On the Lanthanide Effect on Functional Properties of 0.94Na0.5Bi0.5TiO3-0.06BaTiO3 Ceramic.

The beneficial effects of lanthanide incorporation into 0.94Na0.5Bi0.5TiO3-0.06BaTiO3 (BNT-BT) matrix on its functional properties were investigated. The conventional solid-state method was used for synthesizing samples. The structural refinement revealed that all samples crystallized in R3c rhombohedral symmetry. Raman spectroscopy study was carried out using green laser excitation and revealed that no clear perceptible variation in frequency is observed. Dielectric measurements unveiled that the introduction of rare earth obstructed the depolarization temperature promoted in BNT-BT, the diffusive phase transition decreasing with increasing lanthanide size. Only dysprosium addition showed comparable diffusion constant and dielectric behavior as the unmodified composition. Further, the comparison of the obtained ferroelectric hysteresis and strain-electric field loops revealed that only Dy-phase exhibited interesting properties comparing parent composition. In addition, the incorporation of lanthanides Ln3+ into the BNT-BT matrix led to the development of luminescence characteristics in the visible and near infrared regions, depending on the excitation wavelengths. The simultaneous occurrence of photoluminescence and ferroelectric/piezoelectric properties opens up possibilities for BNT-BT-Ln to exhibit multifunctionality in a wide range of applications.

Three novel polysulfide-based conjugated polymers and characterization of their optoelectronic properties.

The aim of this study was to investigate the effect of side chain size on the optical and charge transport properties of thin films prepared from novel conjugated polysulfide-based polymers. Three polymers, labeled P1, P2, and P3, were derived from polysulfide derivatives and had different arylene groups (5,5'- biphenylene, 4,4'-biphenylene, and 2,6-pyridylene). Optical analysis was performed using photoluminescence (PL) and UV-visible absorption spectroscopy, revealing an energy band gap of 2.41-3.02 eV; P1 emitted yellow, P2 blue-green, and P3 green. Cyclic voltammetry measurements of the electrochemical band gap and HOMO and LUMO energy levels revealed that the polymer exhibited p-type semiconductor activity; the electrical properties of diodes based on the ITO/polysulfide derivative/Al structure were explored through analysis of current-voltage characteristics. The current space charge limitation (SCLC) mechanism was used to model the behavior of these diodes; the P2 thin film layer exhibited higher mobility than the other layers. The relationship between the geometry of the polymer thin films and their optical and electrical properties was thoroughly investigated.

Synthesis, Structural, Optical, and Electrical Characterization of Biochitosan/Na0.5Bi0.5TiO3 Composite Thin-Film Materials.

The purpose of this research work was to synthesis bioderived nanocomposite films by incorporating Na0.5Bi0.5TiO3 (NBTO) nanoparticles into a chitosan matrix. The NBTO nanoparticles were synthesized using a traditional solid-state technique. Then, through a solution-casting approach, flexible composite films were fabricated using chitosan polymer. The study presents a range of compelling findings. For structural and morphological insights, scanning electron microscopy (SEM) reveals a fascinating morphology where NBTO nanoparticles are uniformly dispersed and interlocked with other particles, forming interconnected grains with significant interspaces within the chitosan matrix. For the optical properties, the spectral response within the 300-800 nm range is primarily governed by light scattering attributed to NBTO particles with diameter sizes ranging from 100 to 400 nm, as well as the distinctive bandgap exhibited by the NBTO phase. The investigation of dielectric properties demonstrates that composite films exhibit markedly higher dielectric values in comparison to pure chitosan films. It is noteworthy that an increase in the NBTO content results in a corresponding increase in dielectric values, enhancing the versatility of these materials. Local piezoelectric measurements utilizing piezoresponse force microscopy confirm the expected piezoelectric and ferroelectric behavior of NBTO particles when dispersed within the chitosan matrix. This research introduces a novel class of biocompatible nanocomposite materials, combining impressive structural attributes, enhanced dielectric properties, and piezoelectric capabilities. The outcomes of this study hold substantial promise for advanced applications in opto- and piezoelectric technologies, marking a significant advancement in biologically sourced materials with multifunctional properties.

From PEF to PBF: What difference does the longer alkyl chain make a computational spectroscopy study of poly(butylene 2,5-furandicarboxylate).

This work explores the conformational preferences and the structure-property correlations of poly(butylene 2,5-furandicarboxylate) (PBF), a longer chain analogue of the most well-known biobased polyester from the furan family, poly(ethylene 2,5-furandicarboxylate) (PEF). A thorough computational spectroscopic study-including infrared, Raman and inelastic neutron scattering spectroscopy, combined with discrete and periodic density functional theory calculations-allowed the identification of dominant structural motifs in the amorphous and crystalline regions. Discrete calculations and vibrational spectroscopy of semi-crystalline and amorphous samples strongly support the predominance of gauche, trans, gauche conformations of the butylene glycol fragment in both the crystalline and amorphous domains. In what concerns the furandicarboxylate fragment, amorphous domains are dominated by syn,syn conformations, while in the crystalline domains the anti,anti forms prevail. A possible crystalline structure-built from these conformational preferences and including a network of C-H···O hydrogen bond contacts-was optimized using periodic density functional theory. This proposed crystal structure avoids the unrealistic structural features of the previously proposed X-ray structure, provides an excellent description of the inelastic neutron scattering spectrum of the semi-crystalline form, and allows the correlation between microscopic structure and macroscopic properties of the polymer.

Crystallization and molecular mobility in renewable semicrystalline copolymers based on polycaprolactone and polyisosorbide.

A series of novel block copolymers based on two biodegradable polymers, poly(ε-caprolactone), PCL, and poly(isosorbide), PIS, with PIS fractions 5, 10, and 25 wt%, are studied herein. The aim is to assess the effects of the amorphous PIS phase on the properties of the semicrystalline PCL (majority), in addition to the synthesis strategy. The latter involved the polymerization of caprolactone onto initial PIS of low molar mass, resulting, thus, in gradually shorter PCL blocks when the starting amount of PIS is increased. The structure-property relationship investigation, with an emphasis on molecular mobility and crystallization, involves the following sum of complementary techniques: differential scanning calorimetry, dielectric spectroscopy, polarized optical microscopy and X-ray diffraction. The molecular mobility map for these PCL/PIS and initial PIS is drawn here for the first time. Despite the high glass transition temperature of PIS (Tg ∼ 51 °C) compared to that of PCL (-66 °C), the Tg of the copolymers barely changes, as it is mainly ruled by crystallinity. The latter seems to be facilitated in the copolymers, in both the amount and the rate. The local molecular mobility of PCL and PCL/PIS consists of faster γPCL relaxation which is unaffected in the copolymers, whereas the slower ßPCL process arising from the backbone ester group rotation exhibits a systematic deceleration in the presence of PIS. A connection between such local motions and the corresponding segmental α relaxation, observed previously in other polyesters, is also found to be true here. Apart from that, the dielectric Tg as well as the cooperativity of the polymer chains drop moderately, which indicates spatial confinement between the PCL crystals, whereas correlations with the looser lamellar chain packing within the spherulites are gained. The relaxations of initial PIS, i.e., γPIS, ßPIS and αPIS, could not be resolved within the copolymers. Along with other properties, such as ionic conductivity, we conclude to the homogeneity of our systems, with sufficient PCL/PIS distribution.

Isosorbide and 2,5-Furandicarboxylic Acid Based (Co)Polyesters: Synthesis, Characterization, and Environmental Degradation.

Poly(2,5-furandicarboxylate)s incorporating aliphatic moieties represent a promising family of polyesters, typically entirely based on renewable resources and with tailored properties, notably degradability. This study aims to go beyond by developing poly(isosorbide 2,5-furandicarboxylate-co-dodecanedioate) copolyesters derived from isosorbide (Is), 2,5-furandicarboxylic acid (FDCA), and 1,12-dodecanedioic acid (DDA), and studying their degradation under environmental conditions, often overlooked, namely seawater conditions. These novel polyesters have been characterized in-depth using ATR-FTIR, 1H, and 13C NMR and XRD spectroscopies and thermal analysis (TGA and DSC). They showed enhanced thermal stability (up to 330 °C), and the glass transition temperature increased with the content of FDCA from ca. 9 to 60 °C. Regarding their (bio)degradation, the enzymatic conditions lead to the highest weight loss compared to simulated seawater conditions, with values matching 27% vs. 3% weight loss after 63 days of incubation, respectively. Copolymerization of biobased FDCA, Is, and DDA represents an optimal approach for shaping the thermal/(bio)degradation behaviors of these novel polyesters.

Green Chemistry and Molecularly Imprinted Membranes.

Technological progress has made chemistry assume a role of primary importance in our daily life. However, the worsening of the level of environmental pollution is increasingly leading to the realization of more eco-friendly chemical processes due to the advent of green chemistry. The challenge of green chemistry is to produce more and better while consuming and rejecting less. It represents a profitable approach to address environmental problems and the new demands of industrial competitiveness. The concept of green chemistry finds application in several material syntheses such as organic, inorganic, and coordination materials and nanomaterials. One of the different goals pursued in the field of materials science is the application of GC for producing sustainable green polymers and membranes. In this context, extremely relevant is the application of green chemistry in the production of imprinted materials by means of its combination with molecular imprinting technology. Referring to this issue, in the present review, the application of the concept of green chemistry in the production of polymeric materials is discussed. In addition, the principles of green molecular imprinting as well as their application in developing greenificated, imprinted polymers and membranes are presented. In particular, green actions (e.g., the use of harmless chemicals, natural polymers, ultrasound-assisted synthesis and extraction, supercritical CO2, etc.) characterizing the imprinting and the post-imprinting process for producing green molecularly imprinted membranes are highlighted.

Solid-State Polymerization of Poly(Ethylene Furanoate) Biobased Polyester, III: Extended Study on Effect of Catalyst Type on Molecular Weight Increase.

In this study, the synthesis of poly(ethylene furanoate) (PEF), catalyzed by five different catalysts-antimony acetate (III) (Sb Ac), zirconium (IV) isopropoxide isopropanal (Zr Is Ip), antimony (III) oxide (Sb Ox), zirconium (IV) 2,4-pentanedionate (Zr Pe) and germanium (IV) oxide (Ge Ox)-via an industrially common combination of melt polymerization and subsequent solid-state polymerization (SSP) is presented. In all reactions, proper amounts of 2,5-dimethylfuran-dicarboxylate (DMFD) and ethylene glycol (EG) in a molar ratio of DMFD/EG= 1/2 and 400 ppm of catalyst were used. Polyester samples were subjected to SSP procedure, under vacuum application, at different reaction times (1, 2, 3.5, and 5 h) and temperatures of 190, 200, and 205 °C. Carboxyl end-groups concentration (⁻COOH), intrinsic viscosity (IV), and thermal properties, via differential scanning calorimetry (DSC), were measured for all resultant polymers to study the effect of the used catalysts on the molecular weight increase of PEF during SSP process. As was expected, it was found that with increasing the SSP time and temperature, the intrinsic viscosity and the average molecular weight of PEF steadily increased. In contrast, the number of carboxyl end-groups content showed the opposite trend as intrinsic viscosity, that is, gradually decreasing during SSP time and temperature increase. It is worthy to note that thanks to the SSP process an obvious and continuous enhancement in the thermal properties of the prepared PEF samples was attained, in which their melting temperatures (Tm) and degree of crystallinity (Xc) increase progressively with increasing of reaction time and temperature. To predict the time evolution of polymers IV, as well as the hydroxyl and carboxyl content of PEF polyesters during the SSP, a simple kinetic model was developed. From both the theoretical simulation results and the experimental measurements, it was demonstrated that surely the Zr Is Ip catalyst shows the best catalytic characteristics compared to all other used catalysts herein, that is, leading in reducing-in a spectacular way-the activation energy of the involved both transesterification and esterification reactions during SSP.

Microwave-assisted synthesis of isosorbide-derived diols for the preparation of thermally stable thermoplastic polyurethane.

In order to prepare thermally stable isosorbide-derived thermoplastic polyurethane, the synthesis of two new chiral exo-exo configured diols, prepared from isosorbide, and two types of diphenols (bisphenol A and thiodiphenol) was described. The synthesis conditions were optimized under conventional heating and microwave irradiations. To prove their suitability in polymerization, these monomers were successfully polymerized using 4,4'-diphenylmethane diisocyanate (MDI) and hexamethylene diisocyanate (HDI). Both monomers and polymers have been studied by NMR, FT-IR, TGA, DSC; intrinsic viscosity of polymers has also been determined. The results showed the effectiveness of the synthetic strategy proposed; moreover, a dramatic reduction of the reaction time and an important improvement of the monomers yield using microwave irradiation have been demonstrated. The monomers, as well as the polymers, showed excellent thermal stability both in air and nitrogen. It was also shown that the introduction of sulphur in the polyurethane backbone was effective in delaying the onset of degradation as well as the degradation rate.

Solid-State Polymerization of Poly(ethylene furanoate) Biobased Polyester, I: Effect of Catalyst Type on Molecular Weight Increase.

In this work, we report the synthesis of poly(ethylene furanoate) (PEF), catalyzed by three different catalysts, namely, titanium (IV) isopropoxide (TIS), tetrabutyltitanate (TBT), and dibutyltin (IV) oxide (DBTO), via the two-stage melt polycondensation method. Solid-state polymerization (SSP) was conducted at different reaction times (1, 2, 3.5, and 5 h) and temperatures 190, 200, and 205 °C, under vacuum. The resultant polymers were analyzed according to their intrinsic viscosity (IV), end groups (⁻COOH), and thermal properties, via differential scanning calorimetry. DSC results showed that the post polymerization process was favorable to enhance the melting point of the prepared PEF samples. As was expected, the intrinsic viscosity and the average molecular weight of PEF increased with the SSP time and temperature, whereas the number of carboxyl end-groups was decreased. A simple kinetic model was also developed and used to predict the time evolution of polymers IV, as well as the carboxyl and hydroxyl content of PEF during the SSP. From both the experimental measurements and the theoretical simulation results it was proved that the presence of the TIS catalyst resulted in higher transesterification kinetic rate constants and higher reaction rates. The activation energies were not much affected by the presence of different catalysts. Finally, using DBTO as a catalyst, the polyesters produced have higher crystallinity, and as a consequence, higher number of inactive carboxyl and hydroxyl groups.

Optimized Synthesis According to One-Step Process of a Biobased Thermoplastic Polyacetal Derived from Isosorbide.

This paper describes both the synthesis and characterization of a biobased and non-aromatic polyacetal produced from the reaction between isosorbide and methylene chloride. The reaction was conducted in an aprotic dipolar and harmless solvent using a one-step, fast and economical procedure. The chemical composition of this polymer was investigated using Nuclear Magnetic Resonance and Fourier Transform Infra-Red spectroscopies. The molecular weights were examined by size exclusion chromatography and MALDI-TOF spectrometry. The synthesis conditions (concentration, mixing speed, solvent nature, stoichiometry, addition mode of one reactan) were found to strongly influence both polymer architecture and reaction yield. Under moderated stirring conditions, the polyacetal was characterized by a larger amount of macro-cycles. Inversely, under higher intensity mixing and with an excess of methylene chloride, it was mainly composed of linear chains. In this latter case, the polymeric material presented an amorphous morphology with a glass transition temperature (Tg) close to 55 °C. Its degradation temperature was evaluated to be close to 215 °C using thermogravimetry according to multi-ramp methodology. The chemical approach and the physicochemical properties are valuable in comparison with that characteristic of other isosorbide-based polyacetals.

3,3'-Bis(chloro-meth-yl)-4,4'-dieth-oxy-1,1'-biphen-yl.

The asymmetric unit of the title compound, C18H20Cl2O2, consists of a half-mol-ecule, the other half being generated by an inversion center, located at the mid-point of the benzene-benzene bond. Except for the two Cl atoms, all other atoms of the compound are nearly coplanar, with the atomic displacements from the mol-ecular mean plane ranging from 0.0037 (19) to 0.071 (2) Å. The two Cl atoms are in trans positions and are displaced with respect to the mean plane by 1.687 (2) and -1.693 (3) Å. The crystal packing is governed by van der Waals inter-actions.

1-Benz-yloxy-2,5-bis-(chloro-meth-yl)-4-meth-oxy-benzene.

In the title compound, C(16)H(16)Cl(2)O(2), the dihedral angle between the two rings is 52.65 (10)°. The two Cl atoms are trans to one another being displaced by 1.644 (5) and -1.664 (4) Šfrom the plane of the benzene ring. Except for the two Cl atoms and the C atoms of the ring of the benz-yloxy group, all the other atoms of the compound lie in the same plane [maximum deviation = 0.056 (3) Å]. In the crystal, no significant intermolecular interactions are observed.

2,2-Bis(3-chloro-methyl-4-ethoxy-phen-yl)propane.

The title compound, C(21)H(26)Cl(2)O(2), a bis-chloro-methyl derivative of O-ethyl-ated bis-phenol A, exhibits C(2) mol-ecular symmetry. It shows a bent conformation with the two benzene rings nearly perpendicular [dihedral angle = 87.17 (6)°].