Ethyl group as matrix modifier and inducer of ordered domains in hybrid xerogels synthesised in acidic media using ethyltriethoxysilane (ETEOS) and tetraethoxysilane (TEOS) as precursors

Hybrid silica xerogels favourably combine the properties of organic and inorganic components in one material; consequently these materials are useful for multiple applications. The versatility and mild synthetic conditions provided by the sol-gel process are ideal for the synthesis of hybrid materials. The specific aims of this study were to synthesise hybrid xerogels in acidic media using tetraethoxysilane (TEOS) and ethyltriethoxysilane (ETEOS) as silica precursors, and to assess the role of the ethyl group as a matrix modifier and inducer of ordered domains in xerogels. All xerogels were synthesised at pH 4.5, at 60 °C, with 1:4.75:5.5 TEOS:EtOH:H₂O molar ratio. Gelation time exponentially increased with the ETEOS molar ratio. Incorporation of the ethyl groups into the structure of xerogels reduced cross-linking, increased the average siloxane bond length, and promoted the formation of ordered domains. As a result, a transition from Qⁿ to Tⁿ signals detected in the ²⁹Si NMR spectra, the Si–O structural band in the FTIR spectra shifted to lower wavelength, and a new peak in the XRD pattern at 2θ < 10° appeared in the XRD patterns. Mass spectroscopy detected fragments with high numbers of silicon atoms and a polymeric distribution.     

High-temperature stabilization of polypropylene using hindered phenol–thioester stabilizer combinations,Part 1: Optimization and efficacy via nondust blends

The thermal degradation of unstabilized polypropylene has been investigated under long-term processing (twin extruder) and thermal aging at 150°C, with additive concentration studies on combinations of an established hindered phenolic antioxidant (pentaerythritol tetrakis (3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate) [S1010] and two popular thioesters (distearyl-3,3′-thiodipropionate [DSTDP] and didodecyl-3,3′-thiodipropionate [DLTDP]) using melt flow rate, carbonyl index and powder diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) (FTIR), and differential scanning calorimetry (DSC) (oxidation induction time [OIT]) and ultimate embrittlement time (Fracture) on injection-molded test pieces. It was found that 20:80 phenol:thioester ratios provided the best long-term thermal stability (LTTS); however, this was the reverse for processing stabilization (80:20), underlining the antioxidant nature of the two stabilizers (long term vs. melt). Melt preblending of the stabilizers (to form a no-dust blend) gave rise to improved LTTS. DRIFTS FTIR indicated that there was an improvement in preblending the additives, which removed any volatile impurities. Increased additive dispersion and localized potential efficacy in the stabilization cycle is important, as well as possible improved addition of the additives to the extruder rather than fine powder. The data are discussed in relation to the long-term stabilization of polypropylene in high-temperature applications such as under the bonnet of automobiles where minimizing stabilizer losses and maximizing synergy are important.     

Degradation studies of epoxy coatings on printed circuit boards after pressure cooker test

The present work focuses on the investigation of the degradation of screen-printed epoxy coatings on printed circuit boards under multiple corrosion loads realized by the pressure cooker test (PCT). Since methods like the common mechanical shear strength tests are destructive and limited in information, the authors' approach used electrochemical impedance spectroscopy to study the change of their electrochemical behavior and the state of degradation. Complementarily, the Fourier-transformed infrared spectroscopy was used to investigate the possible molecular change of the polymer due to the exposition. The experiments were carried out after different times of load. It could be shown that the complex conditions of the PCT initiate a controversial mechanism. The harsh corrosion load already results in a degradation of the polymer after 8 h but simultaneously the enhanced test temperature leads to ongoing curing processes consuming the remaining parts of resin and curing agents. As a result, the degradation kinetic seems to be delayed and after the test time of 96 h, the epoxy is less degraded than it was expected based on the results after a shorter time exposition.     

Thermo-mechanical,structural characterization and antibacterial performance of solvent casted polylactide/cinnamon oil composite films

Polylactic acid (PLA) based composite films were prepared by incorporating polyethylene glycol (PEG) and cinnamon oil (CIN) (25 and 50% w/w of PLA) via solution casting method. Morphological, structural, thermo-mechanical, spectral, and antibacterial properties of PLA/PEG/CIN films were investigated. Tensile strength (TS) and tensile modulus (TM) of the film decreased, while the elongation at break (EAB) increased by increasing CIN concentration. Using the principle of time-temperature superposition, the viscous modulus and the complex viscosity of composite films at selected temperatures and frequencies (time scales) were superimposed well in an extended frequency range. Thermal properties decreased substantially with incorporation of CIN. Significant changes in molecular organisation and intermolecular interactions between CIN and PLA/PEG matrix were observed through the FTIR spectroscopy. Scanning electron microscopic (SEM) revealed rough surfaces of the composite films. The effectiveness of composite films was tested against Listeria monocytogenes and Salmonella typhimurium inoculated in chicken samples, and it was found that the film containing 50% CIN showed an antibacterial activity during 16 days storage at refrigerated condition. The developed film has a potential for packaging of chicken samples with extended storage.     

Structural and impedance analysis of Bi0.5Na0.5Ti0.80Mn0.20O3 ceramics

The Bi_0.5Na_0.5Ti_0.80Mn_0.20O₃ ceramic was synthesized by a conventional solid-state reaction technique. Rietveld refinement of X-ray diffraction data confirms the rhombohedral crystal structure of the compound with R3c space group. The optical band gap energy of the compound is found to be 1.93 eV. The substitution of 20% Mn ions at the Ti sites results in the improved dielectric characteristics and a shift in the ferroelectric to paraelectric electric phase transition peak from 330 °C to 370 °C in the material. The frequency dispersion of dielectric constant and its footprint in the Nyquist and Cole-Cole plots have been analyzed. The analysis of complex impedance and modulus spectroscopy confirms the non-Debye type of relaxation mechanisms in the material with contributions from both the grain and grain boundary to the electrical properties. The frequency dependence of AC conductivity data exhibits overlapping large polaron tunneling conduction mechanism in the compound.     

Optimization of process parameters and catalytic pyrolysis of Cascabela thevetia seeds over low-cost catalysts towards renewable fuel production

The present study deals with the optimization of process parameters and thermocatalytic pyrolysis of Cascabela thevetia (CT) seeds in a semi-batch cylindrical-shaped reactor. Response surface methodology (RSM) was employed for the optimization of process variables, while commercial catalysts CaO and Al₂O₃ were used for catalytic pyrolysis. From results, it was concluded that 525 °C temperature, 75 °C min⁻¹ heating rate, and 75 mL min⁻¹ flow of nitrogen yielded maximum pyrolytic liquid (45.26 wt%) while with the attendance of catalysts at 20 wt% increased the yield of pyrolytic liquid (49.12 wt% and 46.87 wt% for CaO and Al₂O₃ respectively). Optimization outcomes displayed that linear and quadratic terms of utilized factors were more noteworthy while interaction effects between the factors were not significant. Further, characterization of pyrolytic oil established that utilization of catalysts expressively enhanced its properties by reducing viscosity and boosted the calorific value. FTIR examination of pyrolytic oil showed that the attendance of phenols, ethers, alcohols, ketones, alkanes, acids, etc., while ¹H NMR results supported the FTIR results. GC-MS analysis showed a substantial reduction of phenols and oxygen-rich products and boost the development of alcohol and aldehydes in pyrolytic oil with the introduction of catalysts. These parameters indicate improved properties of pyrolytic oil, which intensified its bioenergy capabilities.     

Analysis of the Content of Fatty Acid Methyl Esters in Biodiesel by Fourier-Transform Infrared Spectroscopy: Method and Comparison with Gas Chromatography

The increasing importance of sustainability in energy production has led to a global commitment to the use of fuels derived from renewable biological sources, such as biodiesel produced from plant crops or biomass residues, that do not compete with human food for their production. For a biofuel to be considered biodiesel, it must satisfy the specifications described in the UNE 14214, with the UNE-EN 14103 referring to the determination of fatty acid methyl ester content. This standard applies gas chromatography as an analytical technique. Gas chromatography is a widely used technique in the analysis of methyl ester although it has a number of drawbacks such as: long analysis times, a high consumption of high-quality gases and internal standards, does not allow the analysis of different compounds with the same column, etc. From an industrial production point of view, is necessary to know the fatty acid methyl ester content in biodiesel samples quickly. This paper studies the development of an analytical method using Fourier transform infrared spectroscopy (FTIR) as alternative to gas chromatography (GC), since it is a simple, rapid, and precise analytical technique to quantify fatty acid methyl ester content in biofuel samples.     

Preparations and tailoring of structural,magnetic properties of rare earths (REs) doped nanoferrites for microwave high frequency applications

Rare earths (Res) doped Mn spinel nanoferrites with nominal composition MnR_0.2Fe_1·8O₄ (REs = Tb, Pr, Ce, Y and Gd) were synthesized using sol gel method. FTIR, XRD and FESEM were employed to evaluate the structure, phase, vibrational bands, morphology, grain size and microstructure respectively. VSM was employed to investigate the magnetic features of the Mn nanoferrite and REs doped Mn nanoferrites. XRD confirmed the single-phase cubic structure of Mn nanoferrite whereas tetragonal phase was observed for all REs doped Mn nanoferrites. Unit cell software was used to determine the structural features such as lattice parameter, cell volume, ‘da’, ‘db’, ‘dc’ and ‘dv’ respectively. FTIR results demonstrated the absorption peaks of Mn and REs doped Mn ferrite at 647-674 cm⁻¹. FESEM results depicted the irregular shapes of the particles with large agglomerations in the prepared samples. The grain size evaluated by LIM (line intercept method) found in the range of 94 to 213 nm respectively. Saturation magnetization was increased from 1.332 to 38.097 emu/g whereas remanence was increased from 1.096 to 25.379 emu/g respectively. In addition, other magnetic parameters such as initial permeability, magnetic anisotropy and magnetic moments were also increased. Moreover, Y–K angles showed significant response with REs doping in Mn ferrites. Furthermore, high frequency response and switching field distribution (SFD) of Mn ferrite and REs doped Mn ferrites were also determined. It is found that Y doped Mn ferrite depicted better high frequency and SFD response as compared to Mn ferrite and REs doped Mn ferrites. The coercivity of all these pure Mn ferrite and rare earth's substituted Mn ferrites (425–246 Oe) was higher as compared to the pure Mn and yttrium substituted Mn ferrite (107–217 Oe. Therefore, it was suggested that Y doped Mn ferrite was more suitable candidate for switching, and high frequency absorption applications in microwave regime.     

Growth and characterization of 4-methyl benzene sulfonamide single crystals

Single crystals of 4-methyl benzene sulfonamide (4MBS) were successfully grown from aqueous solution by low temperature solution growth technique. The grown crystal was characterized by single crystal XRD and powder XRD methods to obtain the lattice parameters and the diffraction planes of the crystal. UV–vis–NIR absorption spectrum was used to measure the range of optical transmittance and optical band gap energy. The optical transmission range was measured as 250–1200 nm. FTIR spectral studies were carried out to identify the presence of functional groups in the grown crystal. The thermal behavior of the crystal was investigated from thermo gravimetric analysis (TGA) and differential scanning calorimetry (DSC) study. The absence of SHG was noticed by Kurtz and Perry powder technique. The third order NLO behavior of the material was confirmed by measuring the nonlinear optical properties using Z-scan technique and it was found that the crystal is capable of exhibiting saturation absorption and self-defocusing performance.