Investigating the properties of ortho-positronium in liquid scintillators under oxygen quenching.

Investigating the mechanism of positron annihilation in liquid-scintillator based neutrino experiments could be helpful for positron reconstruction algorithms and positron-electron discrimination analysis. Based on this, we utilize a novel positron annihilation lifetime spectrometer to characterize a series of liquid scintillator samples without direct contact with the positron source by applying the anti-coincidence method, which facilitates the measurement of liquids with high accuracy and low background. We obtain an ortho-positronium (o-Ps) lifetime value of 3.02 ns for liquid scintillators composed of linear alkylbenzene and two solutes, and we also measure liquid scintillator samples by bubbling different gases to study the interaction of oxygen dissolved with positronium. The discussion of the annihilation behavior of o-Ps in liquid scintillators further clarify the factors affecting the lifetime and intensity of o-Ps, and the calculation of annihilation rate and free volume radius within the samples has potential applications in characterizing gas solubility and free volume in liquids with o-Ps as probe.

Molecular Dynamics Simulation of Hydrogen Barrier Performance of Modified Polyamide 6 Lining of IV Hydrogen Storage Tank with Graphene.

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.

Impact of non-covalent interactions on the solvation of ovalbumin in an aqueous environment of different pHs: Thermodynamic and diffusion studies.

The solvation behavior of protein is an important factor in protein-based food products. In the present study, the xylitol (XY) - ovalbumin (OVN) interaction in an aqueous solution of different pH conditions is analyzed in two methods. In one method, the thermodynamic parameters Gibbs free energy, free volume, and internal pressure are calculated by using ultrasonic velocity, density, and viscosity in addition the refractive index is also measured. The second method is a theoretical method in which using the Laplace transform technique the diffused amount of protein have been calculated for OVN with and without XY in different pH environment. The addition of XY with OVN makes the system with more free energy and free volume as the internal pressure decreases. This trend shows that preferential interaction occurs between solvent-solute molecules. The diffusivity of OVN is reduced after the addition of XY representing the strength of protein-protein interaction. The effect of pH changes is well reflected in both experimental and theoretical results. The results confirm that acidic pH extremity offers more solvation of OVN compared to alkaline pH extremity.

Poisson's Ratio Prediction of Injection Molded Thermoplastics Using Differential Scanning Calorimetry.

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.

Anion Exchange Membrane with Pendulous Piperidinium on Twisted All-Carbon Backbone for Fuel Cell.

As a central component for anion exchange membrane fuel cells (AEMFCs), the anion exchange membrane is now facing the challenge of further improving its conductivity and alkali stability. Herein, a twisted all-carbon backbone is designed by introducing stereo-contorted units with piperidinium groups dangled at the twisted sites. The rigid and twisted backbone improves the conduction of hydroxide and brings down the squeezing effect of the backbone on piperidine rings. Accordingly, an anion exchange membrane prepared through this method exhibits adapted OH- conductivity, low swelling ratio and excellent alkali stability, even in high alkali concentrations. Further, a fuel cell assembled with a such-prepared membrane can reach a power density of 904.2 mW/cm2 and be capable of continuous operation for over 50 h. These results demonstrate that the designed membrane has good potential for applications in AEMFCs.

Investigating the Free Volumes as Nanospaces in Human Stratum Corneum Lipid Bilayers Using Positron Annihilation Lifetime Spectroscopy (PALS).

This work is the first one that provides not only evidence for the existence of free volumes in the human stratum corneum but also focuses on comparing these experimental data, obtained through the unique positron annihilation lifetime spectroscopy (PALS) method, with theoretical values published in earlier works. The mean free volume of 0.269 nm was slightly lower than the theoretical value of 0.4 nm. The lifetime τ3 (1.83 ns with a coefficient of variation CV of 3.21%) is dependent on the size of open sites in the skin. This information was used to calculate the free volume radius R (0.269 nm with CV 2.14%), free volume size Vf (0.081 nm3 with CV 4.69%), and the intensity I3 (9.01% with CV 10.94%) to estimate the relative fractional free volume fv (1.32 a.u. with CV 13.68%) in human skin ex vivo. The relation between the lifetime of o-Ps (τ3) and the radius of free volume (R) was formulated using the Tao-Eldrup model, which assumes spherical voids and applies to sites with radii smaller than 1 nm. The results indicate that PALS is a powerful tool for confirming the existence of free volumes and determining their size. The studies also focused on describing the probable locations of these nanospaces in SC lipid bilayers. According to the theory, these play an essential role in dynamic processes in biological systems, including the diffusion of low-molecular-weight hydrophobic and moderately hydrophilic molecules. The mechanism of their formation has been determined by the molecular dynamics of the lipid chains.

Pendant Group Functionalization of Cyclic Olefin for High Temperature and High-Density Energy Storage.

High-temperature flexible polymer dielectrics are critical for high density energy storage and conversion. The need to simultaneously possess a high bandgap, dielectric constant and glass transition temperature forms a substantial design challenge for novel dielectric polymers. Here, by varying halogen substituents of an aromatic pendant hanging off a bicyclic mainchain polymer, a class of high-temperature olefins with adjustable thermal stability are obtained, all with uncompromised large bandgaps. Halogens substitution of the pendant groups at para or ortho position of polyoxanorborneneimides (PONB) imparts it with tunable high glass transition from 220 to 245 °C, while with high breakdown strength of 625-800 MV/m. A high energy density of 7.1 J/cc at 200 °C is achieved with p-POClNB, representing the highest energy density reported among homo-polymers. Molecular dynamic simulations and ultrafast infrared spectroscopy are used to probe the free volume element distribution and chain relaxations pertinent to dielectric thermal properties. An increase in free volume element is observed with the change in the pendant group from fluorine to bromine at the para position; however, smaller free volume element is observed for the same pendant when at the ortho position due to steric hindrance. With the dielectric constant and bandgap remaining stable, properly designing the pendant groups of PONB boosts its thermal stability for high density electrification.

Optimization of the Thermally Conductive Low-k Polymer Dielectrics Based on Multisource Free-Volume Effects.

Polymers/polymer matrix composites possessing low dielectric constants (low-k polymer dielectrics) contribute to the advance of electronics, for instance, microprocessor chips, mobile phone antennas, and data communication terminals. However, the intrinsic long-chain structural characteristic results in poor thermal conductivities, which draw heat accumulation and undermine the outstanding low-k performance of polymers. Herein, multisource free-volume effects that combine two novel kinds of extra free volume with the known in-cage free volume of polyhedral oligomeric silsesquioxanes (POSSs) are discussed to reduce the capacity for dielectric constant reduction. The multisource free-volume effects of POSSs are associated with the thermal conductive network formed by the hexagonal boron nitride (BN) in the polymer matrix. The results show a decent balance between low-k performance (dielectric constant is 2.08 at 1 MHz and 1.98 at 10 GHz) and thermal conductivity (0.555 W m-1 K-1, 4.91 times the matrix). The results provide a new idea to maximize the free-volume effects of POSSs to optimize dielectric properties together with other desired performances for the dielectrics.

Free volume theory explains the unusual behavior of viscosity in a non-confluent tissue during morphogenesis.

A recent experiment on zebrafish blastoderm morphogenesis showed that the viscosity (η) of a non-confluent embryonic tissue grows sharply until a critical cell packing fraction (ϕS). The increase in η up to ϕS is similar to the behavior observed in several glass-forming materials, which suggests that the cell dynamics is sluggish or glass-like. Surprisingly, η is a constant above ϕS. To determine the mechanism of this unusual dependence of η on ϕ, we performed extensive simulations using an agent-based model of a dense non-confluent two-dimensional tissue. We show that polydispersity in the cell size, and the propensity of the cells to deform, results in the saturation of the available free area per cell beyond a critical packing fraction. Saturation in the free space not only explains the viscosity plateau above ϕS but also provides a relationship between equilibrium geometrical packing to the dramatic increase in the relaxation dynamics.

Twisted Poly(p-terphenyl-co-m-terphenyl)-Based Anion Exchange Membrane for Water Electrolysis.

In order to improve the mechanical and water electrolysis performance of anion exchange membranes (AEMs), we adjusted the ratio between p-terphenyl and m-terphenyl to balance the backbone conformation, which gives it a better suitability for a better combination with cations. The results showed that poly(m-terphenyl-co-p-terphenyl)-based AEMs have excellent mechanical properties. Among them, the m-p-TP-40-BOP-ASU membrane has the highest tensile strength and elongation at break (75.72 MPa and 16.07%). The ionic conductivity reaches 137.14 mS cm-1 at 80 °C owing to the fact that efficient ion-conducting channels are formed by well-balanced molecular structures. The current density of the m-p-TP-40-BOP-ASU membrane reached 1.96 A cm-2 (1 M KOH aq, 2.0 V and 60 °C). After testing for 112 h under a current density of 500 mA cm-2, the voltage increased by 102 mV compared to the initial electrolysis voltage. All results have shown that m-p-TP-x-BOP-ASU has excellent electrolysis performance and electrochemical durability and has a promising application prospect in AEM water electrolyzers.

Bioinspired Organic Porous Coupling Agent for Enhancement of Nanoparticle Dispersion and Interfacial Strength.

Composite materials have significantly advanced with the integration of inorganic nanoparticles as fillers in polymers. Achieving fine dispersion of these nanoparticles within the composites, however, remains a challenge. This study presents a novel solution inspired by the natural structure of Xanthium. We have developed a polymer of intrinsic microporosity (PIM)-based porous coupling agent, named PCA. PCA's rigid backbone structure enhances interfacial interactions through a unique intermolecular interlocking mechanism. This approach notably improves the dispersion of SiO2 nanoparticles in various organic solvents and low-polarity polymers. Significantly, PCA-modified SiO2 nanoparticles embedded in polyisoprene rubber showed enhanced mechanical properties. The Young's modulus increases to 30.7 MPa, compared to 5.4 MPa in hexadecyltrimethoxysilane-modified nanoparticles. Further analysis shows that PCA-modified composites not only become stiffer but also gain strength and ductility. This research demonstrates a novel biomimetic strategy for enhancing interfacial interactions in composites, potentially leading to stronger, more versatile composite materials.

Impact of Glass Free Volume on Femtosecond Laser-Written Nanograting Formation in Silica Glass.

In this study, we investigate the effects of densification through high pressure and temperature (up to 5 GPa, 1000 °C) in the making of nanogratings in pure silica glass, inscribed with femtosecond laser. The latter were monitored through retardance measurements using polarized optical microscopy, and their internal structure was observed under scanning electron microscopy. We reveal the difficulty in making nanogratings in densified silica glasses. Based on this observation, we propose that free volume may be a key precursor to initiate nanograting formation.

Ultrastrong and High-Tough Thermoset Epoxy Resins from Hyperbranched Topological Structure and Subnanoscaled Free Volume.

The strength and toughness of thermoset epoxy resins are generally mutually exclusive, as are the high performance and rapid recyclability. Experimentally determined mechanical strength values are usually much lower than their theoretical values. The preparation of thermoset epoxy resins with high modulus, high toughness, ultrastrong strength, and highly efficient recyclability is still a challenge. Here, novel hyperbranched epoxy resins (Bn, n = 6, 12, 24) with imide structures by a thiol-ene click reaction. Bn shows an excellent comprehensive function in simultaneously improving the strength, modulus, toughness, low-temperature resistance, and degradability of diglycidyl ether of bisphenol-A (DGEBA). All the mechanical properties first increase and then decrease with minimization of the free volume properties. The improvement is attributable to uniform molecular holes or free volume by a molecular mixture of linear and hyperbranched topological structures. The precise measurement and controllability of the molecular free volume properties of epoxy resins is first discovered, as well as the imide structure degradation of crosslinked epoxy resins. The two conflicts are successfully resolved between strength and toughness and between high performance during service and high efficiency during degradation. These findings provide a route for designing ultrastrong, tough, and recyclable thermoset epoxy resins.

Ultrapermeable Gel Membranes Enabling Superior Carbon Capture.

Membrane technology is rapidly gaining broad attraction as a viable alternative for carbon capture to mitigate increasingly severe global warming. Emerging CO2 -philic membranes have become crucial players in efficiently separating CO2 from light gases, leveraging their exceptional solubility-selectivity characteristics. However, economic and widespread deployment is greatly dependent on the boosted performance of advanced membrane materials for carbon capture. Here, we design a unique gel membrane composed of CO2 -philic molecules for accelerating CO2 transportation over other gases for ultrapermeable carbon capture. The molecular design of such soft membranes amalgamates the advantageous traits of augmented permeation akin to liquid membranes and operational stability akin to solid membranes, effectively altering the membrane's free volume characteristics validated by both experiments and molecular dynamics simulation. Surprisingly, gas diffusion through the free-volume-tuned gel membrane undergoes a 9-fold improvement without compromising the separation factor for the superior solubility selectivity of CO2 -philic materials, and CO2 permeability achieves a groundbreaking record of 5608 Barrer surpassing the capabilities of nonfacilitated CO2 separation materials and exceeding the upper bound line established in 2019 even by leading-edge porous polymer materials. Our designed gel membrane can maintain exceptional separation performance during prolonged operation, enabling the unparalleled potential of solubility-selective next-generation materials towards sustainable carbon capture.

High Free Volume Polyelectrolytes for Anion Exchange Membrane Water Electrolyzers with a Current Density of 13.39 A cm-2 and a Durability of 1000 h.

The rational design of the current anion exchange polyelectrolytes (AEPs) is challenging to meet the requirements of both high performance and durability in anion exchange membrane water electrolyzers (AEMWEs). Herein, highly-rigid-twisted spirobisindane monomer is incorporated in poly(aryl-co-aryl piperidinium) backbone to construct continuous ionic channels and to maintain dimensional stability as promising materials for AEPs. The morphologies, physical, and electrochemical properties of the AEPs are investigated based on experimental data and molecular dynamics simulations. The present AEPs possess high free volumes, excellent dimensional stability, hydroxide conductivity (208.1 mS cm-1 at 80 °C), and mechanical properties. The AEMWE of the present AEPs achieves a new current density record of 13.39 and 10.7 A cm-2 at 80 °C by applying IrO2 and nonprecious anode catalyst, respectively, along with outstanding in situ durability under 1 A cm-2 for 1000 h with a low voltage decay rate of 53 µV h-1 . Moreover, the AEPs can be applied in fuel cells and reach a power density of 2.02 W cm-2 at 80 °C under fully humidified conditions, and 1.65 W cm-2 at 100 °C, 30% relative humidity. This study provides insights into the design of high-performance AEPs for energy conversion devices.

Investigation of the Gas Permeation Properties Using the Volumetric Analysis Technique for Polyethylene Materials Enriched with Pure Gases under High Pressure: H2, He, N2, O2 and Ar.

Polyethylene (PE) is widely used as a gas-sealing material in packing films and gas transport pipes. A technique for evaluating the permeability of water-insoluble gases has recently been developed. This technique is a volumetric analysis that is used to calculate the gas permeability by measuring the gas uptake and diffusivity. With this technique, we investigated the permeability of pure gases, such as H2, He, N2, O2 and Ar, enriched under high pressure up to 9 MPa in low-density polyethylene (LDPE), ultrahigh molecular weight polyethylene (UHMWPE) and high-density polyethylene (HDPE). The gas uptake showed a linear pressure-dependent behavior that followed Henry's law, and the diffusivity was independent of the pressure. Furthermore, the logarithmic diffusivity values of the five gases linearly decreased as their molecular kinetic diameters increased. The logarithmic solubility values linearly increased as the critical temperatures of the gases increased. The calculated permeability results were correlated with the volume fraction of the amorphous phase and the fractional free volume. This result newly showed that the amorphous phase was directly correlated to the fractional free volume.

Molecular Dynamics Simulation of Hydrogels Based on Phosphorylcholine-Containing Copolymers for Soft Contact Lens Applications.

The structure and dynamics of copolymers of 2-hydroxyethyl methacrylate (HEMA) with 2-methacryloyloxyethyl phosphorylcholine (MPC) were studied by molecular dynamics simulations. In total, 20 systems were analyzed. They differed in numerical fractions of the MPC in the copolymer chain, equal to 0.26 and 0.74, in the sequence of mers, block and random, and the water content, from 0 to 60% by mass. HEMA side chains proved relatively rigid and stable in all considered configurations. MPC side chains, in contrast, were mobile and flexible. Water substantially influenced their dynamics. The copolymer swelling caused by water resulted in diffusion channels, pronounced in highly hydrated systems. Water in the hydrates existed in two states: those that bond to the polymer chain and the free one; the latter was similar to bulk water but with a lower self-diffusion coefficient. The results proved that molecular dynamics simulations could facilitate the preliminary selection of the polymer materials for specific purposes before their synthesis.

Predicting self-diffusion coefficients in semi-crystalline and amorphous solid dispersions using free volume theory.

The self-diffusion coefficient of active ingredients (AI) in polymeric solid dispersions is one of the essential parameters for the rational formulation design in life sciences. Measuring this parameter for products in their application temperature range can, however, be difficult to realise and time-consuming (due to the slow kinetics of diffusion). The aim of this study is to present a simple and time-saving platform for predicting the AI self-diffusivity in amorphous and semi-crystalline polymers on the basis of a modified version of Vrentas' and Duda's free volume theory (FVT) [A. Mansuri, M. Völkel, T. Feuerbach, J. Winck, A.W.P. Vermeer, W. Hoheisel, M. Thommes, Modified free volume theory for self-diffusion of small molecules in amorphous polymers, Macromolecules. (2023)]. The predictive model discussed in this work requires pure-component properties as its input and covers the approximate temperature range of T < 1.2 Tg, the whole compositional range of the binary mixtures (as long as a molecular mixture is present), and the whole crystallinity range of the polymer. In this context, the self-diffusion coefficients of the AIs imidacloprid, indomethacin, and deltamethrin were predicted in polyvinylpyrrolidone, polyvinylpyrrolidone/vinyl acetate, polystyrene, polyethylene, and polypropylene. The results highlight the profound importance of the kinetic fragility of the solid dispersion on the molecular migration; a property which in some cases might entail higher self-diffusion coefficients despite an increase in the molecular weight of the polymer. We interpret this observation within the context of the theory of heterogeneous dynamics in glass-formers [M.D. Ediger, Spatially heterogeneous dynamics in supercooled liquids, Annu. Rev. Phys. Chem. 51 (2000) 99-128] by attributing it to the stronger presence of "fluid-like" mobile regions in fragile polymers offering facilitated routes for the AI diffusion within the dispersion. The modified FVT further allows for identifying the influence of some structural and thermophysical material properties on the translational mobility of AIs in binary dispersions with polymers. In addition, estimates of self-diffusivity in semi-crystalline polymers are provided by further accounting for the tortuosity of the diffusion paths and the chain immobilisation at the interface of the amorphous and crystalline phases.

Probing the Free Volume in Polymers by Means of Positron Annihilation Lifetime Spectroscopy.

Positron annihilation lifetime spectroscopy (PALS) is a valuable technique to investigate defects in solids, such as vacancy clusters and grain boundaries in metals and alloys, as well as lattice imperfections in semiconductors. Positron spectroscopy is able to reveal the size, structure and concentration of vacancies with a sensitivity of 10-7. In the field of porous and amorphous systems, PALS can probe cavities in the range from a few tenths up to several tens of nm. In the case of polymers, PALS is one of the few techniques able to give information on the holes forming the free volume. This quantity, which cannot be measured with macroscopic techniques, is correlated to important mechanical, thermal, and transport properties of polymers. It can be deduced theoretically by applying suitable equations of state derived by cell models, and PALS supplies a quantitative measure of the free volume by probing the corresponding sub-nanometric holes. The system used is positronium (Ps), an unstable atom formed by a positron and an electron, whose lifetime can be related to the typical size of the holes. When analyzed in terms of continuous lifetimes, the positron annihilation spectrum allows one to gain insight into the distribution of the free volume holes, an almost unique feature of this technique. The present paper is an overview of PALS, addressed in particular to readers not familiar with this technique, with emphasis on the experimental aspects. After a general introduction on free volume, positronium, and the experimental apparatus needed to acquire the corresponding lifetime, some of the recent results obtained by various groups will be shown, highlighting the connections between the free volume as probed by PALS and structural properties of the investigated materials.

Low-Regioregularity Polythiophene for a Highly Sensitive and Stretchable Gas Sensor.

In this study, we examined how the regioregularity of poly(3-hexylthiophene) (P3HT) affects molecular packing, free volume, charge transport, and gas sensing properties. Our results showed that the presence of regular alkyl side chains on the polymer backbone promoted a high degree of structural order in regioregular P3HT molecules, leading to a compact packing density and reduced free volume. Consequently, it was more challenging for NO2 molecules to interact with the hole charge carriers in the conductive channel. On the other hand, the regiorandom P3HT films displayed a larger free volume, attributed to the irregular side chains, which facilitated the gas-analyte interaction while impeding efficient charge transport. Thus, these films exhibited greater sensitivity to analyte gas molecules. The molecular order, packing density, and hardness of P3HT films were confirmed through the use of multiple techniques, including UV-vis spectroscopy, atomic force microscopy, and grazing-incidence X-ray diffraction. Additionally, the regiorandom P3HT films showed enhanced mechanical flexibility compared to the regioregular films. In conclusion, our findings emphasize that the regularity of polymer molecules plays a significant role in determining the charge carrier transport and gas adsorption characteristics.