The Influence of Oxidant on Gelatin–Tannin Hydrogel Properties and Structure for Potential Biomedical Application

Nowadays, there is a widespread usage of sodium periodate as an oxidant for synthesizing gelatin–tannin hydrogels. The impact of iodine compounds could have a harmful effect on human health. The study focuses on the proposal of alternative oxidizing systems for tannin oxidation. Gelatin–tannin hydrogels were obtained based on the usage of H2O2/DMSO/KMnO4/KIO4 oxidants and characterized with sorption, thermal (TGA, DTG, DSC), mechanical, FTIR and other methods. The sorption experiments were carried out in a phosphate buffer (pH = 5.8/7.4/9) and distilled water and were investigated with Fick’s law and pseudosecond order equation. The pH dependence of materials in acid media indicates the possibility of further usage as stimuli-responsive systems for drug delivery. Thermal transitions demonstrate the variation of structure with melting (306 ÷ 319 °C) and glass transition temperatures (261 ÷ 301 °C). The activation energy of water evaporation was calculated by isoconversional methods (Kissinger–Akahira–Sunose, Flynn–Wall–Ozawa) ranging from 4 ÷ 18 to 14 ÷ 38 kJ/mole and model-fitting (Coats–Redfern, Kennedy–Clark) methods at 24.7 ÷ 45.3 kJ/mole, indicating the smooth growth of values with extent of conversion. The network parameters of the hydrogels were established by modified Flory–Rehner and rubber elasticity theories, which demonstrated differences in values (5.96 ÷ 21.27·10−3 mol/cm3), suggesting the limitations of theories. The sorption capacity, tensile strength and permeability for water/oxygen indicate that these materials may find their application in field of biomaterials.

INFLUENCE OF THE POLYETHYLENE GLYCOL MOLECULAR MASS ON THERMAL TRANSITIONS OF NANOSIZED COPPER OXIDE

В данной работе получены образцы наноразмерного оксида меди, стабилизированного полиэтиленгликолем различных марок с молекулярными массами от 200 до 6000 Да. Методом рентгеновской дифрактометрии исследована кристаллическая структура полученных образцов наноразмерного оксида меди. В результате рентгенофазового анализа установлено, что структура образцов представляет собой моноклинную кристаллическую решетку, с пространственной группой C2/ c. Методом фотонно-корреляционной спектроскопии изучено влияние молекулярной массы полимера на размер наночастиц. Анализ результатов исследования показал наличие во всех образцах наноразмерного оксида меди (II), стабилизированного полиэтиленгликолем с различной молекулярной массой, одной фракции частиц, распределение которых по размеру носит мономодальный характер. Установлено, что молекулярная масса полиэтиленгликоля оказывает, влияние на размер частиц CuO в коллоидных растворах, при этом фазовый состав и размеры кристаллитов остаются неизменными. Средний гидродинамический радиус частиц CuO в полученных образцах составляет порядка 140 ± 40 нм. Наименьшие значения гидродинамического радиуса 70 ± 15 нм наблюдаются в образце наноразмерного оксида меди, стабилизированного полиэтиленгликолем с молярной массой 6000 Дa. Методом синхронного термического анализа исследовано влияние стабилизатора с различными молекулярными массами на фазовые переходы образцов при термической обработке. В результате термического анализа установлено, что оптимальной температурой прокаливания порошков наноразмерного CuO является 500°C. In this work, samples of nanosized copper oxide stabilized with polyethylene glycol of various grades with molecular weights from 200 to 6000 Da were obtained. The crystal structure of the samples was investigated by X-ray diffractometry. As a result of the XRD analysis, it was found that the samples have a monoclinic crystal lattice with space group C2 / c . The effect of the molecular weight of the polymer on the size of nanoparticles was studied by the photon correlation spectroscopy method. Analysis of the results showed the presence of one fraction of particles in all samples, the size distribution was monomodal. It was found that the molecular weight of polyethylene glycol has an effect on the CuO particle size in colloidal solutions, while the phase composition and crystallite size remain unchanged. The average hydrodynamic radius of CuO particles in the obtained samples was about 140 ± 40 nm. The smallest hydrodynamic radius of 70 ± 15 nm was observed in a sample of nanosized copper oxide stabilized with polyethylene glycol with a molecular weight of 6000 Da. The effect of stabilizers with different molecular weights on the phase transitions of samples during heat treatment was investigated by the synchronous thermal analysis. As a result of thermal analysis, it was found that the optimum temperature for calcining nanosized CuO powders was 500 °C.

Thermal transitions in metastable Cu – 68.5 at. % Co alloy.

Arc melted and drop tube processed Cu – 68.5 at. % Co alloy has been subjected to differential thermal analysis (DTA). The liquidus temperature determined from the DTA curves in the arc melt sample (1664 K) was found to be close to phase diagram estimate of 1662 K. In contrast as a result of liquid phase separation in the drop tube samples, the values obtained in the powders were much lower mainly because the compositions of the demixed phases vary from that of the parent melt. The liquidus temperature of the 850 + μm powders was 1632 K while that of the < 38 μm sieve size powder was 1616 K. This variance is due to the asymmetric nature of the metastable phase diagram of the system.

Effect of Sulfonated Block Copolymer on the Equilibrium and Thermal Properties of Sulfonated Fluoroblock Copolymer Blend Membranes

Polymeric membrane technologies demand the synthesis of new polymers to enhance their equilibrium, thermal, and transport properties. Therefore, the focus of this investigation was the evaluation of the equilibrium and thermal properties of a sulfonated fluoroblock copolymer blend membrane composed of sulfonated poly(styrene-isobutylene-styrene) (SIBS SO3H) and a novel sulfonated fluoroblock copolymer composed of poly(4-fluo- rostyrene) (P4FS), poly(styrene) (PS) and poly(isobutylene) (PIB). The fluoroblock copolymer was synthesized using Atom Transfer Radical Polymerization (ATRP) and cationic polymerization. First, the molecular weight and the thermal stability of the block copolymer were determined using Gel Permeation Chromatography (GPC) and Thermogravimetric Analysis (TGA). Second, the chemical composition was monitored utilizing Fourier Transform Infrared spectroscopy (FTIR) and Nuclear Magnetic Resonance (NMR) spectroscopy. The molecular weight of P4FS-b-PS was Mn ~ 36,100; this value increased 8% after the cationic polymerization. The equilibrium properties of the membrane were evaluated using the water uptake and Ion-Exchange Capacity. The degradation behavior and the thermal transitions were determined using TGA and Differential Scanning Calorimetry (DSC), respectively. This newly membrane exhibited water uptake higher than 608% related to the improvement of 36% in the ion-exchange capacity and the increment of 25.31% and 25.24% in the energy required to produce the thermal transitions induced by the addition of the sulfonated fluoroblock copolymer.

Towards Higher Electric Conductivity and Wider Phase Stability Range via Nanostructured Glass-Ceramics Processing

This review article presents recent studies on nanostructured glass-ceramic materials with substantially improved electrical (ionic or electronic) conductivity or with an extended temperature stability range of highly conducting high-temperature crystalline phases. Such materials were synthesized by the thermal nanocrystallization of selected electrically conducting oxide glasses. Various nanostructured systems have been described, including glass-ceramics based on ion conductive glasses (silver iodate and bismuth oxide ones) and electronic conductive glasses (vanadate-phosphate and olivine-like ones). Most systems under consideration have been studied with the practical aim of using them as electrode or solid electrolyte materials for rechargeable Li-ion, Na-ion, all-solid batteries, or solid oxide fuel cells. It has been shown that the conductivity enhancement of glass-ceramics is closely correlated with their dual microstructure, consisting of nanocrystallites (5–100 nm) confined in the glassy matrix. The disordered interfacial regions in those materials form “easy conduction” paths. It has also been shown that the glassy matrices may be a suitable environment for phases, which in bulk form are stable at high temperatures, and may exist when confined in nanograins embedded in the glassy matrix even at room temperature. Many complementary experimental techniques probing the electrical conductivity, long- and short-range structure, microstructure at the nanometer scale, or thermal transitions have been used to characterize the glass-ceramic systems under consideration. Their results have helped to explain the correlations between the microstructure and the properties of these systems.

Effect of OMMT reinforcement on morphology and rheology properties of polyurethane copolymer nanocomposites

The remarkable structural features of organic modified montmorillonite particles (OMMT) enable them to complete their important role in enhancing different properties of polyurethane copolymer with 75 wt.% hard segments (PUC/75). Based on the melt intercalation approach, various amounts of OMMT were incorporated into PUC/75 solution followed by the injection moulding process. It is essential to mention that the synthesized PUC/75 in this work relied on using 1,5-Pentanediol as a chain extender in order to produce a long-term and thermal-stable PUC successfully. The effect of incorporating various loading of OMMT on rheological properties of neat PUC/75 and its nanocomposites was investigated. The structure of PUC/OMMT was studied using X-ray diffraction (XRD) and scanning electron microscopy. Additionally, differential scanning calorimetry (DSC) thermograms were utilized to investigate OMMT effect on the thermal transitions and crystallinity of resultant PUC nanocomposites. Interestingly, the dynamic rheological analysis exhibited a remarkable increase in melt rheology behaviour with increasing OMMT loading compared to neat PUC/75. This could imply a good interaction between the functional group on the surface of OMMT and PUC/75 domains; particularly hard domains, herein the DSC results showed moderate improvement in melt temperature (Tm) of PUC/OMMT nanocomposite. However, a decline in crystalline temperature (Tc) was also seen due to aggregation of OMMT, especially at higher OMMT loading. While XRD results exhibited a slight shifting in crystalline peaks of PUC nanocomposites relative to neat PUC/75.