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.     

High Q dielectric resonator material with low dielectric constant for millimeter-wave applications

Al₂O₃TiO₂ ceramics has great promise as a dielectric resonator material for millimeter-wave use. The Al₂O₃TiO₂MnO system provides low dielectric constant and high quality factor (Q). TiO₂ and Al₂O₃ can compensate each other's temperature coefficient of resonant frequency. It is important to suppress the appearance of Al₂TiO₅ phase for obtaining high Q-value. In this study, dense Al₂O₃TiO₂ mixed ceramics without Al₂TiO₅ phase was synthesized by lowering the sintering temperature. The addition of MnO decreases the sintering temperature from 1400 to 1300 °C. In this temperature range, Al₂TiO₅ phase is hardly formed. X-ray powder diffraction (XRD) patterns show that the ceramics is composed of Al₂O₃ and TiO₂ phases only. Dense and well dispersed mixture of Al₂O₃ and TiO₂ grains is observed by scanning electron microscopy (SEM).The 0.9Al₂O₃0.1TiO₂ ceramics doped with 0.4 mol% of MnO has dielectric constant of 12.4, Q × f of 274,000 GHz at 76 GHz, and temperature coefficient of resonant frequency of +0.4 ppm/°C. The dielectric constant and the temperature coefficient of resonant frequency can be controlled by TiO₂ content. This ceramics is suitable for millimeter-wave applications because of its low dielectric constant, high Q-value, and small temperature coefficient of resonant frequency.     

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.     

Thermally stable pseudo-third-generation Grubbs ruthenium catalysts with pyridine–phosphinimine ligand

The ligand precursors 2-(R₃PN)CH₂Py (R = Ph(1a), Cy(2a)) were prepared from reaction of pyridine azide with various phosphine ligands. Reaction of 1a or 2a with RuCl₂(CHPh)(Py)₂(H₂IMes) (Py = pyridine) afforded the ruthenium alkylidene complex RuCl₂(CHPh)(PyCH₂(NPR₃))(H₂IMes) (R = Ph(1), Cy(2)). Both catalysts showed good thermal stability and latent behavior toward RCM and ROMP reactions.     

A novel approach for preparation of dense TiC–SiC nanocomposites by sol–gel infiltration and spark plasma sintering

Dense TiC–SiC nanocomposite ceramics were prepared by infiltration of porous TiC scaffolds with a SiOC sol, followed by spark plasma sintering (SPS). The porous nano TiC scaffold was first synthesized by direct carbothermal reduction of a monolithic TiOC precursor obtained from a controlled sol–gel process. The TiC scaffold was infiltrated with a SiOC sol and then the sample was aged in a container for 48 h at 80 °C to convert the sol into gel. After this, the sample was heated at 550 °C to remove the organic components and then 1350 °C to convert the SiOC gel to SiC by carbothermal reduction reaction. The cycle of the infiltration and carbothermal reduction was repeated several times to obtain relatively dense TiC–SiC composite samples. Dense TiC–SiC composite with a uniform nano-sized grain microstructure was obtained by spark plasma sintering at 1800 °C for 5 min under 40 MPa uniaxial pressure. Compared with conventional powder mixing methods, the sol–gel infiltration approach has shown distinct advantages of achieving dense TiC–SiC composites with uniform nano-sized grain structures.     

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.     

Direct conversion of citrus peel waste into hydroxymethylfurfural in ionic liquid by mediation of fluorinated metal catalysts

A new green technology was developed using citrus peel waste to produce hydroxymethylfurfual (HMF). FT-IR analysis of the waste showed 4 characteristic vibration modes (CH, CO, COH, and CO/COO^?), contributing to sugars. XRD and FESEM elucidated that the waste and its hydrolysate consist of highly amorphous clusters. HCl increased HMF yield by 1.4-fold. CrF₃ increased its yield by 1.7-fold. At 0.2 of the stoichiometric ratio value, HMF yield was highest. The highest HMF yield was achieved in the reaction mixture of 4 g [OMIM]Cl, 1 mL ethyl acetate, 0.1 g CrF₃, 5 mL 0.3 M HCl, and 0.5 g biomass.     

Photocatalytic performance of Ru doped anatase mounted on silica for reduction of carbon dioxide

Ru doped anatase supported on silica was prepared by solid-state dispersion method and examined for the photocatalytic reduction of carbon dioxide in aqueous medium at ambient conditions. To assist in interpreting the photocatalytic behaviour of Ru-TiO₂/SiO₂, reference systems consisting of Ru doped TiO₂ and TiO₂ supported on SiO₂ were also analyzed and the conditions were optimized. Ru/TiO₂ photocatalysts with metal loadings of 0.1, 0.3, 0.5 and 1.0 wt% were prepared by impregnation method and a series of TiO₂/SiO₂ catalysts with low TiO₂ (1, 3, 5 and 10 wt%) contents were prepared by solid-state dispersion method. The photocatalysts were characterized using X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM), UV–vis DRS, FT-IR and Raman spectroscopy. The results showed that TiO₂ particles with Ru ions have higher photocatalytic activity than undoped TiO₂ and the optimum Ru loading was found to be 0.5 wt%. Nevertheless, the yield increased notably when TiO₂ was supported on SiO₂. This strong enhancement suggests that in 10 wt% TiO₂/SiO₂ the efficiency of charge separation is strongly influenced through the presence of TiOSi bridging bonds. On the contrary, Ru-TiO₂/SiO₂ has no significant improvement in activity over TiO₂/SiO₂ except that it shows nearly quadruple times higher activity for the formation of methanol than Ru/TiO₂. The difference in the photocatalytic activity is related to its physico-chemical properties.     

The effects of SiO2 and K2O on glass forming ability and structure of CaOTiO2P2O5 glass system

The effects of SiO₂ and K₂O were investigated on the glass forming ability (GFA) and structural characteristics of CaOTiO₂P₂O₅ system. Differential thermal analyzer (DTA), X-ray diffraction (XRD), scanning electron microscopy (SEM), FT-IR and ³¹P magic angle spinning NMR methods were applied for characterizations of the system.Unwanted crystallization in the initial three components base glass composition was observed by adding SiO₂ and crystalline phases such as TiP₂O₇, rutile (TiO₂) and cristobalite (SiO₂) were formed in it.The results showed that K₂O prevents crystallization of glasses and promotes the formation of glass. FT-IR and X-ray diffraction showed that the addition of K₂O caused the formation of phosphate–silicate network as POSi, and formation of isolated droplet phases (rich of Si and P) separated from the phosphate matrix.The optimum amounts of SiO₂ and K₂O in phosphate structure were respectively 6 and 2 wt.%, 0 in accordance with glass forming ability (GFA) parameters. Despite addition of SiO₂ along with K₂O; the ³¹P MAS NMR and infrared spectrums of glasses show that no Q² sites were in the phosphate network. The Q¹ and the pyrophosphate groups was the predominant structural unit in these glasses.     

Accelerating the crosslinking process of hyperbranched polycarbosilane by UV irradiation

A liquid hyperbranched polycarbosilane (LHBPCS) with stoichiometric C/Si ratio but without unsaturated groups was synthesized. Different from traditional thermal crosslinking, ultraviolet (UV) irradiation crosslinking was taken. The molecular weight, the consumption of SiH group and ceramic yield of LHBPCS showed an increase trend with increasing the UV irradiation time. After 30 min of UV irradiation, 71.8 wt% ceramic yield was obtained. In addition, extra divinyldimethylsilane was added into LHBPCS. Under UV irradiation, both the SiH group and vinyl group of divinyldimethylsilane were consumed. But the reaction extend of vinyl group was much faster than that of SiH group. Compared with pure LHBPCS, the mixture of LHBPCS and 5 wt% divinyldimethylsilane gave a higher ceramic yield of 79 wt% after 30 min of UV irradiation. By heating the crosslinked LHBPCS to 1000 °C, a near stoichiometric SiC ceramic was got. It exhibited excellent thermal stability at 1400 °C in air.     

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.     

XAS study of Ni2P/MCM-41 passivated by O2/He and H2S/H2

Ni₂P/MCM-41 with a stoichiometric Ni/P ratio prepared using a H₂ plasma reduction method was passivated either by 10.0 vol.% H₂S/H₂ (Ni₂P-S) or 1.0 vol.% O₂/He (Ni₂P-O). The XAS characterization demonstrated that the NiP bond of Ni₂P was more sensitive to O₂ than the NiNi bond while H₂S mainly reacted with NiNi site. Moreover, Ni species in Ni₂P-S was more electron-deficient. The different hydrodesulfurization performances of Ni₂P-S and Ni₂P-O were discussed by considering their different structure and electronic properties as well as the formation of a covalent nickel phosphosulfide phase.     

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.     

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.     

Carbothermal synthesis of β-sialon from mechanochemically activated precursors

Reaction mixtures of halloysite clay and fine carbon for carbothermal reduction and nitridation (CRN) synthesis of β-sialon were ground in a planetary ball mill under flowing nitrogen for varying periods before being converted to sialon by heating in nitrogen at 1200–1400 °C. After 4 h grinding the XRD reflections of the halloysite were destroyed and some of the octahedrally-coordinated Al was converted to four- and five-fold coordination. ²⁷Al and ²⁹Si MAS NMR gave no evidence of the formation of AlN or SiN bonds upon grinding. Upon subsequent heating in nitrogen, the ground samples show significant differences from the unground control, the intermediate compound mullite being replaced by β-sialon (z ≈ 2) a temperature at least 100 °C lower, but the formation of corundum (α-Al₂O₃) also occurs at a lower temperature and is more persistent than in the unground control. MAS NMR spectroscopy shows that the products from the ground mixtures contain relatively less AlON units and that the formation of SiC (a transient reaction intermediate) is also facilitated by grinding. The optimum grinding time for this system was found to be 12 h.     

Synthesis,pyrolysis of a novel liquid SiBCN ceramic precursor and its application in ceramic matrix composites

SiBCN ceramic precursor, polyborosilazane, was synthesized through a novel method which used sodium borohydride as boron source. Vinyl silazane with SiCl was converted to vinyl silazane with SiH structure, followed by hydroboration reaction and subsequent high-temperature reaction to form soluble polyborosilazane liquid. The process of precursor-to-ceramic conversion was almost completed before 800 °C and the cross-linked polyborosilazane precursor exhibited higher ceramic yield 75.6% at 1200 °C. The SiBCN ceramic annealed at 1400 °C contained BN, SiN and SiC bonds with smooth and dense surface and still retained principally amorphous structure up to 1600 °C. In addition, the viscosity of the polyborosilazane was 65 mPa.s, which can efficiently prepare ceramic matrix composite by means of precursor infiltration and pyrolysis (PIP). The density of as-obtained ceramic matrix composite (CMC) was 1.82 g/cm³, and the average bending strength, bending modulus and tensile strength were 265.2 MPa, 37.5 GPa and 158.6 MPa, respectively.     

Fabrication of polymer derived ceramic parts by selective laser curing

Polymer derived ceramic parts of complex shape were fabricated by selective laser curing (SLC). The ceramic parts were built similar to the selective laser sintering process by sequentially irradiating layers consisting of SiC loaded polysiloxane powder with a CO₂-laser beam (λ = 10.6 μm), which locally induces curing reaction of the polymer phase at moderate temperatures around 400 °C. The laser-cured bodies were converted to SiOC/SiC ceramic parts in a subsequent pyrolysis treatment at 1200 °C in argon atmosphere. The scanning speed and the power of the CO₂-laser beam were varied, leading to pronounced differences in material properties. Laser irradiating a powder mixture containing 50 vol.% polymer/50 vol.% SiC resulted in relative green densities between 38 and 60%. Relative densities decreased to 32–50% after pyrolysis due to the polymer shrinkage. A post-infiltration with liquid silicon was carried out in order to produce dense parts. While before infiltration the bending strength only attained 17 MPa as a result of both microcracks in the SiOC matrix and a pronounced porosity, an average value of 220 MPa was achieved after post-infiltrating with Si. In the case of 50 vol.% SiC content the linear shrinkage after pyrolysis was only 3%. Thus, the SLC approach can be considered as a near-net-shape forming process of ceramic components with complex geometries.     

The control of BN and BC bonds in BCN films synthesized using pulsed laser deposition

A novel chemical bond transformation from BN to BC was observed in BCN films synthesized using pulsed laser deposition (PLD). BCN film prepared by using green laser (λ=532 nm) induced two IR absorption at 1370 and 800 cm⁻¹. This film was dominated by amorphous carbon phase and sp² hybridized BN bonds. BCN film deposited using an ultraviolet (UV) laser (λ=266 nm ) induced an addition infrared (IR) absorption at 1250 cm⁻¹. As we deposit BCN film by deep-UV laser (λ=213 nm), the absorption at 1370 and 800 cm⁻¹ disappeared while the absorption at 1250 cm⁻¹ remained. According to X-ray photoelectron spectroscopy (XPS), BC bonds with a carbon rich composition were formed. The formation of BC bonds in BCN films was also sensitive to deposition gas pressure and substrate temperature. Reactive carbon and boron species were needed to enable BC bonds that hybridized the carbon and the BN phases. A low substrate temperature was required to avoid competition with sp² hybridized pure BN and pure carbon bonds.     

Efficient reductions of various nitroarenes with scrap automobile catalyst and NaBH4

The effect of scrap automobile catalyst (SAC), a waste material, was investigated as a catalyst for the reduction of nitroarenes to the corresponding amines with sodium borohydride in aqueous ethanol at 5–25 °C. Along with the observed high conversions, the SAC and NaBH₄ combination also exhibits a selectively catalyzed reduction in compounds containing other reducible functionalities, such as CN, Br, Cl and I. Recycling automobile wastes into a catalyst for organic reactions will offer both environmental protection and economic advantages. As a result, an effective, easy to use, low-priced and reliable method has been developed.