Mechanochemical processes with the reaction-induced mechanical activation. Chemo-mechanochemical effect

The review addresses the special case of mechanical activation of solid-state chemical reactions when the stress field, strain, and defects in crystals are induced by the chemical reaction itself rather than by the external mechanical impact (chemo-mechanochemical (CMC) effect). This review presents the analysis and state-of-the-art of research activities in this area. Different cases of the CMC effect in homogeneous and heterogeneous systems are considered: with or without changes in the chemical composition, with or without formation of solid products, etc.     

Physicochemical processes in the nonequilibrium plasma-polymer system

The results of investigation into interaction between nonequilibrium plasma and polymers, including the mechanism of generation of active species in a direct-current discharge in oxygen, air, and oxygen mixtures with argon, are reported, and the formation behavior of gaseous products of the reactions of these species with polymer is discussed. The influence of the gaseous products on the physical characteristics of plasma and the rates of the processes involving electrons is considered.     

Physicochemical principles for developing new materials based on silicate dispersed minerals

We consider the physicochemical principles for obtaining effective new sorbents, catalysts, supports, and fillers made from natural dispersed minerals using heat treatment, modification by inorganic and organic compounds, stratification of carbon layers, introduction of inorganic and organic oligomers and polymers into the structure of the minerals. We discuss the properties and practical use of the new materials.     

Mechanochemical activation of minerals on the cordierite synthesis

The cordierite is commonly prepared by reaction of talc, clay and gibbsite within the range of 1200-1350 °C. This study deals with the effect of the amorphization by grinding of that mixture and its influence on the cordierite formation.The mixture previously mentioned underwent six different treatments: mixing without grinding (A) (only mixing); non-amorphizing grinding (A_M) and amorphizing grinding in oscillating mill at four different times (H samples). The phases formed by thermal treatment were studied using differential thermal analysis (DTA)-thermogravimetric analysis (TG)-DTG, dilatometries and X-ray diffraction (XRD) techniques in certain combinations.The thermal analysis of the A and A_M series were compared and they do not show significant differences, whereas the H samples present remarkable alterations in the DTA peaks as well as in the weight losses (TG). Thus, a great number of DTA peaks tend to decrease the temperature of the maximum and to lower the intensity as the amorphization time increases.Calcination tests performed within the range 900-1200 °C show important differences in the diffractograms obtained from the intermediate products. While at 1350 °C the A and H samples reach the same final phases, within the range 1200-1360 °C they present important differences in the DTA indicating that the sequence and direction of reaction are different. The same behavior can be observed by dilatometric analysis.     

Nature and philosophy of thermal processes in minerals and inorganic materials

Solid-state thermal processes have their own specificity, distinguishing them from the processes in gases and liquids. This specificity includes, among others, their limited reversibility and the limited or modified role of chemical affinity as the main driving force indicating the direction of real solid-state processes. The consequency is the formation of metastable compounds or phases during heating, as intermediate steps towards the state of thermodynamic equilibrium. They are a results of the particular properties of the rigid internal structure of minerals and materials as the thermal reaction medium. The peculiarities of thermal reactions of solids are presented on the example of those of oxides (silicates and borates) with polymeric structures. The significance of crystal-chemical factors for the prediction or explanation of the course of high-temperature processes, as complementing the thermodynamic factors, is discussed.Dedicated to Dr. Robert Mackenzie on the occasion of his 75th birthdayThis work was supported by grant P040703406 from the National Committee of Scientific Research of Poland.     

Physicochemical investigation of anodic processes involved in silver electrowinning in refining technology

During silver electrowinning in refining technology, irrespectively of the nature of electrolyte and anode material, an anode deposit is formed due to oxidation of singly charged silver ions to higher degrees of oxidation (+2 and +3) under polarization. Absorption spectra of Ag(II) have been obtained in solutions with various concentrations of silver ions and nitric acid using anodic polarization in combination with electronic absorption spectroscopy; silver ions of high oxidation degrees were found to be unstable in solutions. At anode potentials φ_a ≥ 1.15–1.22 V, Ag(I) ions in liquid phase are oxidized to Ag(II), which paint the anolyte; their content depends on silver and nitric acid concentrations in the electrolyte. The deposit crystallizes on anode at potential φ_a ≈ 1.5 V. Chemical analysis, X-ray powder diffraction, and a thermogravimetric study of the anode deposit have made it possible to identify its initial composition as Ag₇O₈NO₃. The deposit composition varies in time as a result of reduction of highly oxidized silver.     

Structures and thermochemistry of calcium-containing molecules

A variety of theoretical procedures, including the high-level ab initio methods G3, G3[CC](dir,full), and W2C//ACQ, have been used to predict the structures and heats of formation of several small calcium-containing molecules (CaH, CaH2, CaO, CaOH, Ca(OH)2, CaF, CaF2, CaS, CaCl, and CaCl2). B3-LYP and CCSD(T) with both the (aug-)cc-pWCVQZ and (aug-)cc-pWCVQ+dZ basis sets are found to give molecular geometries that agree well with the experimental results. The CCSD(T)(riv)/(aug-)cc-pWCVQ+dZ results are found to be the most accurate, with a mean absolute deviation from experiment of just 0.008 angstroms. Zero-point vibrational energies (ZPVEs) and thermochemical corrections are found to be relatively insensitive to the level of theory, except in the case of molecules with highly anharmonic calcium-centered bending modes (CaH2, Ca(OH)2, CaF2, CaCl2), where special procedures need to be employed in order to obtain satisfactory results. Several potential improvements to the W2C method were investigated, most of which do not produce significant changes in the heats of formation. It was observed, however, that for CaO and CaS the scalar relativistic corrections are unexpectedly large and highly basis set dependent. In these cases, Douglas-Kroll CCSD(T)/(aug-)cc-pWCV5Z calculations appear to give a converged result. The G3[CC](dir,full) and best W2C-type heats of formation are both found generally to agree well with experimental values recommended in recent critical compendia. However, in some cases (CaO, Ca(OH)2, and CaF2), they differ from one another by more than their predicted error margins. The available experimental data are not sufficiently precise to distinguish definitively between the two sets of results although, in general, when discrepancies exist the W2C heats of formation are lower in energy and tend to be in better agreement with experiment. In the case of CaO, the W2C heat of formation (20.7 kJ mol(-1)) is approximately 20 kJ mol(-1) lower than the G3[CC](dir, full) result and most of the experimental data. Extensive investigation of possible refinements of the W2C method has failed to reveal any weaknesses that could account for this discrepancy. We therefore believe that the heat of formation of CaO is likely to lie closer to the more recent direct experimental determination of 27 kJ mol(-1) than to the value of approximately 40 kJ mol(-1) recommended in recent thermochemical reviews.     

不同活化方法对天然硅铝矿物活化及分子筛合成效果的影响

选取了高岭土、累托土、蒙脱土和伊利石四种天然硅铝矿物,采用热活化、碱熔活化、亚熔盐活化及拟固相活化四种方法对上述四种矿物分别进行活化,对比了不同活化方法对天然硅铝矿物活化效果的影响。结果表明,亚熔盐活化及拟固相活化都具有良好的活化效果,而且能耗较低,明显优于热活化和碱熔活化。其中,拟固相活化由于能耗更低且更有利于实现工业操作,因此,是最具发展前景的天然硅铝矿物活化方法。对比四种天然硅铝矿物,高岭土、累托土及蒙脱土的晶相结构更容易被解聚,而伊利石稳定性更高,经亚熔盐活化及拟固相活化后,活化产物中也只有极少量的高反应活性的硅、铝物种,因此,伊利石不是理想的分子筛合成原料。     

Depicting the dehydration and dehydroxylation processes in very rare hydrogen arsenate minerals

Journal of Thermal Analysis and Calorimetry - The work represents a pioneering attempt to couple TG analysis and hot-stage t-ATR-FTIR spectroscopy to describe the dehydration and dehydroxylation...     

Mechanochemistry and mechanical activation of solids

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2228–2245, October, 1990.     

Single-crystal trace element analysis in rock-forming minerals by instrumental neutron activation analysis

We have developed an INAA techniques for analyzing single crystals extracted from rocks. Trace element contents have been measured in a large variety of mineral species, as well as isotopic ratios of some REE in minerals related to natural fission reactions. The sensitivity of INAA allows to avoid the main shortcomings of usual mineral geochemistry: (1) only very short quantities of minerals are needed (down to a few g), so that even very sparse minerals could be analyzed, (2) purity of minerals is carefully checked, and (3) the heterogeneity of a population may be studied. The method is especially useful when applied to minerals acting as tracers for some element families, e.g. REE in Ca-bearing minerals (fluorite, apatite, titanite, gamet) and Zr-bearing minerals, or chalcophile elements (Co, Ni, As, Sb, Mo, Ag, Au and Se) in sulfides. We present an application of the method to the Oklo U deposit in Gabon showing that features outlined above are of special interest for the study of hydrothermal processes.     

Physicochemical characterization of the retardation of aqueous Cs+ ions by natural kaolinite and clinoptilolite minerals

The aim of this study was to carry out kinetic, thermodynamic, and surface characterization of the sorption of Cs+ ions on natural minerals of kaolinite and clinoptilolite. The results showed that sorption followed pseudo-second-order kinetics. The activation energies were 9.5 and 13.9 kJ/mol for Cs+ sorption on kaolinite and clinoptilolite, respectively. Experiments performed at four different initial concentrations of the ion revealed that the percentage sorption of Cs+ on clinoptilolite ranged from 90 to 95, compared to 28 to 40 for the kaolinite case. At the end of a 1 week period, the percentage of Cs+ desorption from clinoptilolite did not exceed 7%, while it amounted to more than 30% in kaolinite, indicating more stable fixation by clinoptilolite. The sorption data were best described using Freundlich and D-R isotherm models. Sorption showed spontaneous and exothermic behavior on both minerals, with deltaH(0) being -6.3 and -11.4 kJ/mol for Cs+ uptake by kaolinite and clinoptilolite, respectively. Expanding the kaolinite interlayer space from 0.71 to 1.12 nm using DMSO intercalation, did not yield a significant enhancement in the sorption capacity of kaolinite, indicating that the surface and edge sites of the clay are more energetically favored. EDS mapping and elemental analysis of the surface of kaolinite and clinoptilolite revealed more intense signals on the surface of the latter with an even distribution of sorbed Cs+ onto the surfaces of both minerals.     

Microwave activation of catalysts and catalytic processes

The results obtained by using microwave activation in catalytic processes such as the conversion of lower alkanes, the removal of volatile organic compounds and sulfur- and nitrogen-containing compounds from air, and the hydrogenation of aromatic compounds and dehydrogenation of naphthenes are discusses.     

Determination of europium in minerals and rocks by neutron activation and gammagamma-coincidence spectrometry

Neutron activation followed by gammagamma-coincidence measurements of 9-3 hr (152)Eu is shown to be a convenient method for routine determination of europium in minerals and rocks. In the concentration range 10-150 ppm the method is free of interference from other elements, and neutron shielding effects do not interfere seriously in the analysis. The precision of the method is about 5%.     

Physicochemical processes in polymer materials upon exposure at the MIR orbital space station

An overview of papers on the investigation of physicochemical processes occurring in polymer (polyimide, fluoropolymer, fluoropolyimide, unilaterally aluminized polyimide) films during long-term exposure at the Mir orbital space station is presented in the article dedicated to the centenary of the birthday of Professor S. Ya. Pshezhetskii. Anisotropic nano- and micro-structures oriented in the direction of motion of the station have been detected for the first time with the scanning electron microscopy and atomic force microscopy techniques on surfaces of films exposed to the effects of all factors of open space. The formation of anisotropic structures has been confirmed by the investigation of the light scattering circular diagrams and surface properties of the films. It is supposed that the formation of such structures results from collisions of a flux of oxygen atoms having an energy of ∼5 eV, with the outer surface of the films. It has been found with the use of electronic absorption and infrared spectroscopy that the changes in the surface and optical properties of the films are caused by the occurrence of oxidation processes, degradation of macromolecules, and opening of the imide cycles and aromatic rings of polyimide. Unilaterally aluminized polyimide films are the least resistant to the effects of outer space factors, what can be explained by the photoelectron mechanism of polymer destruction.     

The application of photon activation analysis for the characterization of uranium minerals

Instrumental photon activation analysis can be used advantageously for the homogeneity control and the determination of uranium concentration in minerals and ores to be certified as uranium reference materials. The homogeneity control of high contents of uranium can also be performed by passive gamma-ray spectrometry with high energy resolution. Interferences of²³⁷U characteristic lines with gamma-rays from other radionuclides produced in the 44 MeV bremsstrahlung are evaluated.     

Instrumental neutron activation analysis of monomineral fractions of sulfide minerals and quartzes

A method has been worked out of multi-elemental instrumental neutron-activation analysis INAA of small weights some mg of monomineral fractions of sulfide minerals pyrites, galenites, chalcopyrites, arsenopyrites, bornites, chalcosines and quartzes. The samples were irradiated in a nuclear reactor under a flux of 1.3·10¹³ n·cm⁻²·s⁻¹. For measuring the gamma radiation of the exposed samples Ge(Li) gamma-spectrometers with semiconductor detectors were used. Determined in sulfide monofractions were the elements: Co, Sc, Ag, Se, Sb, Cr, Fe, Zr; rare-earth elements: Ce, Sm, Eu and others at content levels of 10⁻¹−10⁻⁴%. In quartzes they were: Mn, Na, Sb, Cr, Sc, Fe, Co at content levels of 10⁻⁵−10⁻⁷% and Au to n×10⁻⁹%. A special method has been worked out for the determination of In in sulfides with the irradiation of samples in a cadmium screen. An example is cited of using the method for studying some peculiar features of the genetics of copper pyrite deposits. The data on the distribution of admixture elements in sulfide monofractions produced in this work made it possible to conclude that the oreformation in the deposits has a stage-by-stage character.     

Determination of Cu in minerals by 14-MeV neutron activation analysis and radiochemical separation

14-MeV neutron activation analysis /NAA/ and radiochemical separation technique were used for the determination of Cu in Hungarian minerals. The separation of Cu from other elements is a possibility to avoid the interferences in the 511 keV -line.     

Dehydrogenation processes via C-H activation within alkylphosphines

Phosphines are commonly used in organometallic chemistry and are present in a wide variety of catalytic systems. This feature article highlights the advances made in dehydrogenation processes occurring within alkylphosphines, with the aim of further developing catalytic processes involving C-H activation together with potential applications in the field of hydrogen storage.     

Preparation of ultrafine metal particles in processes of pulse mechanical action

Ultrafine metal particles (UFMP) (iron and cobalt) have been obtained in solid-state redox reactions of cyclopentadienyl--(3)-1,2-dicarbollyliron or cyclopentadienyl--(3)-1,2-dicarbollylcobalt with elemental sulfur ((C₅H₅)Fe³⁺(C₂B₉H₁₁)-S, (C₅H₅)Co⁵⁺C₂B₉H₁₁-S). These reactions are realized by the action of elastic wave (EW) pulses on powder compositions of these substances. Study of the UFMP obtained by the ferromagnetic resonance (FMR) method has shown that the sizes ofn · Co⁰ UFP lie in the range from 1 to 13 nm. UFP of cobalt and iron are also formed under the action of EW on samples containing (C₅H₅)Fe³⁺(C₂B₉H₁₁)-S or (C₅H₅)Co³⁺(C₂B₉H₁₁)-S within the film of tetrafluoroethylene and perfluoro-4-methyl-3,6-dioxaoct-7-ene-1-sulfonyl fluoride copolymer (CP). It is shown by the FMR method that FMR lines broaden on going from powder systems to systems containing CP films. It is supposed thatn · Co⁰ and n · Fe⁰ particles interact with polymeric matrices in the course of formation and stabilization of UFMP in the matrices.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2355–2358, December, 1995.This work was financially supported by the Russian Foundation for Basic Research (Project No. 94-03-09632).