Thermal Analysis and Optimization of the Phase Diagram of the Cu-Ag Sulfide System

Thermal stabilities of selected ternary phases of industrial interest in the Ag-Cu-S system have been studied by the calorimetric and electromotive force techniques. The ternary compounds Ag1.2Cu0.8S (mineral mackinstryite) and AgCuS (mineral stromeyerite) were equilibrated through high-temperature reaction of the pure Cu2S and Ag2S in an inert atmosphere. The synthesized single solid sample constituting the two ternary phases was ground into fine powders and lightly pressed into pellets before calorimetric measurements. An electrochemical cell incorporating the two equilibrated phase and additional CuS as a cathode material was employed. The measurement results obtained with both techniques were analyzed and thermodynamic properties in the system have been determined and compared with the available literature values. Enthalpy of fusion data of the Ag-richer solid solution (Ag,Cu)2S have also been determined directly from the experimental data for the first time. The thermodynamic quantities determined in this work can be used to calculate thermal energy of processes involving the Ag-Cu-S-ternary phases. By applying the obtained results and the critically evaluated literature data, we have developed a thermodynamic database. The self-developed database was combined with the latest pure substances database of the FactSage software package to model the phase diagram of the Ag2S-Cu2S system.

A Water-Stable 2-Fold Interpenetrating cds Net as a Bifunctional Fluorescence-Responsive Sensor for Selective Detection of Cr(III) and Cr(VI) Ions

Reactions of ZnSO4∙7H2O, N-(pyridin-3-ylmethyl)-4-(pyridin-4-yl)-1,8-naphthalimide (NI-mbpy-34), and 5-bromobenzene-1,3-dicarboxylic acid (Br-1,3-H2bdc) afforded a luminescent coordination polymer, [Zn(Br-1,3-bdc)(NI-mbpy-34)]n (1), under hydro(solvo)thermal conditions. Single-crystal X-ray structure analysis revealed that 1 features a three-dimensional (3-D) 2-fold interpenetrating cds (or CdSO4) net topology with the point symbol of (65·8), where the Zn(II) centers are considered as 4-connected square-planar nodes. X-ray powder diffraction (XRPD) patterns and thermogravimetric (TG) analysis confirmed that 1 shows high chemical and thermal stabilities. Notably, 1 displayed solvent dependent photoluminescence properties; the fluorescence intensity and emission maximum of 1 in different solvent suspensions varied when a solvent was changed. Furthermore, the H2O suspension of 1 exhibited blue fluorescence emission and thus can be treated as a selective and sensitive fluorescent probe for turn-on detection of Cr3+ cations through absorbance caused enhancement (ACE) mechanism and turn-off detection of Cr2O72−/CrO42− anions through collaboration of the absorption competition and energy transfer process, with limit of detection (LOD) as low as μM scale.

Investigations of Thermal Stability and Spectroscopic Features of Sm3+ Doped Strontium Aluminate Glasses

In the present work, a series of Sm3+ doped transparent strontium aluminate glasses with the composition Al2O3-(3-x)SrO: xSm3+ (x = 0, 0.01, 0.03, 0.06, 0.1, 0.2) were fabricated by a containerless process using an aerodynamic levitation furnace. The structural characteristics, density, Vicker’s hardness, and thermal and spectroscopic behaviors of these glasses were investigated. All the glasses exhibit excellent thermal stabilities (Tg ≥ 792 °C) and the glass-forming ability is enhanced with the increasing content of Sm3+. The emission spectra recorded under an excitation of 404 nm show four emission transitions as a result of 4G5/2 translated to the lower states of 6H5/2, 6H7/2, 6H9/2, and 6H11/2, and a bright orange-reddish luminescence can be observed in Al2O3-(3-x)SrO: xSm3+ glasses. The high thermal stability, good glass-forming ability and excellent hardness provide new options for the development of visible orange-reddish lasers and smart photoluminescent glass coating materials.

High-Performance Biocomposite Polyvinyl Alcohol (PVA) Films Modified with Cellulose Nanocrystals (CNCs), Tannic Acid (TA), and Chitosan (CS) for Food Packaging

Polyvinyl alcohol (PVA) has been widely applied in industries for its low cost, nontoxicity, biodegradability, and renewable advantages. However, its unstable structure may not meet some strong physical and mechanical needs. In order to enhance the performances of the PVA film, cellulose nanocrystals (CNCs), tannic acid (TA), and chitosan (CS), working as a reinforcer, a crosslinker, and an antimicrobial agent, respectively, were introduced into the PVA matrix. The results indicated that CNCs, TA, and CS were evenly distributed and cohesively incorporated within the PVA matrix, which contributed to the good mechanical properties and thermal stabilities of biocomposite PVA films. Besides, the addition of TA remarkably improved the antiultraviolet and antioxidant capabilities of PVA films, although the light transmittance declined slightly. It was also observed that the pure PVA film and PVA reinforced with CNCs were incapable of protecting against bacteria, while the ones with CS had prominent antibacterial properties to Escherichia coli and Staphylococcus aureus. Overall, the resulting film presented a high potential utilization as a food packaging material for its outstanding physical and mechanical performances.

Polyyne [3]rotaxanes: Synthesis via dicobalt carbonyl complexes and enhanced stability

New strategies for synthesizing polyyne polyrotaxanes are being developed as an approach to stable carbyne ‘insulated molecular wires’. Here we report an active metal template route to polyyne [3]rotaxanes, using dicobalt carbonyl masked alkyne equivalents. We synthesized two [3]rotaxanes, both with the same C28 polyyne dumbbell component, one with a phenanthroline-based macrocycle and one using a 2,6-pyridyl cycloparaphenylene nanohoop. The thermal stabilities of the two rotaxanes were compared with that of the naked polyyne dumbbell in decalin at 80 °C, and the nanohoop rotaxane was found to be 4.5 times more stable.

Synthesis of a novel UV-curable prepolymer 1,3-bis[(3-ethyl-3-methoxyoxetane)propyl]tetramethyldisiloxane and study on its UV-curing properties

Precursor 3-ethyl-3-hydroxymethyloxetane was synthesized with trihydroxypropane and diethyl carbonate as the main raw materials. Intermediate 3-ethyl-3-allylmethoxyoxetane was synthesized with 3-ethyl-3-hydroxymethyloxetane and allyl bromide. Prepolymer 1,3-bis[(3-ethyl-3-methoxyoxetane)propyl]tetramethyldisiloxane was synthesized with 3-ethyl-3-allylmethoxyoxetane and 1,1,3,3-tetramethyldisiloxane. Cationic photoinitiator triarylsulfonium hexafluoroantimonate of 3 wt% was added to the prepolymer, and a novel kind of photosensitive resin was prepared. Structures of the compounds obtained at individual stages of the synthesis were analyzed and characterized by FTIR and 1H-NMR. Photo-DSC analysis showed that the prepolymer had excellent photosensitivity. Thermogravimetric analysis (TG) revealed that the ultraviolet (UV)-cured samples owned excellent thermal stabilities of up to 405°C. And the mechanical properties of the UV-cured samples were tested by the universal material testing machine, giving 25.95 MPa of tensile strength, 2,935.15 MPa of elastic modulus, and 4.09% of elongation at break.

Polymorphic Phases of Supramolecular Liquid Crystal Complexes Laterally Substituted with Chlorine

New supramolecular complexes, based on H-bonding interactions between 4-(pyridin-4-yl) azo-(2-chlorophenyl) 4-alkoxybenzoates (Bn) and 4-[(4-(n-hexyloxy)phenylimino)methyl]benzoic acid (A6), were prepared and their thermal and mesomorphic properties investigated via differential scanning calorimetry (DSC) and Fourier-transform infrared spectroscopy (FT-IR) in order to confirm their H-bonding interactions. The mesophase behavior of each mixture was examined by DSC and polarized optical microscopy (POM). According to the findings of the study, in all of the designed mixtures, the introduction of laterally polar chlorine atom to the supramolecular complexes produces polymorphic compounds possessing smectic A, smectic C and nematic mesophases, in addition, all products have low melting transitions. Thermal stabilities of the associated phases depend on the position and orientation of the lateral polar Cl− atom as well as the length of terminal flexible alkoxy chain. Comparisons were made between the present lateral Cl− complexes and previously investigated laterally-neat complexes in order to investigate the impact of the addition, nature and orientation of polar substituent on the mesomorphic behavior. The investigations revealed that, the polarity and mesomeric nature of inserted lateral substituent into the base component play an essential role in affecting their mesomorphic properties. Furthermore, for current complexes, induced polymorphic phases have been found by introducing the chlorine atom.

The Influence of Silica Nanoparticles on the Thermal and Mechanical Properties of Crosslinked Hybrid Composites

This paper presents the synthesis and physicochemical characterization of a new hybrid composite. Its main goals are evaluating the structure and studying the thermal and mechanical properties of the crosslinked polymeric materials based on varying chemical properties of the compounds. As an organic crosslinking monomer, bisphenol A glycerolate diacrylate (BPA.GDA) was used. Trimethoxyvinylsilane (TMVS) and N-vinyl-2-pyrrolidone (NVP) were used as comonomers and active diluents. The inorganic fraction was the silica in the form of nanoparticles (NANOSiO2). The hybrid composites were obtained by the bulk polymerization method using the UV initiator Irqacure 651 with a constant weight ratio of the tetrafunctional monomer BPA.GDA to TMVS or NVP (7:3 wt.%) and different wt.% of silica nanoparticles (0, 1, 3%). The proper course of polymerization was confirmed by the ATR/FTIR spectroscopy and SEM EDAX analysis. In the composites spectra the signals correspond to the C=O groups from NVP at 1672–1675 cm−1, and the vibrations of Si–O–C and Si–O–Si groups at 1053–1100 cm−1 from TMVS and NANOSiO2 are visible. Thermal stabilities of the obtained composites were studied by a differential scanning calorimetry DSC. Compared to NVP the samples with TMVS degraded in one stage (422.6–425.3 °C). The NVP-derived materials decomposed in three stages (three endothermic effects on the DSC curves). The addition of NANOSiO2 increases the temperature of composites maximum degradation insignificantly. Additionally, the Shore D hardness test was carried out with original metrological measurements of changes in diameter after indentation in relation to the type of material. The accuracy analysis of the obtained test results was based on a comparative analysis of graphical curves obtained from experimental tests. The values of the changes course of similarity in the examined factors, represented by those of characteristic coefficients were determined based on the Fréchet’s theory.

Influence of the alkyl chain length on the physicochemical properties and microbial biocompatibility of phosphonium based fatty acid ionic liquids

Ionic liquids (ILs) have remarkable properties and applications in many areas of science. Phosphonium ILs have become important because of their unique chemical and thermal stabilities. The present work is focused on the synthesis, characterisation, physicochemical properties, and microbial toxicity assessment of phosphonium ILs bearing seven different fatty acid anions. The structures of the synthesised ILs were confirmed by 1H and 13C nuclear magnetic resonance (NMR) and FTIR spectroscopy. Physicochemical properties such as density and viscosity of pure ILs were measured at temperatures ranging from 298.15 to 313.15 K. The experimental density decreased, whereas the viscosity increased with an increasing number of carbon atoms in the anion. The derived properties were also found to be anion dependent. The thermal decomposition temperature was investigated by TGA. Subsequently, the toxicity profile of the ILs was determined for selected Gram positive and Gram negative bacteria and some species of fungi in terms of minimum inhibitory concentrations (MIC). The results show that the antimicrobial activities of the ILs are strongly related to the structures of the ILs, where an increase in toxicity was observed with increasing alkyl group chain length of the fatty acid anion.