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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.

Abstract With a rapid increase in industrial growth around the world, the demand for an entirely novel category of nanoparticles and technologies for wastewater treatment has become a key concern for environmental protection. Recently, hybrids of layered double hydroxides (LDH), particularly those containing LDH, have gained attention as potential nanoscale adsorbents for water treatment. Recent research has shown that LDH-containing composites are interesting versatile materials with the ability to be used in energy storage, photocatalysis, nanocomposites, and water treatment. In the current work, LDH-containing composites were utilized as adsorbents for the purpose of purifying water. The adsorbents investigated are Zn–Co–Fe/LDH/Chitosan-in situ sample preparation (LDH/CS1) and Zn–Co–Fe/LDH/Chitosan-ex situ sample preparation (LDH/CS2). Furthermore, LDH/CS1 and LDH/CS2 were investigated for wastewater treatment from methyl orange dye (MO) with various adsorption conditions. When the initial MO concentration was 20 mg/L and the amount of adsorbent was 0.1 g, the removal efficiency reached 72.8 and 91.7% for LDH/CS1 and LDH/CS2, respectively. The MO’s maximum adsorption capabilities are 160.78 and 165.89 mg/g for LDH/CS1 and LDH/CS2, respectively, which is much greater than that of comparable commercial adsorbents. MO adsorption onto LDH/CS1 and LDH/CS2 was best characterized by the pseudo-second-order kinetic model. The equilibrium adsorption data was followed by the Freundlich and Langmuir models. The adsorption is favorable as evidenced by the equilibrium parameter R L values for MO adsorption onto LDH/CS1 and LDH/CS2, which were 0.227 and 0.144, respectively. Using the free volume distribution method and the positron annihilation lifetime technique, the nanostructure of the materials was examined.

Abstract In this study, a novel proton-conducting polymer electrolyte membrane based on a mixture of polyvinyl alcohol (PVA)/polyvinyl pyrrolidone (PVP) (1:1) mixed with different ratios of graphene oxide (GO) and plasma-treated was successfully synthesized. Dielectric barrier dielectric (DBD) plasma was used to treat the prepared samples at various dose rates (2, 4, 6, 7, 8, and 9 min) and at fixed power input (2 kV, 50 kHz). The treated samples (PVA/PVP:GO wt%) were soaked in a solution of styrene and tetrahydrofuran (70:30 wt%) with 5 × 10−3 g of benzoyl peroxide as an initiator in an oven at 60 °C for 12 h and then sulfonated to create protonic membranes (PVA/PVP-g-PSSA:GO). The impacts of graphene oxide (GO) on the physical, chemical, and electrochemical properties of plasma-treated PVA/PVP-g-PSSA:x wt% GO membranes (x = 0, 0.1, 0.2, and 0.3) were investigated using different techniques. SEM results showed a better dispersion of nanocomposite-prepared membranes; whereas the AFM results showed an increase in total roughness with increasing the content of GO. FTIR spectra provide more information about the structural variation arising from the grafting and sulfonation processes to confirm their occurrence. The X-ray diffraction pattern showed that the PVA/PVP-g-PSSA:x wt% GO composite is semi-crystalline. As the level of GO mixing rises, the crystallinity of the mixes decreases. According to the TGA curve, the PVA/PVP-g-PSSA:x wt% GO membranes are chemically stable up to 180 °C which is suitable for proton exchange membrane fuel cells. Water uptake (WU) was also measured and found to decrease from 87.6 to 63.3% at equilibrium with increasing GO content. Ion exchange capacity (IEC) was calculated, and the maximum IEC value was 1.91 meq/g for the PVA/PVP-g-PSSA: 0.3 wt% GO composite membrane. At room temperature, the maximum proton conductivity was 98.9 mS/cm for PVA/PVP-g-PSSA: 0.3 wt% GO membrane. In addition, the same sample recorded a methanol permeability of 1.03 × 10−7 cm2/s, which is much less than that of Nafion NR-212 (1.63 × 10−6 cm2/s). These results imply potential applications for modified polyelectrolytic membranes in fuel cell technology.

Abstract The preparation of adsorbents plays a vital role in the adsorption method. In particular, many adsorbents with high specific surface areas and unique shapes are essential for the adsorption strategy. A Zn–Mg–Al/layer double hydroxide (LDH) was designed in this study using a simple co-precipitation process. Adsorbent based on Zn–Mg–Al/LDH was used to remove crystal violet (CV) from the wastewater. The impacts of the initial dye concentration, pH, and temperature on CV adsorption performance were systematically examined. The adsorbents were analyzed both before and after adsorption using FTIR, XRD, and SEM. The roughness parameters and surface morphologies of the produced LDH were estimated using 3D SEM images. Under the best conditions (dose of adsorbent = 0.07 g and pH = 9), the maximum adsorption capacity has been achieved. Adsorption kinetics studies revealed that the reaction that led to the adsorption of CV dye onto Zn–Mg–Al/LDH was a pseudo-second-order model. Additionally, intraparticle diffusion suggests that Zn–Mg–Al/LDH has a fast diffusion constant for CV molecules (0.251 mg/(g min1/2)). Furthermore, as predicted by the Langmuir model, the maximal Zn–Mg–Al/LDH adsorption capacity of CV was 64.80 mg/g. The CV dimensionless separation factor (RL) onto Zn–Mg–Al/LDH was 0.769, indicating that adsorption was favorable. The effect of temperature was performed at 25, 35, and 45 °C in order to establish the thermodynamic parameters ∆Ho, ∆So, and ∆Go. The computed values indicated exothermic and spontaneous adsorption processes. The study presented here might be used to develop new adsorbents with enhanced adsorption capabilities for the purpose of protecting the water environment.

Abstract Finding suitable non-expensive electrocatalyst materials for methanol oxidation is a significant challenge. Waste valorization of spent wastewater nanoadsorbents is a promising route toward achieving circular economy guidelines. In this study, the residual of layered double hydroxide (LDH) can be used as an electrocatalyst in direct methanol fuel cells as a novel approach. The Co–Ni–Zn–Fe LDH was prepared by the co-precipitation method followed by the adsorption of methyl orange (MO). Moreover, the spent adsorbent was calcined at different temperatures (200, 400, and 600 °C) to be converted to the corresponding mixed metal oxides (MMO). The prepared samples were characterized using XRD, FTIR, HRTEM, zeta potential, and hydrodynamic size measurements. The spent adsorbent was tested as an electro-catalyst for direct methanol electro-oxidation. The spent LDH/MO adsorbent showed a maximum current density of 6.66 mA/cm2 at a 50 mV/s scan rate and a 1 M methanol concentration. The spent MMO/MO adsorbent showed a maximum current density of 8.40 mA/cm2 at a 200 °C calcination temperature, 50 mV/s scan rate, and a 3 M methanol concentration. Both samples show reasonable stability over time, as indicated by the chronoamperometric response. Further nanoengineering of used nanoadsorbents could be a promising path to repurposing these wastes as electro-oxidation catalysts.

A casting technique was used to prepare poly(vinyl alcohol) (PVA) blend polymers with different concentrations of Nylon-6,6 to increase the free-volume size and control the ionic conductivity of the blended polymers. The thermal activation energy for some blends is lower than that of pure polymers, indicating that their thermal stability is somewhere in between that of pure Nylon-6,6 and pure PVA. The degree of crystallinity of the blend sample (25.7%) was lower than that of the pure components (41.0 and 31.6% for pure Nylon-6,6 and PVA, respectively). The dielectric properties of the blended samples were investigated for different frequencies (50 Hz–5 MHz). The σac versus frequency was found to obey Jonscher’s universal power law. The calculated values of the s parameter were increased from 0.53 to 0.783 for 0 and 100 wt.% Nylon-6,6, respectively, and values less than 1 indicate the hopping conduction mechanism. The barrier height (Wm) was found to increase from 0.33 to 0.72 for 0 and 100 wt.% Nylon-6,6, respectively. The ionic conductivity decreases as the concentration of Nylon-6,6 is blended into PVA because increasing the Nylon-6,6 concentration reduces the number of mobile charge carriers. Positron annihilation lifetime (PAL) spectroscopy was used to investigate the free volume’s nanostructure. The hole volume size grows exponentially with the concentration of Nylon-6,6 mixed with PVA. The Nylon-6,6/PVA blends’ free-volume distribution indicates that there is no phase separation in the blended samples. Mixing PVA and Nylon-6,6 resulted in a negative deviation (miscible blends), as evidenced by the interaction parameter’s negative value. The strong correlation between the free-volume size and other macroscopic properties like ionic conductivity suggests that the free-volume size influences these macroscopic properties.

Polymer electrolyte membrane (PEM) fuel cells have the potential to reduce our energy consumption, pollutant emissions, and dependence on fossil fuels. To achieve a wide range of commercial PEMs, many efforts have been made to create novel polymer-based materials that can transport protons under anhydrous conditions. In this study, cross-linked poly(vinyl) alcohol (PVA)/poly(ethylene) glycol (PEG) membranes with varying alumina (Al2O3) content were synthesized using the solvent solution method. Wide-angle X-ray diffraction (XRD), water uptake, ion exchange capacity (IEC), and proton conductivity were then used to characterize the membranes. XRD results showed that the concentration of Al2O3 affected the degree of crystallinity of the membranes, with 0.7 wt.% Al2O3 providing the lowest crystallinity. Water uptake was discovered to be dependent not only on the Al2O3 group concentration (SSA content) but also on SSA, which influenced the hole volume size in the membranes. The ionic conductivity measurements provided that the samples were increased by SSA to a high value (0.13 S/m) at 0.7 wt.% Al2O3. Furthermore, the ionic conductivity of polymers devoid of SSA tended to increase as the Al2O3 concentration increased. The positron annihilation lifetimes revealed that as the Al2O3 concentration increased, the hole volume content of the polymer without SSA also increased. However, it was densified with SSA for the membrane. According to the findings of the study, PVA/PEG/SSA/0.7 wt.% Al2O3 might be employed as a PEM with high proton conductivity for fuel cell applications.

We measured the yield of positronium (Ps) in sulfonated aromatic proton conducting membranes for the polymer electrolyte fuel cell (PEFC) with and without −SO2− in their chemical structures by positron annihilation lifetime spectroscopy (PALS). It was observed that Ps formation is almost totally inhibited in the polymers without −SO2− such as sulfonated poly(ether ether ketone) (SPEEK). On the other hand Ps favorably forms in those with −SO2− as sulfonated polyether sulfone (SPES), which is due to the anti-inhibition effect of −SO2−. The high probability of Ps formation in these polymers enables the study of the free volume and the mechanism of gas permeation by PALS. [ABSTRACT FROM AUTHOR]

Variations of the free volume, O2permeability, and structure of the Nafion membrane upon ion exchange of H+with Na+and K+were studied. The free volume was quantified using the positron annihilation lifetime (PAL) technique, whereas the polymer structure was characterized by dynamic mechanical analysis (DMA), nanoindentation, and wide-angle X-ray diffraction (WAXD). It was found that the ion exchange significantly expands the free volume and at the same time decreases the O2permeability. This is opposed to the simple free volume model in which the structure with less open volume is more amenable to lower permeability. Comparison of experimental data collected by different techniques revealed that not only the free volume but also the polymer stiffness plays an essential role in O2permeation. [ABSTRACT FROM AUTHOR]