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The relationship between thermodynamic entropy generation and free volume changes during the tensile deformation of epoxy resin was investigated. Thermodynamic entropy generation was evaluated using differential scanning calorimetry (DSC) for samples at various strain levels, while free volume changes were measured with positron annihilation lifetime spectroscopy (PALS). Volumetric strain was assessed through the digital image correlation (DIC) method. The results showed that both thermodynamic entropy and free volume increase during tensile deformation, and the average free volume radius becomes more uniform. It was observed that thermodynamic entropy generation and free volume each exhibit a linear relationship with volumetric strain. Additionally, thermodynamic entropy generation increased linearly with free volume. These findings suggest that the increase in thermodynamic entropy during tensile deformation is attributed to irreversible changes, such as the expansion of free volume within the material. [ABSTRACT FROM AUTHOR]

High-voltage dielectric and AC conduction behaviors of epoxy resin (EP) insulation are beneficial for the design and application of solid-state power electronic devices. This study investigates the nonlinear dielectric response and AC conduction characteristics of EP. The dielectric relaxation characteristics, including permittivity and AC conductivity of the EP samples, were investigated using high-voltage dielectric spectroscopy and the ionic polarization model. The results demonstrate a nonlinear increase in the relative permittivity and AC conductivity concerning the AC electric field. The increase in AC conduction under a high-frequency electric field is attributed to the reduction in the threshold field for charge injection caused by elevated temperatures. Considering the dielectric response and carrier hopping, it is evident that the nonlinear dielectric response of EP primarily originates from the ionic process under high electric fields. Ionic polarization, in conjunction with ion-hopping conduction, enhances the dielectric loss at high frequencies and electric fields, thereby facilitating the nonlinear conversion of AC conduction. The equivalent free volume is likely to increase in high-frequency fields. This phenomenon leads to an increase in AC conduction and even dielectric breakdown. This study offers a pivotal theoretical framework for the design and application of high-frequency insulation. [ABSTRACT FROM AUTHOR]

Cross-links significantly influence the chain packing efficiency and free volume in elastomeric materials, affecting their segmental dynamics. In this context, ionomeric elastomers serve as model systems that can undergo vulcanization through covalent and ionic cross-linking, enabling tuning their macroscopic properties. In this study, we investigate the effects of sulfur (covalent) and zinc oxide (ionic) cross-linking (with and without stearic acid) on the cross-link density, molecular-scale free volume, segmental relaxation and mechanical properties of carboxylated nitrile butadiene rubber (XNBR) networks by using a combination of analytical techniques including swelling studies, positron annihilation lifetime spectroscopy (PALS), dynamic mechanical analysis (DMA) and tensile testing. PALS measurements revealed a distinctive bimodal distribution of free-volume elements in the ionomeric networks, observed for the first time. This feature provided evidence of ionic aggregation-induced immobilization of polymer chains, which resulted in smaller free volume elements (1.5–2 Å) than in the bulk ionomeric matrix (3.0–3.5 Å). DMA studies revealed two segmental relaxations (α and α′) in the cross-linked elastomers, which could be tailored based on the cross-link density of the networks. The frequency-dependent DMA master curves, derived through time-temperature superposition, showed broad tan δ (loss factor) vs. frequency profiles for the networks with tan δ values exceeding 0.50, indicating their potential suitability for passive vibration damping applications. The ionically cross-linked networks exhibited superior mechanical properties compared to the networks prepared by covalent and mixed modes of curing. Schematic illustration of the structure of XNBR networks; dispersion of the ionic aggregates of zinc carboxylate moieties in the hydrocarbon matrix. The polymer chains surrounding the ionic aggregates are shown to be trapped and are deemed to be the region of relatively higher electron density. The o-Ps localized in this region is the likely source of shorter o-Ps lifetime (τ3) and the o-Ps localized in the spatial region between ionic aggregates, i.e., the bulk of the matrix is posited to be the source of longer o-Ps lifetime (τ4). [ABSTRACT FROM AUTHOR]

Abstract The positron annihilation lifetime (PAL) spectroscopy characteristics of ethylene-propylene-diene monomer rubber (EPDM) composites reinforced with treated wheat husk fibers (WHFs) were investigated for the first time. PAL spectroscopy is employed to study the free volume of polymers. The use of lignocellulosic materials as reinforcement in polymeric composites has gained attention due to their low cost, availability, and eco-friendliness. In this study, the impact of the loading concentration on the interfacial adhesion between the EPDM matrix and WHFs is quantified, along with the evaluation of swelling measurement and tensile properties. Additionally, the nanoscopic properties derived from PAL spectroscopy correlate with the composites’ macroscopic properties. In addition, the dielectric properties of the investigated samples have been studied, and their conductivity has been calculated. To determine the conduction mechanism within these samples and how it is affected by the addition of WHF, the change in electrical conductivity with the frequency of the external electric field applied to the samples was studied, and from this, the conduction mechanism was determined, and the barrier height value was calculated. The experimental results provide insights into the relationship between the structure and properties of EPDM-WHF biocomposites, offering valuable knowledge for developing sustainable and high-performance materials.

The sensitivity of positron annihilation characteristics to changes in the molecular packing in network-forming polymers has been demonstrated since the early 1980s. Positron annihilation lifetime spectroscopy (PALS) is a unique technique that can provide direct information on the free volume in polymers through the experimental parameters of the free volume hole distribution, their mean value, and volume fraction. This knowledge is currently applied for PALS investigations on the main processes that govern the molecular organization in some green polymers when subjected to different synthesis procedures or environmental conditions (humidity, physical aging, temperature). In this article, which includes a wide repertoire of works published in the last two decades, results of PALS studies on eco-sustainable polymer systems based on starch, chitosan, or vegetable oils, are analyzed and discussed. Many examples are taken from the direct experience of the authors. [ABSTRACT FROM AUTHOR]

This study investigates the effect of microstructural changes in polyurethane coatings on their water resistance properties. Polyurethane coatings with varying diluent contents were prepared and tested for water penetration resistance and mechanical property retention. The time-dependent behavior of water within the coatings at different immersion durations was analyzed using low-field nuclear magnetic resonance (NMR). Furthermore, the free volume and characteristic molecular groups of each coating were analyzed using microscopic techniques, including positron annihilation lifetime spectroscopy (PALS) and attenuated total reflectance Fourier-transform infrared spectroscopy (ATR−FTIR). Results indicate that diluent content significantly alters the microstructure of the coatings. With increasing diluent content, both the average pore volume and free volume fraction initially decrease and then increase, while characteristic molecular groups, including hydrophilic groups, gradually decline. The water resistance performance of the coatings was significantly influenced by the combined effects of free volume and characteristic molecular groups. Among the five tested coating formulations, coatings with diluent contents of 20% and 25% showed a superior water penetration resistance, higher retention of mechanical properties after immersion, and relatively low total content of bound and free water at all immersion ages. The entropy weight method and the equal weight method were used to assess the overall water resistance, with the following ranking of scores: f20 > f25 > f30 > f15 > f10. This study offers theoretical support to guide the design and practical application of polyurethane coatings in real-world engineering projects. [ABSTRACT FROM AUTHOR]

The structural and dynamic properties of poly(2-hydroxyethyl methacrylate) (PHEMA) and poly(N-vinylpyrrolidone-co-2-hydroxyethyl methacrylate) [P(VP-co-HEMA)], dry and as hydrogels, were studied by molecular dynamics simulations. The P(VP-co-HEMA) chains differed in the number of VP mers, distributed randomly or in blocks. In all considered configurations, HEMA and VP side chains proved relatively rigid and stable. Water concentration had a significant impact on their dynamic behavior. Oxygen atoms of hydroxyl and carbonyl groups of HEMA and carbonyl groups of VP are preferred sites of hydrogen bonding with water molecules. The copolymer swelling results in diffusion channels, larger in systems with high water content. In low-hydrated materials, water shows subdiffusion, while normal diffusion predominates in the high-hydrated ones. The VP side chains in copolymers with HEMA do not enhance the mobility of water. [ABSTRACT FROM AUTHOR]

A theory for the micelle formation of nonionic head-tail amphiphiles (detergents) in aqueous solutions is derived based on the traditional molecular thermodynamic modeling approach and a variant of the Flory–Huggins theory that goes beyond lattice models. The theory is used to analyze experimental values for the critical micelle concentration of n-alkyl-ß-D-maltosides within a mass action model. To correlate those parts of the micellization free energy, which depend on the transfer of hydrophobic molecule parts into the aqueous phase, with molecular surfaces, known data for the solubility of alkanes in water are reanalyzed. The correct surface tension to be used in connection with the solvent-excluded surface of the alky tail is ~30 mN/m. This value is smaller than the measured surface tension of a macroscopic alkane–water interface, because the transfer free energy contains a contribution from the incorporation of the alkane or alkyl chain into water, representing the change in free volume in the aqueous phase. The Flory–Huggins theory works well, if one takes into account the difference in liberation free energy between micelles and monomers, which can be described in terms of the aggregation number as well as the thermal de Broglie wavelength and the free volume of the detergent monomer. [ABSTRACT FROM AUTHOR]

The positron annihilation lifetime (PAL) spectroscopy characteristics of ethylene-propylene-diene monomer rubber (EPDM) composites reinforced with treated wheat husk fibers (WHFs) were investigated for the first time. PAL spectroscopy is employed to study the free volume of polymers. The use of lignocellulosic materials as reinforcement in polymeric composites has gained attention due to their low cost, availability, and eco-friendliness. In this study, the impact of the loading concentration on the interfacial adhesion between the EPDM matrix and WHFs is quantified, along with the evaluation of swelling measurement and tensile properties. Additionally, the nanoscopic properties derived from PAL spectroscopy correlate with the composites' macroscopic properties. In addition, the dielectric properties of the investigated samples have been studied, and their conductivity has been calculated. To determine the conduction mechanism within these samples and how it is affected by the addition of WHF, the change in electrical conductivity with the frequency of the external electric field applied to the samples was studied, and from this, the conduction mechanism was determined, and the barrier height value was calculated. The experimental results provide insights into the relationship between the structure and properties of EPDM-WHF biocomposites, offering valuable knowledge for developing sustainable and high-performance materials. [ABSTRACT FROM AUTHOR]

The influence of plastic deformation on the formation of nanocrystals in the Al87Ni6Nd7 amorphous alloy was studied using X-ray diffraction analysis. It has been shown that the preliminary deformation of the amorphous alloy accelerates the crystallization of the amorphous phase and can lead to the formation of smaller nanocrystals compared to heat treatment. The size of nanocrystals and their number depend on the treatment conditions of the amorphous phase: when preliminary deformation is used, the size of nanocrystals formed during annealing is smaller than that in an undeformed sample and the proportion of nanocrystals is slightly higher. In samples subjected to preliminary deformation by rolling, a gradient structure is formed: the proportion of nanocrystals decreases with distance from the surface into the depth of the sample. The size of nanocrystals changes slightly with changing distance from the sample surface. The results show that preliminary plastic deformation can be an effective method to obtain a nanocrystalline structure with different proportion and sizes of nanocrystals in the amorphous phase. This is important for creating highly functional materials with outstanding physicochemical properties. The results obtained significantly expand the existing understanding of the mechanisms of formation of nanocrystals in the amorphous phase under external influences. [ABSTRACT FROM AUTHOR]

Abstract The deformation behavior of metallic glasses has been shown in prior studies to be often dependent on its structural state, namely higher energy “rejuvenated” state versus lower energy “relaxed” state. Here, the deformation behavior of thermally rejuvenated Zr-Cu-Al-(Ti) bulk metallic glasses (BMGs) was evaluated. Rejuvenation was achieved by cryogenic thermal cycling with increase of free volume measured in terms of enthalpy of relaxation. Hardness, stiffness, and yield strength of the BMGs were all found to decrease while plasticity increased after rejuvenation. More free volume in the rejuvenated BMG resulted in homogeneous plastic deformation as was evident from the high strain rate sensitivity and more pronounced shear band multiplication during uniaxial compression. Shear transformation zone (STZ) volume was calculated by cooperative shear model and correlated well with the change in structural state after rejuvenation. The enhanced plasticity with the addition of 1 at. % Ti as well as after cryogenic thermal cycling was explained by lower activation energy for shear flow initiation due to increased heterogeneity induced in the system. Molecular dynamics simulation demonstrated that the variation in plastic deformation behavior is correlated with local atomic structure changes.

The microstructure and chemical properties of the corona discharge process could provide an effective method for predicting the performance of high-voltage cable insulation materials. In this work, the depth profile of the microstructure and chemical characteristics of corona discharge-treated PE were extensively investigated using Doppler broadening of position annihilation spectroscopy accompanied with positron annihilation lifetime spectroscopy, attenuated total reflectance Fourier transform infrared spectra, Raman spectra and contact angle measurement. By increasing corona discharge duration, the oxygen-containing polar groups, including hydroxyl, carbonyl and ester groups, strongly contribute to the deterioration of hydrophobicity and the enhancement of hydrophilicity. And the mean free volume size, with a broadening distribution, decreases slightly. The line shape S parameter decreases because of the decrease in free volume elements and the appearance of oxygen-containing groups. Also, the thickness of the degradation layer, determined from the S parameter with positron injection depth, increases and diffuses into the PE matrix. A linear S-W plot within the degradation layer of different corona treatment duration samples indicates the defect type does not change. The S parameter decreases and the W parameter increases with an increasing corona duration. Using a slow positron beam, the nondestructive probe can be used to profile the microstructure and chemical environment across the corona discharge damage depth, which is beneficial for investigating the surface and interfacial insulation materials. [ABSTRACT FROM AUTHOR]

The polymer liner of the hydrogen storage cylinder was studied to investigate better hydrogen storage capacity in Type-IV cylinders. Molecular dynamics methods were used to simulate the adsorption and diffusion processes of hydrogen in a graphene-filled polyamide 6 (PA6) system. The solubility and diffusion characteristics of hydrogen in PA6 systems filled with different filler ratios (3 wt%, 4 wt%, 5 wt%, 6 wt%, and 7 wt%) were studied under working pressures (0.1 MPa, 35 MPa, 52 MPa, and 70 MPa). The effects of filler ratio, temperature, and pressure on hydrogen diffusion were analyzed. The results show that at atmospheric pressure when the graphene content reaches 5 wt%, its permeability coefficient is as low as 2.44 × 10−13 cm3·cm/(cm2·s·Pa), which is a 54.6% reduction compared to PA6. At 358 K and 70 MPa, the diffusion coefficient of the 5 wt% graphene/PA6 composite system is 138% higher than that at 298 K and 70 MPa. With increasing pressure, the diffusion coefficients of all materials generally decrease linearly. Among them, pure PA6 has the largest diffusion coefficient, while the 4 wt% graphene/PA6 composite system has the smallest diffusion coefficient. Additionally, the impact of FFV (free volume fraction) on the barrier properties of the material was studied, and the movement trajectory of H2 in the composite system was analyzed. [ABSTRACT FROM AUTHOR]

In this study, a series of biodegradable poly(butylene alkylene carboxylate‐co‐terephthalate) copolymers with varying methylene numbers in the alkylene units (0, 2, 4, and 8) are synthesized. These copolymers, namely, poly(butylene oxalate‐co‐terephthalate) (PBOT), poly(butylene succinate‐co‐terephthalate) (PBST), poly(butylene adipate‐co‐terephthalate) (PBAT), and poly(butylene sebacate‐co‐terephthalate) (PBSeT), are prepared with nearly identical structural and molar compositions. The objective of this study is to comprehensively examine the impact of alkylene unit length on the barrier properties of the materials, delving into aspects such as crystallinity, free volume, molecular chain mobility, as well as adsorption and diffusion of gases within the materials. The findings indicate a decrease in crystallinity from 17.2% for PBOT to 10.2% for PBSeT as the alkylene chain length increases, while maintaining the same chemical composition. Concurrently, the fractional free volume increases from 0.9% to 2.6%, and the melt flow activation energy decreases from 106.6 to 52.1 kJ mol−1. Importantly, theoretical calculations are performed, demonstrating that the predominant site for gas adsorption and diffusion is within the material's free volume. These combined observations indicate a gradual decrease in barrier properties as the number of methylene groups increases. [ABSTRACT FROM AUTHOR]

Polyethylene (PE) is susceptible to environmental stress cracking (ESC). In the presence of an amphiphilic compound and subjected to stress, ESC starts with cavitation followed by slow crack growth and ends with brittle fracture. In this study, we used molecular dynamics simulation to study how branch ends which were chemically modified with vinyl acetate groups affect free volume coalescence around an amphiphilic compound, nonyl ethoxylate (NE), dispersed in branched PE models. Branch ends modified with vinyl acetate significantly impact the free volume coalescence dynamics around NE. Compared with methyl branch ends, vinyl acetate branch ends show a much higher affinity, as quantified by the corresponding radial distribution functions, for the hydrophilic ethylene oxide‐segment of NE. However, this is not the case for the hydrophobic ethylene‐segment. Interestingly, vinyl acetate branch ends tend to reduce the power (amplitude) of the free volume size fluctuations around both the ethylene oxide‐ and ethylene‐segments. Indeed, the powers of the fluctuations with different PE branching characteristics decrease with increasing vinyl acetate concentration. We believe that free volume coalescence leads to cavitation and that vinyl acetate branches could inhibit cavitation, thereby crack propagation in PE. The power results seem to be consistent with the experimental observation that the addition of copolymer ethylene vinyl acetate to low‐density polyethylene improves the ESC resistance of the blend. Highlights: Vinyl acetate branches reduce free volume coalescence activities.Vinyl acetate branches are attracted to the hydrophilic segment of NE.Cavitation likely starts from the free volume coalescence around NE. [ABSTRACT FROM AUTHOR]

Due to the high‐power environments of electronic components, achieving the exceptional dielectric properties and mechanical behavior necessary for electronic packaging materials presents a significant challenge. In this study, a trifunctional maleimide (HTMI) was synthesized by reacting hexamethylene diisocyanate trimer (HDI trimer) with Maleic anhydride (MA), followed by the preparation of Bismaleimide (BMI) resin featuring a micro‐branching structure through its reaction with diallyl bisphenol A (DBA) ether and BMI. The intentionally designed micro‐branching structure resulted in an increase in the free volume within BMI, leading to an 8.8% reduction in the dielectric constant. Additionally, this micro‐branching architecture imparted superior mechanical properties to the BMI resin, as demonstrated by a 140% increase in bending strength and a 149% increase in impact strength of the cured product. [ABSTRACT FROM AUTHOR]

In this work, 2,2‐bis(3‐amino‐4‐hydroxyphenyl) hexafluoropropane (APAF) was used as the fixed diamine monomer, and 4,4′‐(hexafluoroisopropylidene) diphthalic anhydride (6FDA), 4,4′‐oxydiphthalic anhydride (ODPA), 3,3′,4,4′‐biphenyltetracarboxylic diandhydride (BPDA) and pyromellitic dianhydride (PMDA) were selected as four different dianhydride monomers, respectively, to prepare the thermally rearranged polybenzoxazole (TR‐PBO) gas separation membranes with different structures via a thermal rearrangement reaction at 450°C. The microstructure of TR‐PBO membranes was investigated using X‐ray diffraction and positron annihilation spectroscopy. All the TR‐PBO membranes exhibit bimodal free volume structure, containing ultramicropores (<0.7 nm) and micropores (<2 nm) with size of 3.6–4.6 and 7.6–8.4 Å, respectively. As the steric hindrance of the bridging groups in the dianhydride monomers increases, the radius and number of pores in the membranes increases, leading to an increase in fractional free volume (FFV). The pure gas permeation test shows a positive correlation between gas permeability and FFV in the TR‐PBO membranes, indicating that an increase in FFV is favorable for the diffusion of gas molecules. Particularly, the ultramicropores play a decisive role on the gas selectivity. All the TR‐PBO membranes exhibit excellent gas permeaselectivity. Among them, the H2/CH4 separation performance of APAF‐6FDA and APAF‐ODPA membranes approaches the 2008 Robeson upper bound, which is due to the high number of both micropores and ultramicropores. Our results demonstrate that the free volume structure of polymer membranes can be designed by selecting monomers with different structures and utilizing thermal rearrangement reactions, allowing for the preparation of gas separation membranes with high permeability and selectivity. [ABSTRACT FROM AUTHOR]

In this study, we report the synthesis of 3‐, 4‐, and 6‐arm star poly(ionic liquid)s (PILs) (specifically, star poly(vinylbenzyl methylimidazolium bis(trifluoromethane)sulfonimide) (poly(VBMIm‐TFSI))) via reversible addition‐fragmentation chain transfer (RAFT) polymerization with a core‐first approach, followed by quaternization and anion exchange. The impact of star polymer architecture on properties was explored by measuring the thermal, mechanical, and ion transport properties of each star PIL compared to those of an analogous linear PIL. The star PILs exhibited up to 2‐fold higher ionic conductivity, 150% higher elastic modulus, and 465% higher ultimate tensile strength compared to the analogous linear PIL. The Williams‐Landel‐Ferry (WLF) equation was employed to explore the effect of increased free volume on the improved ion transport properties of the star PILs. These results highlight the impact of star polymer architecture on PILs and star PILs as promising materials for electrochemical energy devices. [ABSTRACT FROM AUTHOR]

The mechanisms behind the polymer glass transition, though not fully elucidated, have garnered significant attention. The Locally Correlated Lattice (LCL) theory [R. P. White, J. E. Lipson, Macromolecules2016, 49, 3987] provides a novel perspective on free volume and establishes the relationship between polymer glass transition and free volume. In this study, we present a dynamic theoretical model based on the thermodynamic LCL theory, focusing on the kinetic evolution of free volume during polymer glass transition. Our analysis simultaneously examines the segmental diffusion coefficient, dynamic correlation length, free volume, and isobaric heat capacity. The results indicate that, upon reaching a critical temperature, heterogeneous dynamics and singular thermodynamics emerge concurrently. This study establishes a comprehensive correlation between thermodynamic singularities and dynamic inhomogeneities, offering valuable insights into the polymer glass transition process. [ABSTRACT FROM AUTHOR]

In the development of thermoplastic products, it is necessary to conduct the necessary mechanical tests and evaluate the reliability of thermoplastics in each case, because the mechanical properties of the same material vary depending on the molding process conditions and product shape. In order to build a sustainable society, it is expected that the evaluation of the mechanical properties of thermoplastics, which are resource and energy saving, will be required. In this paper, the glass transition temperature and melting point of injection-molded thermoplastics were evaluated by differential scanning calorimetry, and the correlation between Poisson's ratio and free volume was obtained by applying the theory proposed by Flory et al. A certain correlation was found between the Poisson's ratio of polymers and the change in free volume determined by the glass transition temperature. It is also clear that this relationship can be approximated by orders of magnitude. The Poisson's ratio of the core layer tended to be smaller than that of the skin layer. It has also been found that there is a negative correlation between the Young's modulus and the free volume of the polymer material. [ABSTRACT FROM AUTHOR]

Physical and chemical indicators of underground waters of the Skole region were studied. The samples were taken from natural water sources of Skole district of Lviv region and analyzed within organoleptic and physicochemical indicators of the quality of water. The organoleptic and physico-chemical indicators of the quality of natural water sources of the studied area meet the requirements of the State sanitary norms and rules. Organic-inorganic ureasil polymers with different precursors were used as holding matrixes in construction of laccase biosensors for analysis of water pollution. Cyclic voltammetry and chronoamperometric measurements were carried out to estimate the main parameters of the constructed biosensors. It is found that the sensitivity of the constructed biosensors correlates well with the network properties (free volume and crosslinking) of the investigated polymers studied using positron annihilation lifetime spectroscopy and swelling measurements. The same correlation was also earlier reported for ureasil composites of different prehistory and photopolymers and it seems to be universal that allows controlled biosensing according to the required needs of analysis. [ABSTRACT FROM AUTHOR]

The temperature and heating rate affecting the shrinkage kinetics are studied for cylindrical workpieces obtained from submicron and fine aluminum oxide powder. The studies involve the powder from three batches: (1) submicron (~0.15 µm) α-Al2O3 powder, (2) submicron (~0.2 µm) α-Al2O3 powder having an amorphous layer deposited on the particle surface, and (3) fine (~1 µm) α-Al2O3 powder. It is established that the powder particles in all batches has a monocrystalline structure. The powder workpieces are sintered using the electric pulse (spark) plasma sintering (SPS) technique. The shrinkage curves are analyzed using the Young–Cutler and the Coble models. The kinetics of sintering workpieces is shown to depend on diffusion developing between the powder particles. The sintering kinetics of workpieces made from submicron powder depends on intensity of the grain-boundary diffusion. In the sintering workpieces made of finely dispersed powder, the kinetics is additionally dependent on simultaneously developing volumetric and grain-boundary diffusion. It is established that the presence of an amorphous layer on the surface of particulate α-Al2O3 having submicron size affects the rate of migration of grain interfaces and the parameters of the Coble equation at the final SPS stage. It is assumed that the accelerated growth of grains and an increase in the microhardness of samples obtained through sintering workpieces made from submicron powder with an amorphous layer on the particle surface is caused by a higher density of defects at the grain interfaces. The elevated density of defects at grain interfaces can result from crystallization of the amorphous layer. [ABSTRACT FROM AUTHOR]

In this work, the influence of aromatic rings on the local free volume of cured mixtures of acrylate epoxidized soybean oil (AESO) and vanillin dimethacrylate (VDM) was investigated. Cross-linking took place under the influence of UV light in the presence or absence of a photoinitiator. The local free volume and its homogeneity were characterized using the Positron Annihilation Lifetime Spectroscopy (PALS) technique. It was found that increasing the content of VDM, which contains aromatic rings, caused a decrease in the local free volume of the cured polymer network, with consequences for the diffusion properties of the polymer, which were tested for the case of water. Another consequence of increasing the content of VDM was a decrease in the conversion of double bonds in the finally cured samples, characterized by near-infrared spectroscopy (NIR). This finding illustrates a case where the decrease in free volume is not necessarily related to an increase in the crosslinking density of the polymer, but is a consequence of the presence of an increase in the occupied volume of aromatic rings in the volume of the polymer. [ABSTRACT FROM AUTHOR]

While efforts have been made to optimize organic semiconducting materials to achieve low-power-consumption organic field-effect transistors (OFETs), it is important to note that the choice of gate dielectric materials is equally critical. In general, a high-k polymer dielectric material is highly preferred for low-power-consumption OFETs. In this perspective, we highlight several newly emerged strategies for high dielectric constant polymer dielectrics. By exploiting the recent advances in molecular modulation and morphology control, these new strategies enable remarkably high dielectric constant up to 25–30 for polymer dielectrics, while still maintaining dielectric losses below 0.01 at 1 kHz. We further analyze the advantages and disadvantages of these strategies and propose four design principles—side-chain dipole, rigid free volume, self-assembly, and thermosets—for future polymer gate dielectrics in OFETs. [ABSTRACT FROM AUTHOR]

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