Platinum-Group Minerals of Pt-Placer Deposits Associated with the Svetloborsky Ural-Alaskan Type Massif, Middle Urals, Russia

The alteration of platinum group minerals (PGM) of eluval, proximal, and distal placers associated with the Ural-Alaskan type clinopyroxenite-dunite massifs were studied. The Isovsko-Turinskaya placer system is unique regarding its size, and was chosen as research object as it is PGM-bearing for more than 70 km from its lode source, the Ural-Alaskan type Svetloborsky massif, Middle Urals. Lode chromite-platinum ore zones located in the Southern part of the dunite “core„ of the Svetloborsky massif are considered as the PGM lode source. For the studies, PGM concentrates were prepared from the heavy concentrates which were sampled at different distances from the lode source. Eluvial placers are situated directly above the ore zones, and the PGM transport distance does not exceed 10 m. Travyanistyi proximal placer is considered as an example of alluvial ravine placer with the PGM transport distance from 0.5 to 2.5 km. The Glubokinskoe distal placer located in the vicinity of the Is settlement are chosen as the object with the longest PGM transport distance (30⁻35 km from the lode source). Pt-Fe alloys, and in particular, isoferroplatinum prevail in the lode ores and placers with different PGM transport distance. In some cases, isoferroplatinum is substituted by tetraferroplatinum and tulameenite in the grain marginal parts. Os-Ir-(Ru) alloys, erlichmanite, laurite, kashinite, bowieite, and Ir-Rh thiospinels are found as inclusions in Pt-Fe minerals. As a result of the study, it was found that the greatest contribution to the formation of the placer objects is made by the erosion of chromite-platinum mineralized zones in dunites. At a distance of more than 10 km, the degree of PGM mechanical attrition becomes significant, and the morphological features, characteristic of lode platinum, are practically not preserved. One of the signs of the significant PGM transport distance in the placers is the absence of rims composed of the tetraferroplatinum group minerals around primary Pt-Fez alloys. The sie of the nuggets decreases with the increasing transport distance. The composition of isoferroplatinum from the placers and lode chromite-platinum ore zones are geochemically similar

Ultramicroporous Polyphenylenes via Diels–Alder Polycondensation Approach

Development of new microporous organic polymers attracts significant attention due to a wide scope of promising applications. In addition, the synthesis of soluble, non-crosslinking polymers of high surface area and uniform microporosity is very challenging, and the methods for soluble microporous polymers formation are rather limited. In this work, we report a new approach to construct porous polyphenylenes which employs the Diels–Alder polycondensation of multifunctional ethynyl-containing monomers of different spatial architecture with bis(cyclopentadienone)s. The resulting polymers were soluble in common organic solvents, and their structure and properties were assessed by NMR, TGA, DSC, and SEC studies. The polymers demonstrated a specific surface area up to 751 m2·g−1 and ultramicroporous (pore size ≤ 0.6 nm) structure. N2 and CO2 adsorption–desorption data revealed that porosity parameters, e.g., specific surface area and pore sizes, can be tuned selectively by varying the type of monomers and reaction conditions

Polydimethylsiloxanes with Grafted Dibenzoylmethanatoboron Difluoride: Synthesis and Properties

A method for the preparation of polydimethylsiloxanes with grafted methoxy-substituted dibenzoylmethanatoboron difluoride has been described. The structures of prepared polymers were confirmed using NMR, IR spectroscopy and gel permeation chromatography methods. Their thermal properties were investigated using thermal gravimetric analysis, differential scanning calorimetry and thermomechanical analysis. The prepared polymers had good thermal (Td5% up to 393 °C) and thermo-oxidative (Td5% = 413 °C) stability. The polymers started to transit in a viscous flow state at about 40 °C (for 3 a) and at about 20 °C (for 3 b). The viscoelastic characteristics of prepared polymers were determined in the sinusoidal oscillating vibrations mode. It was shown that the studied polymers at low frequencies at room temperature are viscoelastic fluids (G′ < G″). Increasing the frequency led to inversion (crossover) of dependences G′ and G″, which indicated the transition of polymers from viscous to elastomeric behavior characteristics, and the beginning of the formation of a physical network. Optical properties were studied using electron absorption, steady-state and time-resolved fluorescence spectroscopy. It was shown that intramolecular H-dimers exist in the ground state. The polymers studied had a bright fluorescence in the solution and in the solid state, consisting of bands of monomer and excimer emission. Thermally-activated delayed fluorescence was observed in the solution and the solid state. The prepared polymers possess intriguing properties that make them useful as optical materials, sensors or imaging agents

Synthesis of Aromatic Polyimides Based on 3,4&prime;-Oxydianiline by One-Pot Polycondensation in Molten Benzoic Acid and Their Application as Membrane Materials for Pervaporation

A series of aromatic polyimides based on the asymmetrical diamine 3,4&#884;-oxydianiline and various tetracarboxylic acid dianhydrides, both &ldquo;rigid&rdquo; and &ldquo;flexible&rdquo; structure, have been synthesized using the original method of one-pot high-temperature catalytic polycondensation in molten benzoic acid. The synthesized polyimides were investigated using fourier-transform infrared (FTIR) and 1H NMR spectroscopy, gel permeation chromatography (GPC), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), thermomechanical analysis (TMA) and wide-angle X-ray scattering (WAXS). It was found that the synthesized polyimides, depending on the used dianhydride, are characterized by different solubility in organic solvent and molten benzoic acid, molecular weight, glass transition temperature (Tg) from 198 to 270 &deg;C, an amorphous or semi crystalline structure with the degree of crystallinity from 41 to 52%. The influence of the method of synthesis on the formation of the crystalline phase of polyimides was studied, and the obtained results were compared with the literature data. The effect of dianhydride chemical structure on the performance of polyimide in pervaporation more specifically, dehydratation of azeotropic isopropanol solution was investigated and compared with the commercially available polyetherimide Ultem 1000&trade;. Membrane structure was studied using scanning electron microscopy. It was found that polyimide PI-DA is the most effective for separation of 88 wt.% isopropanol/12 wt.% water mixture compared to the polyimide PI-6FDA and commercial polyetherimide Ultem 1000&trade; demonstrating normalized permeation flux of 2.77 kg &micro;m m&minus;2 h&minus;1 and separation factor of 264 (water content in permeate 97 wt.%)

Phase Evolution from Volborthite, Cu3(V2O7)(OH)2&middot;2H2O, upon Heat Treatment

In the experiments on volborthite in situ and ex situ heating, analogues of all known natural anhydrous copper vanadates have been obtained: ziesite, pseudolyonsite, mcbirneyite, fingerite, stoiberite and blossite, with the exception of borisenkoite, which requires the presence of As in the V site. The evolution of Cu-V minerals during in situ heating is as follows: volborthite Cu3(V2O7)(OH)2&middot;2H2O (30&ndash;230 &deg;C) &rarr; X-ray amorphous phase (230&ndash;290 &deg;C) &rarr; ziesite &beta;-Cu2(V2O7) (290&ndash;430 &deg;C) &rarr; ziesite + pseudolyonsite &alpha;-Cu3(VO4)2 + mcbirneyite &beta;-Cu3(VO4)2 (430&ndash;510 &deg;C) &rarr; mcbirneyite (510&ndash;750 &deg;C). This trend of mineral evolution agrees with the thermal analytical data. These phases also dominate in all experiments with an ex situ annealing. However, the phase compositions of the samples annealed ex situ are more complex: fingerite Cu11(VO4)6O2 occurs in the samples annealed at ~250 and ~480 &deg;C and quickly or slowly cooled to room temperature, and in the sample annealed at ~850 &deg;C with fast cooling. At the same time, blossite and stoiberite have been found in the samples annealed at ~480&ndash;780 and ~780&ndash;850 &deg;C, respectively, and slowly cooled to room temperature. There is a trend of decreasing crystal structure complexity in the raw phases obtained by the in situ heating with the increasing temperature: volborthite &rarr; ziesite &rarr; mcbirneyite (except of pseudolyonsite). Another tendency is that the longer the sample is cooled, the more complex the crystal structure that is formed, with the exception of blossite, most probably because blossite and ziesite are polymorphs with identical crystal structure complexities. The high complexity of fingerite and stoiberite, as well as their distinction by Cu:V ratio, may explain the uncertain conditions of their formation

Phase Evolution from Volborthite, Cu₃(V₂O₇)(OH)₂·2H₂O, upon Heat Treatment

In the experiments on volborthite in situ and ex situ heating, analogues of all known natural anhydrous copper vanadates have been obtained: ziesite, pseudolyonsite, mcbirneyite, fingerite, stoiberite and blossite, with the exception of borisenkoite, which requires the presence of As in the V site. The evolution of Cu-V minerals during in situ heating is as follows: volborthite Cu3(V2O7)(OH)2·2H2O (30–230 °C) → X-ray amorphous phase (230–290 °C) → ziesite β-Cu2(V2O7) (290–430 °C) → ziesite + pseudolyonsite α-Cu3(VO4)2 + mcbirneyite β-Cu3(VO4)2 (430–510 °C) → mcbirneyite (510–750 °C). This trend of mineral evolution agrees with the thermal analytical data. These phases also dominate in all experiments with an ex situ annealing. However, the phase compositions of the samples annealed ex situ are more complex: fingerite Cu11(VO4)6O2 occurs in the samples annealed at ~250 and ~480 °C and quickly or slowly cooled to room temperature, and in the sample annealed at ~850 °C with fast cooling. At the same time, blossite and stoiberite have been found in the samples annealed at ~480–780 and ~780–850 °C, respectively, and slowly cooled to room temperature. There is a trend of decreasing crystal structure complexity in the raw phases obtained by the in situ heating with the increasing temperature: volborthite → ziesite → mcbirneyite (except of pseudolyonsite). Another tendency is that the longer the sample is cooled, the more complex the crystal structure that is formed, with the exception of blossite, most probably because blossite and ziesite are polymorphs with identical crystal structure complexities. The high complexity of fingerite and stoiberite, as well as their distinction by Cu:V ratio, may explain the uncertain conditions of their formation