Effect of a halogen bond on the crystal structure of terphenyldicarboxylic acid derivatives.

The syntheses and structures of dimethyl [11,21:24,31-terphenyl]-14,34-dicarboxylate (1), dimethyl 22,25-diiodo[11,21:24,31-terphenyl]-14,34-dicarboxylate (2), potassium [11,21:24,31-terphenyl]-14,34-dicarboxylate (3) and dimethyl [1,1'-biphenyl]-4,4'-dicarboxylate (4) are reported. Neighboring phenyl rings in compounds 1, 3 and 4 have a planar structure (torsion angles are 0.6-4.1°) and the molecules are packed into regular layers. In the structure of the iodinated derivative of terphenyldicarboxylic acid (2), the middle benzene ring of the terphenyl fragment is rotated relative to the other rings by 64° due to the repulsion between the protons and the iodine atoms of neighboring rings. The formation of halogen bonds between iodine and oxygen atoms of the carbonyl group leads to the movement of molecules of one layer into another layer and the loss of layered structure. Potassium [11,21:24,31-terphenyl]-14,34-dicarboxylate (3) forms crystals with an ionic structure. The coordination number of the potassium cation is eight and the resulting coordination polyhedron is a distorted square antiprism. Dianions in the potassium salt crystal are packed in layers similar to the layers in the dimethyl ethers 1 and 4. Salt 3 has high thermal stability to 500°C.

1D and 2D coordination polymers with a new rigid chelating linker: diacetylenedisalicylic acid.

Diacetylenedisalicylic acid is a new rigid linker molecule, capable of forming strong chelate bonds with metal cations. Its monosubstituted salts with dimethylamine and sodium form 1D and 2D coordination polymers, whose structures were solved from single crystals, along with the dimethyl ester of diacetylenedisalicylic acid. The structure of the dimethyl ester is characterized by a dense co-facial π-stacking of molecules with a dominance of van der Waals interactions between the stacks. The angle between the stack direction and the butadiyne groups does not meet the Enkelmann criterion for polymerization in a crystal. In contrast to the dimethyl ester, both salts have a rigid framework with channels filled with disordered solvent molecules. Photoluminescence spectra of the acid and its dimethyl ester have been studied. Thermal analysis of the acid confirms its high thermal stability to 286°C. The acid and its dimethyl ester are prone to polymerization on further heating followed by 50-52% mass loss, forming an amorphous carbon residue at 1000°C.

Enhancement of intermolecular aggregation on solvent-influenced strong hydrogen-bonded single crystal.

The intermolecular aggregation between the solvent and organic molecules is covered in the current article. 4,4'-(Buta-1,3-diyne-1,4-diyl)dibenzoic acid (DADBA) was used as an organic molecule and dimethyl sulfoxide (DMSO) as a solvent to create the target compound DADBA-DMSO. The material's hydrogen bonding and intermolecular aggregation were determined by appropriate characterization methods, including single-crystal X-ray diffraction (XRD), Fourier-transform infrared (FTIR), photoluminescence (PL), and cyclic voltammetry (CV) analysis. Each hydrogen of the carboxylic group is coordinated by oxygen from the DMSO molecule in the stiff planar layer packing that makes up the DADBA-DMSO crystal structure.

Fracture Toughness of Moldable Low-Temperature Carbonized Elastomer-Based Composites Filled with Shungite and Short Carbon Fibers.

This work evaluated the fracture toughness of the low-temperature carbonized elastomer-based composites filled with shungite and short carbon fibers. The effects of the carbonization temperature and filler content on the critical stress intensity factor (K1c) were examined. The K1c parameter was obtained using three-point bending tests for specimens with different l/b ratio (notch depth to sample thickness) ranging from 0.2 to 0.4. Reliable detection of the initiation and propagation of cracks was achieved using an acoustic sensor was attached to the samples during the bending test. The critical stress intensity factor was found to decrease linearly with increasing carbonization temperature. As the temperature increased from 280 to 380 °C, the K1c parameter was drastically reduced from about 5 to 1 MPa·m1/2 and was associated with intense outgassing during the carbonization step that resulted in sample porosity. The carbon fiber addition led to some incremental toughening; however, it reduced the statistical dispersion of the K1c values.

On the Structural Peculiarities of Self-Reinforced Composite Materials Based on UHMWPE Fibers.

The structure of self-reinforced composites (SRCs) based on ultra-high molecular weight polyethylene (UHMWPE) was studied by means of Wide-Angle X-ray Scattering (WAXS), X-ray tomography, Raman spectroscopy, Scanning Electron Microscopy (SEM) and in situ tensile testing in combination with advanced processing tools to determine the correlation between the processing conditions, on one hand, and the molecular structure and mechanical properties, on the other. SRCs were fabricated by hot compaction of UHMWPE fibers at different pressure and temperature combinations without addition of polymer matrix or softener. It was found by WAXS that higher compaction temperatures led to more extensive melting of fibers with the corresponding reduction of the Herman's factor reflecting the degree of molecular orientation, while the increase of hot compaction pressure suppressed the melting of fibers within SRCs at a given temperature. X-ray tomography proved the absence of porosity while polarized light Raman spectroscopy measurements for both longitudinal and perpendicular fiber orientations showed qualitatively the anisotropy of SRC samples. SEM revealed that the matrix was formed by interlayers of molten polymer entrapped between fibers in SRCs. Moreover, in situ tensile tests demonstrated the increase of Young's modulus and tensile strength with increasing temperature.

Polymers under Load and Heating Deformability: Modelling and Predicting.

The polymer deformability under load and heating is the determining factor in calculating reinforced polymer structures used under heating. Deformability-load/temperature relations make it possible to calculate temperature stresses and deformations in bearing cross-sections of polymer structures such as chimneys, smokestacks, etc. The present study suggests a method of calculating deformability of polymers subjected to the temperature loads. The method is based on the structure model of pack or layer bonded polymer domains where the elasticity of rigid bonds decreases with heating according to entropy principles. The method has been successfully tested on various polymers and compounds with due account for the effect of mineral additives on the deformation modulus increase.

Hybrid Self-Reinforced Composite Materials Based on Ultra-High Molecular Weight Polyethylene.

The properties of hybrid self-reinforced composite (SRC) materials based on ultra-high molecular weight polyethylene (UHMWPE) were studied. The hybrid materials consist of two parts: an isotropic UHMWPE layer and unidirectional SRC based on UHMWPE fibers. Hot compaction as an approach to obtaining composites allowed melting only the surface of each UHMWPE fiber. Thus, after cooling, the molten UHMWPE formed an SRC matrix and bound an isotropic UHMWPE layer and the SRC. The single-lap shear test, flexural test, and differential scanning calorimetry (DSC) analysis were carried out to determine the influence of hot compaction parameters on the properties of the SRC and the adhesion between the layers. The shear strength increased with increasing hot compaction temperature while the preserved fibers' volume decreased, which was proved by the DSC analysis and a reduction in the flexural modulus of the SRC. The increase in hot compaction pressure resulted in a decrease in shear strength caused by lower remelting of the fibers' surface. It was shown that the hot compaction approach allows combining UHMWPE products with different molecular, supramolecular, and structural features. Moreover, the adhesion and mechanical properties of the composites can be varied by the parameters of hot compaction.

Effect of Glass Fibers Thermal Treatment on the Mechanical and Thermal Behavior of Polysulfone Based Composites.

The effect of thermal treatment of glass fibers (GF) on the mechanical and thermo-mechanical properties of polysulfone (PSU) based composites reinforced with GF was investigated. Flexural and shear tests were used to study the composites' mechanical properties. A dynamic mechanical analysis (DMA) and a heat deflection temperature (HDT) test were used to study the thermo-mechanical properties of composites. The chemical structure of the composites was studied using IR-spectroscopy, and scanning electron microscopy (SEM) was used to illustrate the microstructure of the fracture surface. Three fiber to polymer ratios of initial and preheated GF composites (50/50, 60/40, 70/30 (wt.%)) were studied. The results showed that the mechanical and thermo-mechanical properties improved with an increase in the fiber to polymer ratio. The interfacial adhesion in the preheated composites enhanced as a result of removing the sizing coating during the thermal treatment of GF, which improved the properties of the preheated composites compared with the composites reinforced with initial untreated fibers. The SEM images showed a good distribution of the polymer on the GF surface in the preheated GF composites.

High Entropy Oxide Phases with Perovskite Structure.

The possibility of the formation of high entropy single-phase perovskites using solid-state sintering was investigated. The BaO-SrO-CaO-MgO-PbO-TiO2, BaO-SrO-CaO-MgO-PbO-Fe2O3 and Na2O-K2O-CaO-La2O3-Ce2O3-TiO2 oxide systems were investigated. The optimal synthesis temperature is found between 1150 and 1400 °C, at which the microcrystalline single phase with perovskite structure was produced. The morphology, chemical composition, crystal parameters and dielectric properties were studied and compared with that of pure BaTiO3. According to the EDX data, the single-phase product has a formula of Na0.30K0.07Ca0.24La0.18Ce0.21TiO3 and a cubic structure.

Porous Open-Сell UHMWPE: Experimental Study of Structure and Mechanical Properties.

Ultra-high molecular weight polyethylene (UHMWPE) is a bioinert polymer that is widely used as bulk material in reconstructive surgery for structural replacements of bone and cartilage. Porous UHMWPE can be used for trabecular bone tissue replacement, and it can be used in living cell studies as bioinert 3D substrate permeable to physiological fluids. It is important to develop techniques to govern the morphology of open-cell porous UHMWPE structures (pore size, shape, and connectivity), since this allows control over proliferation and differentiation in living cell populations. We report experimental results on the mechanical behavior of porous open-cell UHMWPE obtained through sacrificial removal (desalination) of hot-molded UHMWPE-NaCl powder mixtures with pore sizes in the range 75 µm to 500 µm. The structures were characterized using SEM and mechanically tested under static compression and dynamic mechanical analysis (DMA), bending, and tensile tests. Apparent elastic modulus and complex modulus were in the range of 1.2 to 2.5 MPa showing a weak dependence on cell size. Densification under compression caused the apparent elastic modulus to increase to 130 MPa.

Extremely Polysubstituted Magnetic Material Based on Magnetoplumbite with a Hexagonal Structure: Synthesis, Structure, Properties, Prospects.

Crystalline high-entropy single-phase products with a magnetoplumbite structure with grains in the µm range were obtained using solid-state sintering. The synthesis temperature was up to 1400 °C. The morphology, chemical composition, crystal structure, magnetic, and electrodynamic properties were studied and compared with pure barium hexaferrite BaFe12O19 matrix. The polysubstituted high-entropy single-phase product contains five doping elements at a high concentration level. According to the EDX data, the new compound has a formula of Ba(Fe6Ga1.25In1.17Ti1.21Cr1.22Co1.15)O19. The calculated cell parameter values were a = 5.9253(5) Å, c = 23.5257(22) Å, and V = 715.32(9) ų. The increase in the unit cell for the substituted sample was expected due to the different ionic radius of Ti/In/Ga/Cr/Co compared with Fe3+. The electrodynamic measurements were performed. The dielectric and magnetic permeabilities were stable in the frequency range from 2 to 12 GHz. In this frequency range, the dielectric and magnetic losses were -0.2/0.2. Due to these electrodynamic parameters, this material can be used in the design of microwave strip devices.

Structure, Mechanical and Thermal Properties of Polyphenylene Sulfide and Polysulfone Impregnated Carbon Fiber Composites.

The paper studies new high-temperature thermoplastic impregnated unidirectional carbon fiber composites. The research focuses on the effect of thermal and chemical oxidation of the carbon fibers surface on the interfacial interaction between fibers and polysulfone and polyphenylene sulfide as well as thermal and mechanical properties of the composites. The research reveals the interaction between carbon fibers and the polymer matrix depend both on the type of surface treatment and nature of the polymer. The chemical oxidation of carbon fibers results in good interfacial interaction, and the best mechanical properties were observed for tows impregnated with polyphenylene sulfide.

Structure and Properties of Polysulfone Filled with Modified Twill Weave Carbon Fabrics.

Carbon fabrics are widely used in polymer based composites. Nowadays, most of the advanced high-performance composites are based on thermosetting polymer matrices such as epoxy resin. Thermoplastics have received high attention as polymer matrices due to their low curing duration, high chemical resistance, high recyclability, and mass production capability in comparison with thermosetting polymers. In this paper, we suggest thermoplastic based composite materials reinforced with carbon fibers. Composites based on polysulfone reinforced with carbon fabrics using polymer solvent impregnation were studied. It is well known that despite the excellent mechanical properties, carbon fibers possess poor wettability and adhesion to polymers because of the fiber surface chemical inertness and smoothness. Therefore, to improve the fiber-matrix interfacial interaction, the surface modification of the carbon fibers by thermal oxidation was used. It was shown that the surface modification resulted in a noticeable change in the functional composition of the carbon fibers' surface and increased the mechanical properties of the polysulfone based composites. Significant increase in composites mechanical properties and thermal stability as a result of carbon fiber surface modification was observed.

Why are reactions of 2- and 8-thioquinoline derivatives with iodine different?

The crystal structures of 1,2-dihydro-1,1'-bi[thiazolo[3,2-a]quinoline]-10a,10a'-diium diiodide hemihydrate, C22H16N2S22+·2I-·0.5H2O, and 1,2-dihydro-1,1'-bi[thiazolo[3,2-a]quinoline]-10a,10a'-diium iodide triiodide, C22H16N2S22+·I-·I3-, obtained during the reaction of 1,4-bis(quinolin-2-ylsulfanyl)but-2-yne (2TQB) with iodine, have been determined at 120 K. The crystalline products contain the dication as a result of the reaction proceeding along the iodocyclization pathway. This is fundamentally different from the previously observed reaction of 1,4-bis(quinolin-8-ylsulfanyl)but-2-yne (8TQB) with iodine under similar conditions. A comparative analysis of the possible conformational states indicates differences in the relative stabilities and free rotation for the 2- and 8-thioquinoline derivatives which lead to a disparity in the convergence of the potential reaction centres for 2TQB and 8TQB.

Influence of Powder Characteristics on Processability of AlSi12 Alloy Fabricated by Selective Laser Melting.

Selective laser melting (SLM) is one of the additive manufacturing technologies that allows for the production of parts with complex shapes from either powder feedstock or from wires. Aluminum alloys have a great potential for use in SLM especially in automotive and aerospace fields. This paper studies the influence of starting powder characteristics on the processability of SLM fabricated AlSi12 alloy. Three different batches of gas atomized powders from different manufacturers were processed by SLM. The powders differ in particle size and its distribution, morphology and chemical composition. Cubic specimens (10 mm × 10 mm × 10 mm) were fabricated by SLM from the three different powder batches using optimized process parameters. The fabrication conditions were kept similar for the three powder batches. The influence of powder characteristics on porosity and microstructure of the obtained specimens were studied in detail. The SLM samples produced from the three different powder batches do not show any significant variations in their structural aspects. However, the microstructural aspects differ and the amount of porosity in these three specimens vary significantly. It shows that both the flowability of the powder and the apparent density have an influential role on the processability of AlSi12 SLM samples.

Magnetic and Structural Properties of Barium Hexaferrite BaFe12O19 from Various Growth Techniques.

Barium hexaferrite powder samples with grains in the µm-range were obtained from solid-state sintering, and crystals with sizes up to 5 mm grown from PbO, Na2CO3, and BaB2O4 fluxes, respectively. Carbonate and borate fluxes provide the largest and structurally best crystals at significantly lower growth temperatures of 1533 K compared to flux-free synthesis (1623 K). The maximum synthesis temperature can be further reduced by the application of PbO-containing fluxes (down to 1223 K upon use of 80 at % PbO), however, Pb-substituted crystals Ba1-xPbxFe12O19 with Pb contents in the range of 0.23(2) ≤ x ≤ 0.80(2) form, depending on growth temperature and flux PbO content. The degree of Pb-substitution has only a minor influence on unit cell and magnetic parameters, although the values for Curie temperature, saturation magnetization, as well as the coercivity of these samples are significantly reduced in comparison with those from samples obtained from the other fluxes. Due to the lowest level of impurities, the samples from carbonate flux show superior quality compared to materials obtained using other methods.

Three Oxidation States of Manganese in the Barium Hexaferrite BaFe12-xMnxO19.

The coexistence of three valence states of Mn ions, namely, +2, +3, and +4, in substituted magnetoplumbite-type BaFe12-xMnxO19 was observed by soft X-ray absorption spectroscopy at the Mn-L2,3 edge. We infer that the occurrence of multiple valence states of Mn situated in the pristine purely iron(III) compound BaFe12O19 is made possible by the fact that the charge disproportionation of Mn3+ into Mn2+ and Mn4+ requires less energy than that of Fe3+ into Fe2+ and Fe4+, related to the smaller effective Coulomb interaction of Mn3+ (d4) compared to Fe3+ (d5). The different chemical environments determine the location of the differently charged ions: with Mn3+ occupying positions with (distorted) octahedral local symmetry, Mn4+ ions prefer octahedrally coordinated sites in order to optimize their covalent bonding. Larger and more ionic bonded Mn2+ ions with a spherical charge distribution accumulate at tetrahedrally coordinated sites. Simulations of the experimental Mn-L2,3 XAS spectra of two different samples with x = 1.5 and x = 1.7 led to Mn2+:Mn3+:Mn4+ atomic ratios of 0.16:0.51:0.33 and 0.19:0.57:0.24.