Electrically conductive silicon carbide with the addition of TiNbC

The work deals with the preparation of dense SiC based ceramics with high electrical conductivity. SiC samples with different content of conductive TiNbSiCO based phase were hot pressed at 1820 °C for 1 h in Ar atmosphere under mechanical pressure of 30 MPa. The conductive phase is a mixture of 50 wt% TiNbC (molar ratio of Ti/NbC is 1:1.8) and 50 wt% eutectic composition of Y₂O₃SiO₂. Composite with 30% of conductive TiNbSiCO phase showed the highest electrical conductivity 28.4 S mm^?1, while the good mechanical properties of SiC matrix were preserved (fracture toughness K_IC = 5.4 MPa m^1/2 and Vickers hardness 17.8 GPa).The obtained results show that the developed additive system is suitable for the preparation of SiC-based composite with sufficient electrical conductivity for electric discharge machining.     

Preparation of high-temperature stable SiBCN fibers from tailored single source polyborosilazanes

Bulk SiBCN ceramics derived from polyborosilazanes of the type [B(C₂H₄SiRNH)₃]_n (1a, R = CH₃; 2a, R = H; C₂H₄ = CHCH₃, CH₂CH₂) exhibit an exceptional structural stability at high temperature. Therefore, such quaternary systems are of great scientific and technical interest as fibrous reinforcements intended for high-temperature applications. In this context, the design of novel polyborosilazanes, which display properties tailored for the preparation of SiBCN fibers, is studied. Boron-modified polysilazanes of the type [B(C₂H₄SiRNCH₃)₃]_n (1b, R = CH₃; 2b, R = H) are prepared via aminolysis of the tris(dichlorosilylethyl)boranes B(C₂H₄SiRCl₂)₃ (1, R = CH₃; 2, R = H). It is shown that the functionalisation of the precursors with NCH₃ units improves their processability (i.e. solubility) compared to that of their ammonolysed analogs [B(C₂H₄SiRNH)₃]_n (1a, R = CH₃; 2a, R = H). In addition to the influence of the NCH₃ units, the presence of the SiCH₃ functions in such polymers offers the best potential for the preparation of fibers by melt-spinning. As-spun fibers are then converted under controlled atmosphere into high-temperature stable SiBCN fibers according to the polymer-derived ceramic route.     

The effect of density functional and dispersion interaction on structure and bonding analysis of uranium(VI) nitride complex [NU{N(CH2CH2NSiMe3)3}]: A theoretical study

Geometry and bonding energy analysis of uranium(VI) nitride complex [NU{N(CH₂CH₂NSiMe₃)₃}] were investigated with the DFT, DFT-D3 and DFT-D3(BJ) methods using density functionals (BLYP, BP86, PW91, PBE, revPBE and TPSS). The BLYP functional yields a UN bond distance of 1.788 Å for the model complex [NU{N(CH₂CH₂NSiMe₃)₃}] which is in close agreement with the experimental value of the UN bond distance of 1.799(7) Å for [NU{N(CH₂CH₂NSiⁱPr₃)₃}]. The calculated Mayer bond order (2.95) and Gopinathan–Jug bond order (3.18) indicate that the UN bond in this complex is essentially UN triple bonds. The electrostatic interaction is significantly smaller than the covalent bonding. The bond dissociation energy (BDE) is largest for the functional PBE and smallest for the functional TPSS. The DFT-D3 dispersion corrections are 5.3 kcal/mol (BLYP) and 5.0 kcal/mol (TPSS).     

Preparation and characterization of carboximidate iron(II) complexes

The reactions of C₅H₄NCHNNHC(O)Ph (1) with Fe(II) chloride gave [Fe₂(C₅H₄NC(OEt)NNHC(O)Ph)₂(μ-OEt)₂Cl₂]) (2) in ethanol and [Fe₂(C₅H₄NC(OMe)NNHC(O)Ph)₂(μ-OMe)₂Cl₂] (3) in methanol as well as [Fe(C₅H₄NCHNNHC(O)Ph)Cl₂] (4) in tetrahydrofuran, respectively. The X-ray diffraction analysis reveals their structures and complex 4 is proposed as an intermediate of formation of complexes 2 and 3.     

Infrared spectroscopy of some carbon-based materials relevant in combustion: Qualitative and quantitative analysis of hydrogen

A detailed procedure for the quantitative analysis of aromatic and aliphatic hydrogen based on infrared spectroscopy was set up and implemented on some carbon-based materials produced from organic precursors (naphthalene pitch) and/or relevant in combustion field (asphaltenes, carbon particulate matter, carbon black), spanning in the H/C atomic ratio range from 0.1 to 1. The quantitative FT-IR analysis involved the spectral deconvolution in the CH vibrations regions and the calibration factors of diverse standard species having spectral characteristics suitable for the detailed peak-to-peak analysis of the CH stretching (3100–2800 cm⁻¹) and aromatic CH bending (900–700 cm⁻¹) regions. The good agreement between the H/C atomic ratio obtained by quantitative FT-IR analysis and elemental analysis showed a reasonable reliability of the procedure. The major value of the developed FT-IR quantitative technique relies also on the capacity of discriminating between the different kinds of aliphatic and aromatic hydrogen. The quantitative and detailed analysis of hydrogen in form of CH₃, CH₂ and CH groups and in form of solo, duo and trio/quatro aromatic hydrogens showed to be useful also for inferring the structure of the aromatic moieties constituting the CC backbone of carbon materials.     

Palladium (II) and platinum (II) complexes containing organometallic thiosemicarbazone ligands: Synthesis,characterization, X-ray structures and antitubercular evaluation

A new series of palladium (II) and platinum (II) complexes containing ferrocenyl and cyrhetrenyl thiosemicarbazone ligands were synthesized and characterized. The two-step reaction of the organometallic thiosemicarbazones with i) K₂MCl₄ and ii) PPh₃ and their subsequent recrystallization from CH₂Cl₂/hexane yielded the binuclear complexes [Mˋ{ML_n(η⁵-C₅H₄)C(H)NNC(S)NHR}–(Cl)(PPh₃)] (M′Pd, Pt; ML_nRe(CO)₃, FeCp; RH, CH₃). The structures of the products were inferred from elemental analyses and IR, ¹H and ³¹P NMR spectroscopies. The molecular structures of 2b and 3d were confirmed by single crystal X-ray analysis. All complexes were screened in vitro against Mycobacterium tuberculosis and exhibited only moderate activity in the low micromolar range.     

In situ synthesis of nano size silicon carbide and fabrication of CSiC composites during the siliconization process of mesocarbon microbeads preforms

CSiC composites with carbon-based mesocarbon microbeads (MCMBs) preforms are a new type of high-performance and high-temperature structural materials for aerospace applications. In the present study, MCMB-SiC composites were fabricated by liquid silicon infiltration (LSI). Physical and mechanical properties such as density, porosity and bending strength were measured before and after siliconization. The results show the CSiC composites have excellent bending strength, density and porosity of 210 MPa, 2.41 g/cm³ and 0.62%, respectively. The chemical analysis shows that the composite is composed of 89% SiC, 2% Si and 9% C. The microstructural results also show the existence of two different areas of SiC, one zone of coarse micron size SiC at SiCSi interface and the other zone consists of fine nano-SiC particles at SiCC interfaces. The formation mechanism governing the siliconization of porous MCMB preform was also investigated.     

Periodic,vdW-corrected density functional theory investigation of the effect of Al siting in H-ZSM-5 on chemisorption properties and site-specific acidity

Twelve crystallographically distinct Al substitution sites of H-ZSM-5 are modeled by periodic density functional theory using the vdW-DF functional. While the stability of Al substitution and Brønsted acid OH bond length at different active site positions are similar, the OH stretch frequency, SiOAl bond angle, and adsorption energies of various probe molecules differ notably without observable correlations between these properties. Comparison of adsorption energy values with and without van der Waals corrections demonstrates the significance of the inclusion of dispersion interactions. Our data indicate that theoretical investigations of H-ZSM-5 require a careful selection of the location of the active site.     

Towards osseointegration of bioinert ceramics: Can biological agents be immobilized on alumina substrates using self-assembled monolayer technique?

Immobilization of biological agents on inert alumina surfaces could promote bone growth and improve osseointegration. We hypothesize that functional groups on alumina surfaces can be used to link biological agents as a supporting factor e.g. for cell attachment. CH₂, OH, COOH, and NH₂ groups were linked to alumina surfaces using self-assembled monolayer technique (SAM). Subsequently, bovine serum albumin (BSA) was immobilized on each functionalized surface. Contact angle, bicinchoninic acid assay and immunofluorescence were used to detect immobilized BSA. The amount of BSA linked to functionalized surfaces increased in the following order CH₂ < OH < COOH = NH₂. The greatest amount, 26.1 μg/cm² of BSA was found on both, NH₂- and COOH-terminated surfaces. Cell tests confirmed cytocompatibility of all surfaces. The highest proliferation was detected on NH₂-terminated samples. Using the model protein, the results confirmed feasibility for immobilization of biological agents to inert alumina ceramic surfaces using SAM technique.     

Degradation of mechanical and electrical properties after long-term oxidation and corrosion of non-oxide structural ceramic composites

This work summarizes the results related to the influence of the starting composition and of microstructure on properties degradation, due to oxidation and corrosion, relatively to the following structural ceramics: Si₃N₄TiN, Si₃N₄MoSi₂, AlNSiCMoSi₂, AlNSiC.The effects of: (i) long-term oxidation in air (100 h), in the temperature range 600–1500 °C and (ii) of long-term corrosion (400 h) in acid or basic aqueous solution at RT, 40 and 70 °C, on the electrical resistivity and mechanical strength of the composites are analysed and compared. The degradation of the properties are related to the characteristics of the surface and sub-surface damage after oxidation and corrosion treatments.     

Growth of junctions in 3D carbon nanotube-graphene nanostructures: A quantum mechanical molecular dynamic study

Junctions are the key component for 3D CNT-graphene seamless hybrid nanostructures attractive for numerous innovative applications. Growth mechanism of junctions of vertical carbon nanotubes (CNTs) growing from graphene in the presence of iron nanoparticles as catalysts was simulated using quantum mechanical molecular dynamics methods. When nanotube grew on graphene via a “base-growth” mechanism, it was found that the junctions were a mixture of CC and FeC covalent bonds. We further explored the formation mechanisms of pure CC bonded junctions by moving the catalyst during CNT growth or etching and annealing after growth. Our simulations provided possible avenues to produce pure CC bonded junctions that seamlessly connect graphene and nanotubes in the 3D nanostructures.     

Investigation of bifurcated hydrogen bonds within the thermotropic liquid crystalline polyurethanes

The polyurethanes are synthesized from the biphenyl-4,4′-diol (mesogenic biphenol) and 1,3-Bis(isocyanatomethyl) cyclohexane, using (CH₂) of 2, 6 and 11 units as flexible alkylene spacer, respectively. FTIR detects the hydrogen bond in the thermotropic liquid crystalline polyurethane. FTIR spectra show a new CO absorption with lower wavenumber at around 1658 cm^?1 is assigned to “bifurcated” hydrogen bonded CO group—a CO with higher strength hydrogen bonds. The distributions of “bifurcated” hydrogen bonded CO are increased substantially along with increasing the flexible spacer length in polymer backbone. The “bifurcated” hydrogen bond existed not only at the temperature below T_g, but also existed at the temperature far higher than T_m and T_i. It almost is independent of temperature and exhibits a stable interaction (or strucuture) throughout a wide temperature range, differences from the normal liquid crystalline polyurethanes. It is worthy of predicting the thermotropic liquid crystalline polyurethane with “bifurcated” hydrogen bond would enhance its performances.     

Controlled grafting of cationic poly[(ar-vinylbenzyl)trimethylammonium chloride] on hydrogen-terminated silicon substrate by surface-initiated RAFT polymerization

Controlled grafting of well-defined cationic poly[(ar-vinylbenzyl)trimethylammonium chloride] [poly(VBTAC)] brushes on a hydrogen-terminated silicon substrate (SiH) was performed via surface-initiated RAFT polymerization. The azo-initiator was immobilized on the SiH surface via a three step process involving (i) coupling of the t-butyloxycarbonyl (t-BOC) protected allylamine to the SiH surface under UV irradiation, (ii) conversion of the t-BOC protected allylamine groups into the free amine groups by trifluoroacetic acid, and (iii) the amide reaction of allylamine with the 4,4′-azobis(4-cyanopentanoyl chloride) initiator. The living polymerization produced silicon substrate coated with well-defined cationic poly(VBTAC) with a target molecular weight and a grafting density as high as 0.93 chains/nm².     

Benzyne-functionalized graphene and graphite characterized by Raman spectroscopy and energy dispersive X-ray analysis

The benzyne functionalization of chemical vapor deposition grown large area graphene and graphite was performed using a mixture of o-trimethylsilylphenyl triflate and cesium fluoride that react with the carbon surface. The reaction requires at least 2 days of treatment before the appearance of Raman and energy-dispersive X-ray spectral signatures that verify modification. Raman spectra of modified graphene and graphite show a rich structure of lines corresponding to CCC, CH, and low frequency modes of surface-attached benzyne rings.     

Catalytic reactions of dioxygen with ethane and methane on platinum clusters: Mechanistic connections,site requirements,and consequences of chemisorbed oxygen

C₂H₆ reactions with O₂ only form CO₂ and H₂O on dispersed Pt clusters at 0.2–28 O₂/C₂H₆ reactant ratios and 723–913 K without detectable formation of partial oxidation products. Kinetic and isotopic data, measured under conditions of strict kinetic control, show that CH₄ and C₂H₆ reactions involve similar elementary steps and kinetic regimes. These kinetic regimes exhibit different rate equations, kinetic isotope effects and structure sensitivity, and transitions among regimes are dictated by the prevalent coverages of chemisorbed oxygen (O^*). At O₂/C₂H₆ ratios that lead to O^*-saturated surfaces, kinetically-relevant CH bond activation steps involve O^*O^* pairs and transition states with radical-like alkyls. As oxygen vacancies (¹) emerge with decreasing O₂/alkane ratios, alkyl groups at transition states are effectively stabilized by vacancy sites and CH bond activation occurs preferentially at O^** site pairs. Measured kinetic isotope effects and the catalytic consequences of Pt cluster size are consistent with a monotonic transition in the kinetically-relevant step from CH bond activation on O^*O^* site pairs, to CH bond activation on O^** site pairs, to O₂ dissociation on ^** site pairs as O^* coverage decrease for both C₂H₆ and CH₄ reactants. When CH bond activation limits rates, turnover rates increase with increasing Pt cluster size for both alkanes because coordinatively unsaturated corner and edge atoms prevalent in small clusters lead to more strongly-bound and less-reactive O^* species and lower densities of vacancy sites at nearly saturated cluster surfaces. In contrast, the highly exothermic and barrierless nature of O₂ activation steps on uncovered clusters leads to similar turnover rates on Pt clusters with 1.8–8.5 nm diameter when this step becomes kinetically-relevant at low O₂/alkane ratios. Turnover rates and the O₂/alkane ratios required for transitions among kinetic regimes differ significantly between CH₄ and C₂H₆ reactants, because of the different CH bond energies, strength of alkylO^* interactions, and O₂ consumption stoichiometries for these two molecules. Vacancies emerge at higher O₂/alkane ratios for C₂H₆ than for CH₄ reactants, because their weaker CH bonds lead to faster scavenging of O^* and to lower O^* coverages, which are set by the kinetic coupling between CH and OO activation steps. The elementary steps, kinetic regimes, and mechanistic analogies reported here for C₂H₆ and CH₄ reactions with O₂ are consistent with all rate and isotopic data, with their differences in CH bond energies and in alkyl binding, and with the catalytic consequences of surface coordination and cluster size. The rigorous mechanistic interpretation of these seemingly complex kinetic data and cluster size effects provides useful kinetic guidance for larger alkanes and other catalytic surfaces based on the thermodynamic properties of these molecules and on the effects of metal identity and surface coordination on oxygen binding and reactivity.     

Effects of potassium doping on CO hydrogenation over MoS2 catalysts: A first-principles investigation

The effects of potassium (K) doping on the reactivity of CO hydrogenation over MoS₂(100) catalysts are investigated using periodic density functional theory (DFT) calculations. The surface doped K species enhances the CO adsorption by providing both KO and KC bonding. DFT results show that K-doping promotes the CC coupling step forming the H₂CCO precursor that leads to the formation of mixed higher C_2 + oxygenates. Different reaction routes for CO hydrogenation on the Mo and the S edges over MoS₂(100) catalysts are identified.     

Structural relaxation of sputtered amorphous carbon nitride films during thermal annealing

A study of the stress relaxation caused by post-deposition thermal annealing of carbon nitride thin films (CN_x) deposited onto Si substrates has been carried out. The intrinsic stress values were correlated with Fourier transform spectrometer (FTIR) and thermal desorption mass spectroscopy (TDMS) results. FTIR spectra showed the existence of N–Csp³, NCsp² and C≡N triple bonds in the deposited films and indicates the occurrence of their porous character. The analysis of the spectra versus annealing temperature (T_A) reveals two rearrangement mechanisms of the microstructure. Up to 200 °C, the reversion of NCsp² to N–Csp³ and CCsp² respectively, and then an increase of the connectivity of the C–C network for higher T_A. These dissociation/recombination mechanisms are used to describe the stress release occurring within the (CN_x) films upon heating.     

Clean borrowing hydrogen methodology using hydrotalcite supported copper catalyst

The catalytic activity of Mg–Al hydrotalcite supported copper catalyst was investigated for clean CC and CN bond forming reactions using alcohols as alkylating agent via borrowing hydrogen methodology. The catalyst showed excellent conversion of ketone and amine substrates (71–99%) to alkylated products with high selectivity in alkylation reactions.     

Direct measurements of gas diffusivity in a washcoat layer under steady state conditions at ambient temperature

A method for directly measuring gas diffusivity in a washcoat layer was established by preparing a simulated washcoat layer and modifying a Wicke–Kallenbach type counter-current diffusion cell. Three pairs of gases, N₂Ar, CO₂Ar and C₃H₈Ar, were used in the measurements. It was found to be possible to evaluate the pore-transport parameters of the washcoat layer based on the mean transport pore model and the modified Stefan–Maxwell equation. Analysis of the gas diffusion mechanism in the washcoat layer showed that bulk and Knudsen diffusion took place simultaneously, and the percentage value of the contribution by Knudsen transport to net diffusion transport was evaluated.     

Crystalline MoVO based complex oxides as selective oxidation catalysts of propane

Three single crystalline MoVO based oxides, MoVO, MoVTeO and MoVTeNbO, all of which have the same orthorhombic layer-type structure with the particular arrangement of MO₆ (M = Mo, V, Nb) octahedra forming slabs with pentagonal, hexagonal, and heptagonal rings in (1 0 0) plane, were synthesized by hydrothermal method and their catalytic performance in the selective oxidation of propane to acrylic acid were compared in order to elucidate the roles of constituent elements and crystal structure in the course of the propane oxidation. It was observed that the rate of propane oxidation was almost the same over all three catalysts, revealing that Mo and V, which were indispensable elements for the structure formation, were responsible for the catalytic activity for propane oxidation. The Te-containing catalysts showed much higher selectivity to acrylic acid than the MoVO catalyst. Since propene was formed as a main product at low conversion levels over every catalyst, it can be concluded that Te located in the central position of the hexagonal ring promoted the conversion of intermediate propene effectively to acrylic acid. The catalyst with Nb occupying the same structural position of V clearly showed the improved selectively to acrylic acid particularly at high conversion region, because the further oxidation of acrylic acid to CO_x was greatly suppressed. These conclusions were further supported by the additional studies of the determination of activation energy and catalytic oxidations of intermediate products of the propane oxidation.