Tuning of shear thickening behavior and elastic strength of polyvinylidene fluoride via doping of ZnO-graphene

ZnO rice like nonarchitects are grafted on the graphene carbon core via a rapid microwave synthesis route. The prepared grafted systems are characterized via XRD, SEM, RAMAN, and XPS to examined the structural and morphological parameters. Zinc oxide grafted graphene sheets (ZnO-G) are further doped in β-phase of polyvinylidene fluoride (PVDF) to prepare the polymer nanocomposites (PNCs) via mixed solvent approach (THF/DMF). β-phase confirmation of PVDF PNCs is done by FTIR studies. It is observed that ZnO-G filler enhances the β-phase content in the PNCs. Non-doped PVDF and PNCs are further studied for rheological behavior under the shear rate of 1–100 s⁻¹. Doping of ZnO-G dopant to the PVDF matrix changes its discontinuous shear thickening (DST) behavior to continues shear thickening behavior (CST). Hydrocluster formation and their interaction with the dopant could be the reason for this striking DST to CST behavioral change. Strain amplitude sweep (10⁻³% -10%) oscillatory test reveals that the PNCs shows extended linear viscoelastic region with high elastic modulus and lower viscous modulus. Effective shear thickening behavior and strong elastic strength of these PNCs present their candidature for various fields including mechanical and soft body armor applications.     

Structural drivers controlling sulfur solubility in alkali aluminoborosilicate glasses

If the direct feed approach to vitrify the Hanford's tank waste is implemented, the low activity waste (LAW) will comprise higher concentrations of alkali/alkaline-earth sulfates than expected under the previously proposed vitrification scheme. To ensure a minimal impact of higher sulfate concentrations on the downstream operations and overall cost of vitrification, advanced glass formulations with enhanced sulfate loadings (solubility) are needed. While, the current sulfate solubility predictive models have been successful in designing LAW glasses with sulfate loadings <2 wt.%, it will be difficult for them to design glass compositions with enhanced loadings due to our limited understanding of the fundamental science governing these processes. In this pursuit, this article unearths the underlying compositional and structural drivers controlling the sulfate solubility in model LAW glasses. It has been shown that the preferentially removes non-framework cations from the modifier sites in the silicate network, thus, leading to the polymerization in the glass network via the formation of ring-structured borosilicate units. Furthermore, though the sulfate solubility slightly decreases with increasing Li⁺/Na⁺ in the glasses, the prefers to be charge compensated by Na⁺, as it is easier for to break Na–O bonds instead of Li–O bonds.     

Proton Nuclear Magnetic Resonance-Based Method for the Quantification of Epoxidized Methyl Oleate

Epoxidized methyl esters (EMO) with their high oxirane ring reactivity, acts as a raw material in the synthesis of various industrial chemicals including polymers, stabilizers, plasticizers, glycols, polyols, carbonyl compounds, biolubricants etc. EMO has been generally quantified by the gas chromatography (GC) and high-performance liquid chromatography (HPLC) techniques. Taking into the account of the limitations of these techniques, two qHNMR-based equations have been proposed for the quantification of EMO in the mixture of EMO and methylesters (MO). The validity of the proposed method was determined using standard mixtures of MO and EMO having different molar concentrations. The developed equations have been applied on the samples of EMO prepared from oleic acid in two-step process viz., esterification followed by epoxidation. The qHNMR-based EMO quantification showed acceptable agreement with the results obtained from HPLC analysis.     

Excess Molar Volumes and Viscosities of Mixtures of Diethylene Glycol Dibutyl Ether with Dialkyl Carbonates at 298.15, 308.15, and 318.15 K

Excess molar volumes,V ^E _m, and viscosities,, were measured as a function of composition for the binary mixtures of diethylene glycol dibutyl ether+dimethyl carbonate, +diethyl carbonate, and +propylene carbonate at temperatures of 298.15, 308.15, and 318.15 K and atmospheric pressure over the whole range of mixture compositions. From the experimental results, deviations in the viscosity,ln, and excess free energies of activation of viscous flow,G*^E, were calculated. The experimental results were correlated using the Redlich–Kister equation. The experimental and calculated quantities were used to analyze the mixing behavior of the components. Furthermore, activation enthalpies,H*, and entropies,S*, of viscous flow were evaluated and their variation with concentration is discussed.     

A study on dynamic rheological characterisation of electron beam crosslinked high vinyl styrene butadiene styrene block copolymer

Crosslinking of elastomers using electron beam radiation has several advantages over conventional method. It is accomplished much faster, in a more environmental friendly approach and in a much simpler manner. When fast moving electrons that are generated from electron accelerators are targeted on a polymer matrix, they primarily crosslink the polymer. However, in the process, some chain scission may also occur. In this work, a high vinyl (~50%) styrene–butadiene–styrene (S–B–S) block copolymer was used as the base polymer. Radiation doses were varied from 25 to 300 kGy. A detailed investigation was made to understand the effect of electron beam radiation on the rheological properties such as storage modulus, loss modulus, storage viscosity and complex viscosity of the block copolymer under strain and frequency sweeps performed in a Rubber Process Analyzer (RPA). Recyclability of the crosslinked S–B–S polymer was also explored by RPA and mechanical studies.     

Modeling and simulation of temperature drift for ISFET-based pH sensor and its compensation through machine learning techniques

The paper presents modeling and simulation of ion-sensitive field-effect transistor (ISFET)-based pH sensor with temperature-dependent behavioral macromodel and proposes to compensate the temperature drift in the sensor using intelligent machine learning (ML) models. The macromodel is built using SPICE by introducing electrochemical parameters in a metal-oxide-semiconductor field-effect transistor (MOSFET) model to simulate ISFET characteristics. We account for the temperature dependence of electrochemical and semiconductor parameters in our macromodel to increase its robustness. The macromodel is then exported as a subcircuit element, which is used to design the readout interface circuit. A simple constant-voltage, constant-current (CVCC) topology is utilized to generate the data for temperature drift in ISFET pH sensor, which is used to train and test state-of-the-art ML-based regression models in order to compensate the drift behavior. The experimental results demonstrate that the random forest (RF) technique achieves the best performance with very high correlation and low error rate. Corresponding curves for output signal using the trained models show highly temperature-independent characteristics when tested for pH 2, 4, 7, 10, and 12, and we obtained a root mean squared error (RMS) variation of ΔpH ≤ 0.024 over a temperature range of 15°C to 55°C in comparison with ΔpH ≤ 1.346 for uncompensated output signal. This work establishes the framework for integration of ML techniques for drift compensation of ISFET chemical sensor to improve its performance.     

Fatty Acids in Vernonia Produced in the Mid-Atlantic Region of the United States

Vernonia galamensis [(Cass.) Less.] is a native of Ethiopia and Eritrea. Seed of vernonia contain substantial quantities of naturally epoxidized oil, which is used in the paint industry to reduce emissions of volatile organic compounds that produce smog resulting from the use of petroleum-based (alkyd-resin) paint. Epoxidized oil is also used in the manufacture of plasticizers, additives to polyvinyl chloride, polymer blends and coatings, and cosmetic and pharmaceutical applications. Previous research has indicated that vernonia has potential for commercialization in the mid-Atlantic region of the United States. This study characterized fatty acids in oil from vernonia grown in this latter region. Vernonia oil, from 14 vernonia lines grown during 1995 and 1996 under field conditions in Virginia, contained 3.3, 3.0, 5.0, 15.0, 0.2, 0.5, 0.4, and 72.7%, respectively, of C16:0, C18:0, C18:1, C18:2, C18:3, C20:0, C20:1, and vernolic (C18:1 epoxy) fatty acids. Effects of genotypes on vernonia oil quality were generally not significant whereas the effects of years were significant. The concentration of vernolic acid was positively correlated with oil concentration but negatively correlated with concentrations of all individual fatty acids, except for C18:3. Contribution of Virginia State University Agricultural Research Station, journal article series number 253. The use of any trade names or vendors does not imply approval to the exclusion of other products or vendors that may also be suitable.     

Supported Gold Nanoparticles‐Catalyzed Microwave‐Assisted Hydration of Nitriles to Amides under Base‐Free Conditions

Polystyrene‐supported gold (Au@PS) nanoparticles were synthesized by the reduction deposition approach and well characterized by UV‐visible, XRD, TEM, SAED, EDX, and XPS studies. The Au@PS was applied as catalyst for the hydration of nitriles to amides in water under microwave irradiation. Several functionalized aromatic, heterocyclic and aliphatic nitriles were found to be active for synthesis of the corresponding amides where no activation of water by base, ligand and support is needed. Easy recovery, negligible leaching and recyclability for up to eight runs are added advantages of the catalyst under water‐mediated reaction conditions.

     

Development and Characterization of Inorganic-Organic (Si-O-Al) Hybrid Geopolymeric Precursors via Solid State Method

Silicon - In this study, an innovative one part, solution free concept applied for the development of hybrid inorganic–organic geopolymeric precursors having Si-O-Al networks at the precursor...