity profiles are determined by the inherent additive characteristics with strong shear thinning effects for epoxy/CNF, while the epoxy/mCMF provides lower viscosity and better matrix compatibility owing to the lubrication of encapsulated wax. The crosslinking of epoxy/CNF is favored and postponed for epoxy/(CNC, CMF, mCMF), as the stronger interactions between epoxy and CNF are confirmed by an increase in the glass transition temperature and reduction in the dampening factor. The mechanical properties indicate the highest hardness and impact strength for epoxy/CNF resulting in the lowest abrasion wear rates, but ductility enhances and wear rates mostly reduce for epoxy/mCMF together with hydrophobic protection. In addition, the mechanical reinforcement owing to the specific organization of a nanocellulose network at percolation threshold concentrations of 0.75 wt.% is confirmed by microscopic analysis: the latter results in a 2.6 °C (CNF) or 1.6 °C (CNC) increase in the glass transition temperature, 50% (CNF) or 20% (CNC) increase in the E modulus, 37% (CNF) or 32% (CNC) increase in hardness, and 58% (CNF) or 33% (CNC) lower abrasive wear compared to neat epoxy, while higher concentrations up to 1.5 wt.% mCMF can be added. This research significantly demonstrates that nanocellulose is directly compatible with a waterborne phenalkamine crosslinker and actively contributes to the crosslinking of waterborne epoxy coatings, changing the intrinsic glass transition temperatures and hardness properties, to which mechanical coating performance directly relates.

Protection of bovine serum albumin through encapsulation in hybrid vesicles

This study focuses on hybrid vesicles (HVs) formed through co-assembly of soy phosphatidylcholine (SPC) and a triblock copolymer (F127). After elucidating the superior stability of HVs over the assemblies of neat SPC and F127, these were encapsulated with bovine serum albumin (BSA), as model a thermolabile protein. Characterizations were performed using dynamic light scattering (DLS), electron microscopy, circular dichroism and high-sensitivity differential scanning calorimetry. The size of HVs increased slightly at higher proportion of F127 and upon encapsulation of BSA. In spite of this, vesicles remained spherical and displayed a smooth surface. They showed superior dilution stability in comparison to neat copolymer micelles and phospholipid vesicles. Their stability can be ascribed to hydrophobic association between the phospholipid and copolymer, and manifested into increase in phase transition temperature of the former. We found that HVs could protect BSA from denaturation and unfolding when challenged by high solution temperature, pH changes and salt incorporation.

Effect of catalysts on the mechanical, thermal, and adhesive properties of polyrotaxane-modified epoxy resin

Polyrotaxane (PR) is a supramolecular polymer, in which an axial polymer extends through multiple cyclic molecules. PR specifically comprises polyethylene glycol, α-cyclodextrin, and adamantane as the axial polymer, cyclic molecule, and terminal blocking group, respectively. It is a useful stress-relaxing material because the cyclic polymers can freely slide and rotate in cyclic motions on the axial polymer. In this study, epoxy resin (DGEBA) cured with phenolic resin (PN) was blended with PR, which has methacryl groups at the ends of side chains of the cyclic molecules, as a toughness modifier. The effect of the methacryl group polymerization catalyst (DCP) on the cured properties of epoxy resin was reported. PR was homogeneously dispersed in the DGEBA/PN resin matrix. Increasing the PR concentration significantly improved the toughness, impact resistance, and adhesive properties of the DGEBA/PN/PR alloy. Moreover, adding DCP resulted in an increase in the glass transition temperature due to the decreased molecular mobility of the network. This phenomenon was attributed to the synergistic effect of the formation of an interpenetrating polymer network, which is an entangled network of the curing reaction of the DGEBA/PN resin and polymerization of PR, and the intermolecular hydrogen bonds between carbonyl and hydroxyl groups of PR and hydroxyl groups of the DGEBA/PN resin. In contrast, the increased interfacial adhesion between PR and the DGEBA/PN did not result in significant improvement of flexural properties.

Double perovskite oxides Ba2-xAgxFeMoO6 (x = 0.0, 0.025, 0.05)

Double perovskite Ba2FeMoO6 (BFMO) substituted with monovalent Ag ions was synthesized using the sol-gel method, and its structure and magnetic properties were systematically studied. Rietveld refinement showed that the samples had a single phase with a cubic structure and an Fm-3m space group. With Ag substitution, the lattice parameter and unit cell of BFMO increased linearly, and the morphology of the samples was altered. X-ray photoelectron spectroscopy (XPS) examination showed mixed valence in the sample with x = 0.025 due to the Ag doping. The doped samples exhibited a decrease in magnetization, an increase in transition temperature, and anti-site (AS) defects. The AC magnetic susceptibility of the sample with x = 0.025 showed two peaks attributed to the two critical temperatures.

Multiscale Carbon Fibre-Carbon Nanotube Composites of Poly(Vinyl Chloride)-An Evaluation of Their Properties and Structure.

To date, there has been limited information in the literature on the application of carbon fibre-carbon nanotube systems for the modification of poly(vinyl chloride) (PVC) matrixes by micro- and nanometric fillers and an evaluation of the properties of the unique materials produced. This paper presents the results of newly designed unique multiscale composites. The advantages of the simultaneous use of carbon fibres (CFs) and carbon nanotubes (CNTs) in PVC modification are discussed. To increase the dispersibility of the nanofiller, CFs together with nanotubes were subjected to a sonication process. The resulting material was introduced into PVC blends, which were processed by extrusion. The ratio of components in the hybrid filler with CF_CNT was 20:1, and its proportion in the PVC matrix was 1, 5, and 10 wt.%, respectively. Comparatively, PVC composites modified only with carbon fibres were obtained. The structure, thermal, electrical, and mechanical properties and swelling resistance of the composites were studied. The study showed a favourable homogeneous dispersion of nanotubes in the PVC matrix. This enabled effective modification of the structure at the nanometric level and the formation of an interpenetrating network of well-dispersed hybrid filler, as evidenced by a decrease in volume resistivity and improvement in swelling resistance, as well as an increase in glass transition temperature in the case of PVC/CF_CNT composites.

In silico Characterization of Natural Blending Agents in Conjunction with Polyhydroxybutyrate (PHB) to Solicit Biopolymer film with Improved Thermal Stability

Polyhydroxybutyrate (PHB) is known to exhibit limitations in terms of thermal stability. Its susceptibility to thermal degradation, particularly when exposed to high temperatures, can hinder its performance in various applications. This study addresses the thermal stability limitations of Polyhydroxybutyrate (PHB) by exploring strategies to enhance its performance through blending with biodegradable polymers. Focusing on the PHB-pectin blend, computational simulations unveil a remarkable 346.92 K increase in the glass transition temperature (Tg), surpassing pure PHB. This elevation indicates strong intermolecular interactions, potentially involving hydrogen bonding, leading to a more rigid and thermally stable polymer system. The heightened Tg has practical implications for critical applications, such as automotive components and electronic devices, where resistance to elevated temperatures is essential. Emphasizing environmental benefits, the study highlights the use of biodegradable and bio-based polymers as eco-friendly alternatives to traditional plastics, contributing to reduced plastic waste. Overall, this research underscores the potential of thermally stable polymers to both enhance material performance and address environmental concerns across diverse industries.

Enhancement of the rheological, dynamic mechanical, and morphological properties of thermoplastic natural rubber based on NR/PP blends using ENR/PP-g-MA as a compatibilizer

This study investigates the effects of incorporating a 50/50 blend of Epoxidized Natural Rubber/Polypropylene-grafted maleic anhydride (ENR/PP-g-MA) as a compatibilizing agent (CA) for a 70/30 Natural Rubber/Polypropylene (NR/PP) thermoplastic elastomer (TPE) on the technical properties such as structural analysis, rheological, dynamic mechanical and morphological properties. Formulations with varying CA concentrations (5 to 15 phr) were prepared using a Brabender plasticorder at 180°C for 10 min. The structural analysis was examined by Fourier transform infrared spectroscopy (FTIR), and proton nuclear magnetic resonance (1H-NMR). The rheological behavior was examined using a Rubber Process Analyser (RPA). The dynamic mechanical properties were investigated by DMA. Atomic Force Microscopy (AFM) was used for the morphological examination. FTIR analysis confirmed reactions between the MA group in PP-g-MA and the epoxy groups in ENR, resulting in ENR-grafted PP with an ester and acid-based linkage. This reaction was evident during compatibilizer preparation. RPA results showed increased viscosity for both types of CAs compared to their individual values, confirming crosslinking reactions. Higher CA concentrations led to elevated viscosity and storage modulus. DMA results indicated that the compatibilization led to a significant enhancement in the storage modulus of the blends. Moreover, an increase in the glass transition temperatures (Tg) of the blends was produced. AFM examination revealed a more homogenous distribution of the dispersed PP phase for the CA-containing blends compared to the control NR/PP system.

Effects of carbon‐based nanoparticles on the properties of poly(lactic acid) hybrid composites containing basalt fibers and carbon‐based nanoparticles processed by injection molding

AbstractIn this study, we developed composites with a poly(lactic acid) matrix and reinforced with basalt fiber, carbon‐based nanoparticles (carbon nanotube [CNT] and expanded graphene [GNP]), and both basalt fiber and nanoparticles (hybrid composites). The composites were produced by extrusion, and then tensile specimens were injection molded from the composites. The hybrid composites exhibited enhanced mechanical properties. The reinforcing materials increased crystallinity; this was more pronounced for hybrid composites. We experienced significant increase in the glass transition temperature, which proves the better interaction between the reinforcing and the matrix phases. Dynamic mechanical thermal analysis showed that the nanoparticles increased the storage modulus both alone and in combination with basalt fibers. Furthermore, the basalt fiber‐reinforced composites and hybrids exhibited significant modulus above the glass transition temperature. Based on scanning electron microscopy images of the fracture surfaces, we concluded that adding basalt fibers during compounding resulted in better dispersion of the nanoparticles.Highlights Poly(lactic acid) (PLA) reinforced with basalt fiber has good strength properties. Graphene hybrid exhibits notable tensile modulus improvement in hybrids. Graphene and carbon nanotubes are crystalline nucleating agents for PLA. Enhanced nanoparticle distribution was discovered for hybrid composites. The glass transition temperature of PLA increases with reinforcement.

Development of starch-rich thermoplastic polymers based on mango kernel flour and different plasticizers

This work reports on the development of starch-rich thermoplastic based formulations produced by using mango kernel flour, avoiding the extraction process of starch from mango kernel to produce these materials. Glycerol, sorbitol and urea at 15 wt% are used as plasticizers to obtain thermoplastic starch (TPS) formulations by extrusion and injection-moulding processes. Mechanical results show that sorbitol and urea allowed to obtain samples with tensile strength and elongation at break higher than the glycerol-plasticized sample, achieving values of 2.9 MPa of tensile strength and 42 % of elongation at break at 53 % RH. These results are supported by field emission scanning electron microscopy (FESEM) micrographs, where a limited concentration of voids was observed in the samples with sorbitol and urea, indicating a better interaction between starch and the plasticizers. Thermogravimetric analysis (TGA) shows that urea and sorbitol increase the thermal stability of TPS in comparison to the glycerol-plasticized sample. Differential scanning calorimetry (DSC) and dynamic-mechanical-thermal analysis (DMTA) verify the increase in stiffness of the sorbitol and urea plasticized TPS and also illustrate an increase in the glass transition temperature of both samples in comparison to the glycerol-plasticized sample. Glass transition temperatures of 45 °C were achieved for the sample with sorbitol.

Irradiation microstructures and hardening in commercial nuclear reactor pressure vessel steels at high extended life fluence

Nuclear reactor lifetimes up to and beyond 80 years may be limited by nano-scale Cu-Mn-Ni-Si precipitates (CRPs and MNSPs) that form under neutron irradiation in pressure vessel (RPV) steels, resulting in hardening and ductile to brittle transition temperature increases, or embrittlement. Here, Atom Probe Tomography (APT) is used to characterize precipitation in nine actual RPV steels, irradiated in the ATR-2 test reactor, to a high fluence 1.38 × 1020 n/cm2 at 292 °C and 3.68 × 1012 n/cm2 s. APT quantifies the relation between a wide range surveillance alloy Cu, Ni, Mn, and Si contents and the corresponding precipitate volume fractions, number densities, sizes, and compositions. The precipitate volume fraction (fp) is dominated by the dissolved steel Cu and Ni contents. Irradiation hardening shows the expected dependence on the √fp. The APT results also provide an opportunity to evaluate flux effects by direct comparisons with corresponding archival data from low flux surveillance irradiations. Most notably, this work establishes a strong microstructural and mechanistic foundation for the new data-driven Odette, Wells, Almirall, and Yamamoto (OWAY) model to predict high fluence RPV steel embrittlement.

Enhancing fracture toughness of carbon fiber/epoxy composites using polyphenylene ether as a modifier

AbstractIn this study, carbon fiber/epoxy composites (CFRP) were fabricated by vacuum‐assisted resin infusion molding (VARIM) with polyphenylene ether (PPE) as a toughening agent. The PPE contained hydroxyl end groups that facilitated chemical bonding with epoxy during curing. PPE was incorporated into the epoxy matrix by dissolution, and spreading in the interlaminar regions. The presence of PPE as a toughener exhibited significant improvement in the Mode‐I fracture toughness of the composites. The CFRP samples, which were toughened with 5 wt.% and 10 wt.% PPE, showed about 191% to 380% enhancement, respectively, in the critical energy release rate (GIC) compared to the unmodified sample. Dynamic mechanical analysis (DMA) showed about a 6°C increase in the glass transition temperature of the toughened composites, which is an interesting aspect of this work. These results indicate the potential of using PPE as a toughening agent in CFRP composites.

Development of Sustainable and Active Food Packaging Materials Composed by Chitosan, Polyvinyl Alcohol and Quercetin Functionalized Layered Clay.

In order to solve the problems of insufficient active functions (antibacterial and antioxidant activities) and the poor degradability of traditional plastic packaging materials, biodegradable chitosan (CS)/polyvinyl alcohol (PVA) nanocomposite active films reinforced with natural plant polyphenol-quercetin functionalized layered clay nanosheets (QUE-LDHs) were prepared by a solution casting method. In this study, QUE-LDHs realizes a combination of the active functions of QUE and the enhancement effect of LDHs nanosheets through the deposition and complexation of QUE and copper ions on the LDHs. Infrared and thermal analysis results revealed that there was a strong interface interaction between QUE-LDHs and CS/PVA matrix, resulting in the limited movement of PVA molecules and the increase in glass transition temperature and melting temperature. With the addition of QUE-LDHs, the active films showed excellent UV barrier, antibacterial, antioxidant properties and tensile strength, and still had certain transparency in the range of visible light. As QUE-LDHs content was 3 wt%, the active films exhibited a maximum tensile strength of 58.9 MPa, representing a significant increase of 40.9% compared with CS/PVA matrix. Notably, the UV barrier (280 nm), antibacterial (E. coli) and antioxidant activities (DPPH method) of the active films achieved 100.0%, 95.5% and 58.9%, respectively. Therefore, CS/PVA matrix reinforced with QUE-LDHs has good potential to act as an environmentally and friendly active packaging film or coating.

Development of Curcumin Composite Gel Inhibitor for Preventing Spontaneous Combustion of Coal

ABSTRACT To improve their whole-stage inhibition effects on the spontaneous combustion of coal, curcumin (CCM) and chitosan (CTS) were grafted, and the natural nanomaterial montmorillonite (MMT) was used for intercalation to prepare the composite gel inhibitor CTS-CCM/MMT. Its macro effect and micro mechanism of inhibition were studied. SEM analysis revealed a significant increase in the surface folds and pores of CTS-CCM, suggesting enhanced mechanical properties and thermal stability. XRD and DSC experiments demonstrated a reduction in the diffraction angle 2θ from 21.148° to 20.011° for CTS-CCM/MMT, along with a 21.3% increase in glass transition temperature. This supports the effective improvement of thermal stability through intercalation treatment. Thermogravimetric analysis indicated a higher characteristic temperature point for the inhibitor composite. Infrared diffuse reflection experiments showed deactivation of oxidation activity for the hydroxyl and aliphatic groups through combined inhibition treatment. These findings collectively suggest that the gel exhibits heightened stability and flame retardancy, and can effectively inhibit the entire spontaneous combustion reaction of coal.

Programming molecular switches in water and ethanol via thermo-sensitive polymers for phase control in energetic crystals

The practical application of energetic materials, particularly 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20), is frequently impeded by phase transition challenges. In this study, we propose a novel strategy to enhance the stability of CL-20 by employing a thermo-sensitive polymer, poly(N-isopropylacrylamide) (PNIPAM), to modulate its phase transitions. Our approach involves the use of an in-situ polymerized polydopamine (PDA) shell as a platform for surface grafting through atom transfer radical polymerization, yielding a core-shell structured CL-20@PDA-PNIPAM. Through comprehensive characterization, the successful grafting of PNIPAM is confirmed, significantly enhanced the phase stability of CL-20. Notably, our core-shell structure exhibits a 13 °C increase in phase transition temperature compared to raw CL-20, thereby delaying the ε→α phase transition by over 80 min under combined thermal and solvent conditions. The enhanced stability is attributed to the hydrophobic nature of PNIPAM above its low critical solution temperature in water, which effectively shields the CL-20 crystal. These findings provide new insights into enhancing the stability and safety of energetic materials in complex environments, highlighting the potential of our molecular switch mechanism.

Mechanically interlocked [c2]daisy chain backbone enabling advanced shape-memory polymeric materials

The incorporation of mechanically interlocked structures into polymer backbones has been shown to confer remarkable functionalities to materials. In this work, a [c2]daisy chain unit based on dibenzo-24-crown-8 is covalently embedded into the backbone of a polymer network, resulting in a synthetic material possessing remarkable shape-memory properties under thermal control. By decoupling the molecular structure into three control groups, we demonstrate the essential role of the [c2]daisy chain crosslinks in driving the shape memory function. The mechanically interlocked topology is found to be an essential element for the increase of glass transition temperature and consequent gain of shape memory function. The supramolecular host-guest interactions within the [c2]daisy chain topology not only ensure robust mechanical strength and good network stability of the polymer, but also impart the shape memory polymer with remarkable shape recovery properties and fatigue resistance ability. The incorporation of the [c2]daisy chain unit as a building block has the potential to lay the groundwork for the development of a wide range of shape-memory polymer materials.

Ion Conductivity in Salt-Doped Polymers: Combined Effects of Temperature and Salt Concentration.

We construct a coarse-grained molecular dynamics model based on poly(ethylene oxide) and lithium bis(trifluoromethane)sulfonimide salt to examine the combined effects of temperature and salt concentration on the transport properties. Salt doping notably slows the dynamics of polymer chains and reduces ion diffusivity, resulting in a glass transition temperature increase proportional to the salt concentration. The polymer diffusion is shown to be well represented by a modified Vogel-Fulcher-Tamman (M-VFT) equation that accounts for both the temperature and salt concentration dependence. Furthermore, we find that, at any temperature, the concentration dependence of the conductivity is well described by the product of its infinite dilution value and a correction factor accounting for the reduced segmental mobility with increasing salt concentration. These results highlight the important role of polymer segmental mobility in the salt concentration dependence of ion conductivity for temperatures near and above the glass transition.

The Influence of Hydroxyapatite Crystals on the Viscoelastic Behavior of Poly(vinyl alcohol) Braid Systems.

Composites of poly(vinyl alcohol) (PVA) in the shape of braids, in combination with crystals of hydroxyapatite (HAp), were analyzed to perceive the influence of this bioceramic on both the quasi-static and viscoelastic behavior under tensile loading. Analyses involving energy-dispersive X-ray spectroscopy (EDS) and scanning electron microscopy (SEM) allowed us to conclude that the production of a homogeneous layer of HAp on the braiding surface and the calcium/phosphate atomic ratio were comparable to those of natural bone. The maximum degradation temperature established by thermogravimetric analysis (TGA) showed a modest decrease with the addition of HAp. By adding HAp to PVA braids, an increase in the glass transition temperature (Tg) is noticed, as demonstrated by dynamic mechanical analysis (DMA) and differential thermal analysis (DTA). The PVA/HAp composite braids' peaks were validated by Fourier transform infrared (FTIR) spectroscopy to be in good agreement with common PVA and HAp patterns. PVA/HAp braids, a solution often used in the textile industry, showed superior overall mechanical characteristics in monotonic tensile tests. Creep and relaxation testing showed that adding HAp to the eight and six-braided yarn architectures was beneficial. By exhibiting good mechanical performance and most likely increased biological qualities that accompany conventional care for bone applications in the fracture healing field, particularly multifragmentary ones, these arrangements can be applied as a fibrous fixation system.

Silver/Antimony-Base Multifunctional Double Perovskite with H/F Substitution Enhance Properties.

Two-dimensional double perovskites have experienced rapid development due to their outstanding optoelectronic properties and diverse structural characteristics. However, the synthesis of high-performance multifunctional compounds and the regulation of their properties still lack relevant examples. Herein, we synthesized two multifunctional compounds, (C6H14N)4AgSbBr8 (1) and (F2-C6H12N)4AgSbBr8 (2), which exhibit high solid-state phase transition temperature, bistable dielectric constant switching, second harmonic generation (SHG), and bright emission. Through H/F substitution, the transition temperature increases and achieves a smaller band gap attributed to reduced interlayer spacing. Furthermore, we investigated the broad emission mechanism of the compounds through first-principles calculation and variable-temperature fluorescence, confirming the presence of the STE1 emission. Our work provides insight into the further development of multifunctional compounds and chemical modification that enhances compound properties.