Effective Enhancement of Water Absorbency of Itaconic Acid Based-Superabsorbent Polymer via Tunable Surface—Crosslinking

A superabsorbent polymer (SAP) was synthesized by copolymerizing itaconic acid and vinyl sulfonic acid. The typically low absorbency of itaconic acid-based SAPs under mechanical loads was improved by introducing surface crosslinking. Fourier-transform infrared spectroscopy and X-ray photoelectron spectroscopy were used to characterize the synthesis and surface-crosslinking reactions in the SAP. Various conditions for surface-crosslinking reactions, such as the surface-crosslinking solution, content of surface-crosslinking agent, and reaction temperature, were explored and correlated with the gel strength and absorption characteristics of the resulting SAP particles. The distilled water content in the surface-crosslinking solution strongly influenced the absorption capacity of the SAP, but this sensitivity decreased when acetone was used as a co-solvent. Itaconic acid-based SAP that was crosslinked under optimal conditions exhibited centrifuge retention capacity and absorbency under a load of 31.1 and 20.2, respectively.

A high-performance silicon-containing arylacetylene resin with conjugated naphthalene rings

2,7-Diphenyloxynaphthalene with large conjugated structure has been introduced into the main chain of silicon-containing arylacetylene resin and then poly(dimethylsilylene-ethynylenephenoxynaphthyloxyphenylene-ethynylene) ( m-PPNSA-MM) was synthesized. The m-PPNSA-MM resin shows good solubility and a wide processing window. A stable three-dimensional cross-linking network formed due to thermal crosslinking reactions of acetylene groups and intermolecular π–π stacking interactions after m-PPNSA-MM was cured through the process of 180°C/2 h + 220°C/2 h + 260°C/4 h. The flexural strength and modulus of the cured m-PPNSA-MM resin at room temperature are 49.2 MPa and 2.75 GPa, respectively. The cured m-PPNSA-MM resin show high thermal stabilities, the 5% temperature of weight loss ( Td5) reaches 560°C in nitrogen.

Rotational Rheology of Wood Flour Composites Based on Recycled Polyethylene

In this paper, we study the effect of the addition of wood flour as a filler in a recycled polyethylene (r-PE) in view of its potential applications in 3D printing. The composites, prepared by melt mixing, are characterized with torque measurements performed during the compounding, dynamic rotational rheology, and infrared spectroscopy. Data show that the introduction of wood results in increased viscosity and in sensible viscous heating during the compounding. The r-PE appear to be stable at temperatures up to 180 °C while at higher temperatures the material shows a rheological response characterized by time-increasing viscoelastic moduli that suggests a thermal degradation governed by crosslinking reactions. The compounds (with wood loading up to 50% in wt.) also shows thermal stability at temperatures up to 180 °C. The viscoelastic behavior and the infrared spectra of the r-PE matrix suggests the presence of branches in the macromolecular structure due to the process. Although the addition of wood particles determines increased viscoelastic moduli, a solid-like viscoelastic response is not shown even for the highest wood concentrations. This behavior, due to a poor compatibility and weak interfacial adhesion between the two phases, is however promising in view of common processing technologies as extrusion or injection molding.

Ameliorated Dielectric Performances of UV-Initiated Auxiliary Crosslinking Polyethylene

In photon-initiated crosslinking reactions of polyethylene molecules, the auxiliary crosslinkers in form of either monomer or homopolymer will cause bridging connections between polymeric molecules by transforming the irradiated photon energy to chemical energy under the assistance of photon-initiators, which can improve photon-initiation quantum efficiency and crosslinking uniformity. In the present study, the auxiliary crosslinkers of TAIC, TAC and TMPTA combining the macromolecular photon-initiator of BPL are employed into the ultraviolet (UV)-initiation technology to develop high-level crosslinked polyethylene (XLPE) insulation materials, whilst elucidating the structural and electrical mechanisms of the dielectric amelioration deriving from auxiliary crosslinking schemes. The specified photosensitive auxiliary crosslinkers can chemically bridge polyethylene molecules in the UV-initiated polyethylene crosslinking process, which can effectively promote polyethylene crosslinking degree but will slightly abate polyethylene crystallinity. Whereas, the orientation polarization and relaxation of molecular electric-dipoles on auxiliary crosslinkers cause additional dielectric permittivity and loss respectively, which will probably reduce insulation performances of XLPE. By contrast to XLPE benchmark, especially for grafting auxiliary crosslinker TAIC with the multiple-coupling carbonyl groups in a ring-conjugation, the preferable deep charge-traps can be introduced into polyethylene matrix to effectively improve electrical conductance and AC dielectric breakdown strength. This study provides experimental basis for developing the photon-initiated XLPE insulation materials with advanced dielectric performances required for manufacturing high-voltage grade cables.

Visualizing Electron Beam-Capping Ligand Reactions for Controlled Nanoparticle Imaging with Liquid Phase Transmission Electron Microscopy

Liquid phase transmission electron microscopy (LP-TEM) enables real-time imaging of nanoparticle self-assembly, formation, and etching with single nanometer resolution. Despite the importance of organic nanoparticle capping ligands in these processes, the effect of electron beam irradiation on surface bound and soluble capping ligands during LP-TEM imaging has not been investigated. Here we use correlative LP-TEM and fluorescence microscopy (FM) to demonstrate that polymeric nanoparticle ligands undergo competing crosslinking and chain scission reactions that non-monotonically modify ligand coverage over time. Branched polyethylenimine (BPEI) coated silver nanoparticles were imaged with dose-controlled LP-TEM followed by labeling their primary amine groups with fluorophores to visualize the local thickness of adsorbed capping ligands. FM images showed that free ligands crosslinked in the LP-TEM image area over imaging times of tens of seconds, enhancing local capping ligand coverage on nanoparticles and silicon nitride membranes. Nanoparticle surface ligands underwent chain scission over irradiation times of minutes to tens of minutes, which depleted surface ligands from the nanoparticle and silicon nitride surface. Conversely, solutions of only soluble capping ligand underwent successive crosslinking reactions with no chain scission, suggesting nanoparticles enhanced the chain scission reactions by acting as radiolysis hotspots. The addition of a hydroxyl radical scavenger, tert-butanol, eliminated chain scission reactions and slowed the progression of crosslinking reactions. These experiments have important implications for performing controlled and reproducible LP-TEM nanoparticle imaging as they demonstrate the electron beam can significantly alter ligand coverage on nanoparticles in a non-intuitive manner. They emphasize the need to understand and control the electron beam radiation chemistry of a given sample to avoid significant perturbations to the nanoparticle capping ligand chemistry, which are invisible in electron micrographs.<br>

Visualizing Electron Beam-Capping Ligand Reactions for Controlled Nanoparticle Imaging with Liquid Phase Transmission Electron Microscopy

Liquid phase transmission electron microscopy (LP-TEM) enables real-time imaging of nanoparticle self-assembly, formation, and etching with single nanometer resolution. Despite the importance of organic nanoparticle capping ligands in these processes, the effect of electron beam irradiation on surface bound and soluble capping ligands during LP-TEM imaging has not been investigated. Here we use correlative LP-TEM and fluorescence microscopy (FM) to demonstrate that polymeric nanoparticle ligands undergo competing crosslinking and chain scission reactions that non-monotonically modify ligand coverage over time. Branched polyethylenimine (BPEI) coated silver nanoparticles were imaged with dose-controlled LP-TEM followed by labeling their primary amine groups with fluorophores to visualize the local thickness of adsorbed capping ligands. FM images showed that free ligands crosslinked in the LP-TEM image area over imaging times of tens of seconds, enhancing local capping ligand coverage on nanoparticles and silicon nitride membranes. Nanoparticle surface ligands underwent chain scission over irradiation times of minutes to tens of minutes, which depleted surface ligands from the nanoparticle and silicon nitride surface. Conversely, solutions of only soluble capping ligand underwent successive crosslinking reactions with no chain scission, suggesting nanoparticles enhanced the chain scission reactions by acting as radiolysis hotspots. The addition of a hydroxyl radical scavenger, tert-butanol, eliminated chain scission reactions and slowed the progression of crosslinking reactions. These experiments have important implications for performing controlled and reproducible LP-TEM nanoparticle imaging as they demonstrate the electron beam can significantly alter ligand coverage on nanoparticles in a non-intuitive manner. They emphasize the need to understand and control the electron beam radiation chemistry of a given sample to avoid significant perturbations to the nanoparticle capping ligand chemistry, which are invisible in electron micrographs.<br>

An Investigation on the Thermally Induced Compatibilization of SBR and α-Methylstyrene/Styrene Resin

The miscibility between two polymers such as rubbers and performance resins is crucial to achieve given targeted properties in terms of tire performances. To this aim, α-methylstyrene/styrene resin (poly(αMSt-co-St)) are used to modify the viscoelastic behavior of rubbers and to fulfill the requirements of the final applications. The initial aim of this work was to understand the influence of poly(αMSt-co-St) resins blended at different concentrations in a commercial styrene-butadiene rubber (SBR). Interestingly, while studying the viscoelastic properties of SBR blends with poly(αMSt-co-St), crosslinking of the rubber was observed under conditions where it was not expected to happen. Surprisingly, after the crosslinking reactions, the poly(αMSt-co-St) resin was irreversibly miscible with SBR at concentrations far above its immiscibility threshold. A detailed investigation involving characterization technics including solid state nuclear magnetic resonance led to the conclusion that poly(αMSt-co-St) is depolymerizing under heating and can graft onto the chains of SBR. It results in an irreversible compatibilization mechanism between the rubber and the resin.

HEAT AGING OF A BROMOBUTYL TIRE INNER LINER UNDER AEROBIC AND ANAEROBIC CONDITIONS

ABSTRACT A bromobutyl tire inner liner compound was prepared and subjected to aerobic and anaerobic heat aging at a temperature of 100 °C for seven aging times up to 8 weeks. Hardness and mechanical properties were monitored, and the evolution of the crosslink density was followed using equilibrium solvent swell and low field double quantum (DQ) nuclear magnetic resonance (NMR). The hardness and the 300% tensile stress increased with heat aging, while both tensile strength and elongation at break dropped. Both chain scission and crosslinking reactions were taking place. Equilibrium swelling and DQ NMR results confirmed that a larger crosslink density increase was seen under aerobic versus anaerobic aging conditions. The network distribution consisting of a dominant low crosslinking zone and small areas of higher crosslinking slowly broadened and shifted toward higher crosslink densities upon heat aging. The compounds aged heterogeneously. Attenuated total reflectance–Fourier transform infrared spectroscopy confirmed the presence of an oxidized surface layer, and therefore diffusion-limited oxidation effects, but only under aerobic aging conditions. Reaction mechanisms are proposed to explain the net crosslink rise with heat aging.

Manganese and Nickel Acetylacetonates as Curatives for Chloroprene Rubber Based on Heck’s Reaction

The commonly used curing system for chloroprene rubber (CR) is a combination of two metal oxides, such as magnesium oxide (MgO) and zinc oxide (ZnO). Application of MgO and ZnO enables to obtain a good balance between processability of rubber compounds and mechanical properties of the vulcanizates. Despite high activity in crosslinking reactions, ZnO is classified as ecotoxic to aquatic organisms, thus environmental legislation requires its quantity in technology to be limited. In our studies more environmentally friendly curing systems were applied, which enabled eliminating ZnO from CR compounds. These curing systems consisted of manganese acetylacetonate (Mn(acac)) or nickel acetylacetonate (Ni(acac)) and triethanolamine (TEOA) used as a base necessary to perform Heck’s reaction. Both metal acetylacetonates exhibited high activity in crosslinking reactions, which was confirmed by a great torque increment during rheometric measurements and high degree of elastomer crosslinking. The type of metal acetylacetonate and the amount of TEOA seemed to have less influence on the efficiency of the curing system than the filler used. Rubber compounds filled with carbon black (CB) were characterized by definitely shorter optimal vulcanization times and higher degree of crosslinking compared to CR composites filled with nanosized SiO2. Moreover, application of the proposed curing systems allowed to obtain CR vulcanizates with mechanical properties comparable with the benchmarks cured with metal oxides.

Effects of Boron Carbide on Coking Behavior and Chemical Structure of High Volatile Coking Coal during Carbonization

Modified cokes with improved resistance to CO2 reaction were produced from a high volatile coking coal (HVC) and different concentrations of boron carbide (B4C) in a laboratory scale coking furnace. This paper focuses on modification mechanism about the influence of B4C on coking behavior and chemical structure during HVC carbonization. The former was studied by using a thermo-gravimetric analyzer. For the latter, four semi-cokes prepared from carbonization tests for HVC with or without B4C at 450 °C and 750 °C, respectively, were analyzed by using Fourier transform infrared spectrum and high-resolution transmission electron microscopy technologies. It was found that B4C will retard extensive condensation and crosslinking reactions by reducing the amount of active oxygen obtained from thermally produced free radicals and increase secondary cracking reactions, resulting in increasing size of aromatic layer and anisotropic degree in coke structure, which eventually improves the coke quality.