Electrical characterization of the boron trifluoride doped poly(3‐aminoacetophenone)/p‐Si junction

Electrical and interface state properties of the borontrifluoride doped poly(3‐aminoacetophenone)/p‐Si junction have been investigated by current‐voltage and impedance spectroscopy methods. Al/p‐Si/P₃APBF₃/Aldiode indicates a nonideal behavior with electrical parameters (n = 3.53, ?_B = 0.82 eV, and R_s = 1.48 kΩ), which result from the interfacial layer, series resistance, and resistance of the organic semiconductor. The obtained barrier height value of the Al/p‐Si/P₃APBF₃/Aldiode is higher than that of the conventional Al/p‐Si (?_B = 0.58 eV) Schottky diode. The interface state density of the diode was of the order of 1.05× 10¹² eV^?1 cm^?2. It is evaluated that the barrier height and interface state density values of the diode are modified using the boron trifluoride doped poly (3‐aminoacetophenone) organic semiconductor. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Autowave synthesis of cast binary silicides of molybdenum,tungsten, niobium,and titanium from thermite mixtures

The processes of combustion and phase separation in thermite SHS systems in the synthesis of cast composite materials based on the silicides of molybdenum, tungsten, niobium, and titanium in a wide range of ratios between them have been studied. Thermodynamic calculations for the hot MoO₃/2Al/2Si and WO₃/2Al/2Si systems have shown that the pressure has a the strong effect on the combustion temperature and yield of gaseous products, and for the cold 3Nb₂O₅/10Al/12Si and 3TiO₂/4Al/6Si systems, this effect has not been found. The effect of the ratio of the initial reagents and the activating high-temperature additive (CaO₂ + Al) on the combustion and phase-separation parameters have been studied experimentally.     

Mechanical Behavior and Electromagnetic Interference Shielding Properties of C/SiC–Ti3Si(Al)C2

In this paper, a low‐temperature densification process of Al–Si alloy infiltration was developed to fabricate C/SiC–Ti₃Si(Al)C₂, and then the microstructure, mechanical, and electromagnetic interference (EMI) shielding properties were studied compared with those of C/SiC–Ti₃SiC₂ and C/SiC–Si. The interbundle matrix of C/SiC–Ti₃Si(Al)C₂ is mainly composed of Ti₃Si(Al)C₂, which can bring various microdeformation mechanisms, high damage tolerance, and electrical conductivity, leading to the high effective volume fraction of loading fibers and electrical conductivity of C/SiC–Ti₃Si(Al)C₂. Therefore, C/SiC–Ti₃Si(Al)C₂ shows excellent bending strength of 556 MPa, fracture toughness 21.6 MPa·m^1/2, and EMI shielding effectiveness of 43.9 dB over the frequency of 8.2–12.4 GHz. Compared with C/SiC–Si and C/SiC–Ti₃SiC₂, both the improvement of mechanical properties and EMI shielding effectiveness can be obtained by the introduction of Ti₃Si(Al)C₂ into C/SiC, revealing great potential as structural and functional materials.     

The First Study of SCR of NO x by Acetylene in Excess Oxygen

Acetylene as a reducing agent for the selective catalytic reduction (C₂H₂-SCR) of NO in the presence of excess oxygen on various Ce-exchanged zeolites was investigated for the first time. Under the conditions of 1600 ppm NO, 800 ppm C₂H₂, and 9.95 % O₂ in He, the Ce-H-ZSM-5 (Si/Al=25) catalyst shows about 83% NO conversion to N₂ at the temperatures ranged from 300 to 350 °C. It is followed by the other zeolites in the activity order of Ce-H-Y (Si/Al=2.5), Ce-H-_ (Si/A1=20∼30), and Ce-H-SAPO (Si/Al=34), Ce-H-5A (Si/Al=12). Almost no NO conversion was obtained over Ce-Na-ZSM-5 (Si/Al=25) and Na-ZSM-5 (Si/Al=25) catalyst samples. The Conversion of NO to N₂ increased with O₂ concentration in the range of 0.1 ∼ 9.95% over the CeH-ZSM-5 (Si/Al=25) catalyst. It is suggested that O₂ plays an important role in the C₂H₂-SCR of NO reaction, by oxidizing NO to NO₂ on acid sites in assistant with cerium species of the catalyst. A large amount of CO, which seems to be in proportion with the NO conversion to N₂, was produced. Long-term experiments up to 56 h combined with a excursion of the reaction temperature up to 650 °C over the Ce-H-ZSM-5 (Si/A1=25) confirmed the catalyst’s durable performance under the reaction conditions. It is found that the de-NO_x activity of Ce-H-ZSM-5 catalyst can be enhanced by the presence of 50 ppm of sulfur dioxide in the dry-feed reaction conditions.     

Effect of TiO2 addition on the properties of Ti3Si(Al)C2 based ceramics fabricated by reactive melt infiltration

In this paper, Ti₃Si(Al)C₂ based ceramics were fabricated by reactive melt infiltration (RMI) of TiC/TiO₂ preforms with liquid silicon. The microstructure, phase composition, and mechanical properties of the Ti₃Si(Al)C₂ based ceramics have been investigated to understand the effect of phase composition of the preforms on the formation mechanisms of Ti₃Si(Al)C₂. The preforms with different content of TiO₂ infiltrated at 1500 °C with liquid silicon for 1 h were composed of Ti₃Si(Al)C₂, Al₂O₃, TiC, TiSi_xAl_y and residual Al. The prior generated Al₂O₃ phases inhibited the dispersion of Ti₃Si(Al)C₂ phases, resulting in the drastically grain growth of Ti₃Si(Al)C₂. Subsequently, the microstructure with gradually increasing Ti₃Si(Al)C₂ grain size resulted in the decrease of the bending strength and fracture toughness of samples. When the content of TiO₂ reached 20 wt%, the bending strength reached the maximum, 326.6 MPa. The fracture toughness attained the maximum, 4.3 MPa m^1/2, when the content of TiO₂ was 10 wt%.     

Electronic and structural properties of reduced-charge montmorillonites

Solid state silicon (²⁹Si) and aluminum (²⁷Al) nuclear magnetic resonance (NMR) spectroscopies were applied to a series of reduced-charge montmorillonites (RCMs) to discern changes in electronic and structural properties that are induced by Li fixation. Room temperature ²⁹Si MAS NMR spectra revealed a consistent chemical shift to more negative values and increased line width of the main Q³(0Al) Si resonance with increasing levels of Li fixation in the RCM series. A decreased line width of the octahedral Al (Al_[6]) environment was observed and may be attributed to formation of a more uniform electronic environment surrounding Al_[6] as charge reduction occurs. No appreciable changes in the tetrahedral Al (Al_[4]) peak were observed for the series, except for line broadening. Correlations of ²⁹Si NMR chemical shifts with layer charge and infrared-active structural vibrations indicated that distortions in the Si–O–T bond angles (T=tetrahedral Si or Al) occurred, with the mean Si–O–T bond angle increasing, following charge reduction. These results are interpreted as evidence of a redistribution both of layer charge and an abatement of the fit between octahedral and tetrahedral sheets following Li fixation and charge reduction. Our results are consistent with the formation of pyrophyllite-like character in reduced-charge montmorillonite.     

High performance tribological coatings on a secondary cast Al–Si alloy generated by Plasma Electrolytic Oxidation

Due to their outstanding properties, including low density or high-strength-to-weight ratio, cast Al–Si alloys are attractive materials. Nevertheless, their low wear and corrosion resistance still remain a critical issue for several applications. The present work is focused on the obtention of PEO coatings on a secondary cast Al–Si alloy (EN AC-46500) and the in-depth study of the properties derived from the use of two developed aluminate-based electrolytes.All the obtained PEO coatings have been characterized in terms of their thickness and roughness, morphology, and composition. Reciprocal wear tests have been performed in order to evaluate the tribological behavior of the PEO layers, while their anti-corrosion properties have been analyzed throughout Potentiodynamic Polarization and Electrochemical Impedance Spectroscopy.Our findings suggest that the aluminate-based electrolytes led to an increase in coating thickness of density, while providing a notable improvement on the surface hardness in comparison with the uncoated Al–Si alloy. All the PEO coatings tested exhibited excellent wear resistance and an improved anti-corrosion behavior compared with the uncoated Al–Si alloy. Furthermore, K₂TiF₆-containing electrolyte promoted the obtention of PEO coatings that provided the highest protection against wear and corrosion to the cast Al–Si alloy treated.     

Microcalorimetric and FTIR Study of the Adsorption of Carbon Dioxide on Alkali-Metal Exchanged FER Zeolites

Adsorption of CO₂ on alkali-metal exchanged (Li⁺, Na⁺, K⁺) FER zeolites was investigated by means of microcalorimetry and FTIR spectroscopy. The adsorption enthalpies strongly depend on coverage for all investigated materials and they are also influenced by concentration of Al in the framework. Especially, samples of Na- and K-FER with lower Si/Al ratio (8.6) exhibited substantially larger initial interaction energy than samples with Si/Al 27.5. Differences in zero-coverage adsorption energy of zeolites with different cation concentration (Si/Al ratio) are 9 and 7.2 kJ/mol for Na- and K-FER zeolites respectively. This phenomenon is attributed to formation of bridged CO₂ adsorption complexes formed between two cations, which are characterized by IR absorption band of ν₃ stretching vibration mode at 2370 and 2357 cm^?1 for Na- and K-FER respectively.     

Annealing-temperature-modulated optical,electrical properties,and leakage current transport mechanism of sol–gel-processed high-k HfAlOx gate dielectrics

Deposition of HfAlO_x gate dielectric films on n-type Si and quartz substrates by sol-gel technique has been performed and the optical, electrical characteristics of the as-deposited HfAlO_x thin films as a function of annealing temperature have been investigated. The optical properties of HfAlO_x thin films related to annealing temperature are investigated by ultraviolet-visible spectroscopy (UV–vis) and spectroscopy ellipsometry (SE). By measurement of UV–vis, average transmission of all the HfAlO_x samples are about 85% owing to their uniform composition. And the increase in band gap has been observed with the increase of annealing temperature. Moreover, the increase of refractive index (n) and density with the increase of annealing temperature are obtained by SE measurements. Additionally, the electrical properties based on Al/Si/HfAlO_x/Al capacitor are analyzed by means of the high frequency capacitance-voltage (C-V) and the leakage current density-voltage (J-V) characteristics. Results have shown that 400 °C-annealed sample demonstrates good electrical performance, including larger dielectric constant of 12.93 and lower leakage current density of 3.75×10⁻⁷ A/cm² at the gate voltage of 1 V. Additionally, the leakage current conduction mechanisms as functions of annealing temperatures are also discussed systematically.     

Self oscillatory behaviour in N2O decomposition over Co-ZSM-5 catalysts

Isothermal oscillations developed during N₂O decomposition over Co-ZSM-5 catalysts with different Si/Al ratios have been investigated. Spontaneous oscillations were observed between 350 and 450 °C. The maximum amplitude has been obtained for the catalysts having Si/Al of 40 and 50. The activation energies of the obtained oscillations were calculated in respect to cobalt concentration. The results showed that the E_a values increase linearly with an increasing Si/Al ratio of the zeolite. For Co-ZSM-5 catalyst (Si/Al = 25), increasing cobalt content in the catalyst led to a decrease in the frequency as well as the amplitude of the oscillations. Meanwhile, the increase in the E_a values was observed. The calculated reaction rate was found to be first order with respect to nitrous oxide concentration. Moreover, the developed oscillations were found to be sensitive to inlet N₂O concentration, catalyst weight and milling time duration. Decreasing the N₂O inlet concentration as well as the catalyst weight and increasing the milling time would lead to a quenching of the developed oscillations.     

Influence of initial Si/Al ratios on the structural,acidic and catalytic properties of nanosized-ZSM-5/SBA-15 analog composites prepared from ZSM-5 precursors

Nano-ZSM-5/SBA-15 analog composites (ZSC) were prepared in a two-step process from ZSM-5 precursors with different Si/Al molar ratios (10–50) via high-temperature synthesis in mildly acidic media (200 °C, pH 3.5) aiming to evaluate the influence of the initial Si/Al ratio on their structural, acidic and catalytic properties. The resulting materials were characterized by SAXS, XRD, FTIR, TEM, N₂ sorption, ²⁷Al solid state-NMR, NH₃-TPD, FTIR spectroscopy of adsorbed pyridine, AAS and ICP-AES. Under the applied synthesis conditions, a ZSC material with controlled distribution of nano-ZSM-5 and SBA-15 analog phases can be prepared from ZSM-5 precursors by adjusting the initial Si/Al ratio in the range of 20–30. Increasing the initial Si/Al ratio to 50, only ZSM-5 nanocrystals were obtained whereas reducing the initial Si/Al ratio to 10 led to the formation of a disordered mesoporous SBA-15 analog. The total acidity increases with the crystallinity of the ZSM-5 phase as varying the Si/Al ratio from 10 to 30 despite the decreased amount of incorporated aluminum. However, the acidity declines slightly when raising the Si/Al ratio to 50 because of the low incorporated aluminum. The catalytic performance of the ZSC materials compared to the reference materials, i.e. purely mesoporous Al-SBA-15 and purely microporous H-ZSM-5 was assessed in the gas phase cracking of cumene and 1,3,5-tri-isopropylbenzene (TIPB) as test reactions. The results show that a balanced ratio of nano-ZSM-5 and SBA-15 analog phases obtained by tuning the initial Si/Al ratio is crucial to achieve superior catalytic performance of the ZSC materials in the cracking of both cumene and TIPB.     

The Effect of Alkali Ions on the Incorporation of Aluminum in the Calcium Silicate Hydrate (C–S–H) Phase Resulting from Portland Cement Hydration Studied by 29Si MAS NMR

The incorporation of aluminum in the calcium–silicate–hydrate (C–S–H) phases formed by hydration of three different white Portland cements has been investigated by ²⁹Si MAS NMR. The principal difference between the three cements is their bulk Al₂O₃ contents and quantities of alkali (Na⁺ and K⁺) ions. ²⁹Si MAS NMR allows indirect detection of tetrahedral Al incorporated in the silicate chains of the C–S–H structure by the resonance from Q²(1Al) sites. Analysis of the relative ²⁹Si NMR intensities for this site, following the hydration for the three cements from 0.5 d to 30 weeks, clearly reveals that the alkali ions promote the incorporation of Al in the bridging sites of the dreierketten structure of SiO₄ tetrahedra in the C–S–H phase. The increased incorporation of Al in the C–S–H phase with increasing alkali content in the anhydrous cement is in accord with a proposed substitution mechanism where the charge deficit, obtained by the replacement of Si⁴⁺ by Al³⁺ ions in the bridging sites, is balanced by adsorption/binding of alkali ions in the interlayer region most likely in the near vicinity of the AlO₄ tetrahedra. This result is further supported by similar ²⁹Si MAS NMR experiments performed for the white Portland cements hydrated in 0.30M NaOH and NaAlO₂ solutions.     

Composition,structure, and morphology of nanostructured aluminosilicates

The data on synthesizing nanosized potassium aluminosilicates (PAS) with a ratio of Si/Al of 1–5 obtained in the KOH–Al₂(SO₄)₃ · 18H₂O–SiO₂ · nH₂O–H₂O multicomponent system have been presented. Their composition, morphology, and IR and NMR spectra have been studied.     

Dissolution kinetics of calcined kaolinite and montmorillonite in alkaline conditions: Evidence for reactive Al(V) sites

Calcined clays are attracting significant research attention because of their potential to partially replace CO₂-intensive portland cement. This potential depends largely on their reactivity, especially dissolution under alkaline conditions. Identification and characterization of reactive sites in these amorphous calcined clays has so far not been reported. Here, we investigate kaolinite (1:1 clay) and montmorillonite (2:1 clay) calcined at different temperatures under alkaline conditions (0.1 mol/L NaOH). Solution compositions are determined in batch dissolution experiments, whereas ²⁷Al and ²⁹Si MAS and CP/MAS NMR are used to investigate the structure of the undissolved residues to identify sites that are reactive and undergo preferential dissolution. The highest Si and Al dissolution rates for kaolinite are observed for calcination at 700°C, corresponding to the temperature of optimum reactivity, whereas the rates decrease and become increasingly incongruent at higher temperatures. The Si and Al dissolution rates for optimally calcined kaolinite are 4 and 12 times larger than the corresponding rates for optimally calcined montmorillonite, in accord with the much higher reactivity of calcined kaolinite compared to calcined 2:1 clays. This superior performance of kaolinite is explained by novel ²⁷Al NMR results, which show strong evidence for preferential dissolution of highly reactive pentahedral aluminum sites.     

Raman and X-ray photoelectron spectroscopy study on the influence of La2O3 on the melt structure of SiO2–CaO–Al2O3–MgO

In order to gain more insights into the influence of rare earth elements on the melt structure of SiO₂–CaO–Al₂O₃–MgO glass ceramics, Raman and X-ray photoelectron spectroscopy techniques were used to study the influence of La₂O₃ on the Si–O/Al–O tetrahedron structure within SiO₂–CaO–Al₂O₃–MgO–quenched glass samples in this study. Results showed that some Raman peak shapes at low frequencies (200–840 cm^?1) changed significantly after the addition of La₂O₃, compared to the high frequency (840–1200 cm^?1) region that corresponds to the [SiO₄] structure, suggesting that the depolymerization of the low-frequency T–O–T (T=Si or Al) structure was more prevalent with La³⁺ addition. Besides, the depolymerization extent of the Si–O/Al–O tetrahedral network varied when the melt composition altered. Most notably, depolymerization is the most significant at a low CaO/SiO₂ ratio (0.25) and a high Al₂O₃ content (8%). Meanwhile, La³⁺ can promote the transformation of Si–O–Si and Al–O–Al bonds to the Si–O–Al ones, thereby forming a complex ionic cluster network interwoven with Si–O and Al–O tetrahedrons.     

Cast silicides of molybdenum,tungsten, and niobium by combustion synthesis

Cast silicides of molybdenum, tungsten, and niobium were prepared by combustion synthesis under nitrogen pressure from powder mixtures of respective metal oxides with Al and Si. Upon variation in green composition, cast MoSi₂, WSi₂, NbSi₂, and their solid solutions with variable phase composition have been synthesized. NbSi₂ was obtained by combustion in the presence of added heat-generating CaO₂-Al powder mixture.     

Wetting of SiC by Al-Ti alloys and joining by in-situ formation of interfacial Ti3Si(Al)C2

Two pressureless and reliable procedures for brazing SiC-based materials have been designed. The joining was obtained by the in-situ formation of a Ti₃Si(Al)C₂ MAX phase using simple Al-Ti interlayers. Wettability studies were conducted using several Al-Ti alloys in contact with SiC at 1500?°C. The interfacial microstructures and thermodynamic analysis demonstrated that liquid Al₃Ti in contact with SiC formed a well-bonded Ti₃Si(Al)C₂ interfacial layer. These findings guided the design of two joining methods: one consisted of the simple infiltration of Al₃Ti into the brazing seam, while an Al₃Ti paste/Ti/Al₃Ti paste interlayer assembly was designed for the second process. Sound interfaces without cracks were obtained in both processes. The average shear strength was very high, 296?MPa, for the infiltration method; the drawback was the presence of residual Al. Joining through Al₃Ti/Ti/Al₃Ti interlayers avoided the presence of low-temperature melting phases, with lower shear strength: 85 or 89?MPa depending on the testing method.     

Synthesis of hierarchical MFI zeolite microspheres with stacking nanocrystals

MFI nanozeolite microspheres with intercrystal mesopores were synthesized by a steam-assisted crystallization–aggregation method, starting with close packed amorphous SiO₂ or Al-containing SiO₂ colloidal nanoparticles. The obtained samples with different Si/Al ratios were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy (SEM)/ transmission electron microscopy (TEM) observations, nitrogen adsorption analyses and ²⁷Al magic angle spinning nuclear magnetic resonance (NMR). The SEM images clearly showed that the mean size of nanozeolite microspheres was ca. 0.5–3 μm, agglomerated from zeolite nanocrystals and varied with different Si/Al ratios. N₂ sorption analyses as well as TEM micrographs indicated the dual-porosity of samples, one is from intracrystal micropores, and the other is from intercrystal mesopores. ²⁷Al MAS-NMR suggested nearly all of the Al atoms were located at tetrahedral-coordinated sites in the framework. Furthermore, nanozeolite microspheres with various Si/Al ratios, even Si/Al equal to five, could be prepared by this facile route and less structure-directing agent was needed compared to conventional approach. This simple method could be easily extended to prepare other hierarchically structured zeolites.     

The effect of Si/Al ratio and moisture on an organic/inorganic hybrid material: Thioindigo/montmorillonite

Colored Organic/Inorganic Hybrid Materials (OIHM) with reversible properties were prepared by a solid-state reaction between several montmorillonites (MMT) with different Si/Al ratio (Bentolite L^®, Texas, Wyoming and Kunipia deposits) and a neutral organic dye (thioindigo) at 413 K for nine hours. Spectroscopic and thermogravimetric analysis of the above mentioned interactions were evaluated. Results obtained by these techniques revealed an influence of Si/Al ratio in dehydrated MMT, where the intramolecular charge-transfer (IMCT) in thioindigo progressively red-shifted and increased in intensity in the following order: BentoT (Si/Al = 8.2) > TexasT (Si/Al = 7) > WyomingT (Si/Al = 5.6) > KunipiaT (Si/Al = 4.8). Moreover, a disturbance of thioindigo C=O at 1654 cm^?1 to lower frequencies occurred due to C=O---Lewis acid sites (LAS) and Brønsted (B) interaction in MMT with high Si/Al ratio. In the presence of water, a smaller C=O shift due to C=O---(H₂O)LAS or B interaction was identified. In addition, displacement of the basal spacing (001) in all MMT confirmed the effect of water on the reversible color changes displayed by UV–Vis diffuse reflectance spectroscopy. The existence of different binding strengths in OIHM was also evaluated by TGA and UV–Vis spectroscopy of their ethanol Soxhlet extractions.     

Structural dependence of crystallization in phosphorus-containing sodium aluminoborosilicate glasses

The article reports on the structural dependence of crystallization in Na₂O–Al₂O₃–B₂O₃–P₂O₅–SiO₂-based glasses over a broad compositional space. The structure of melt-quenched glasses has been investigated using ¹¹B, ²⁷Al, ²⁹Si, and ³¹P magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy, while the crystallization behavior has been followed using X-ray diffraction and scanning electron microscopy combined with energy dispersive spectroscopy. In general, the integration of phosphate into the sodium aluminoborosilicate network is mainly accomplished via the formation of Al–O–P and B–O–P linkages with the possibility of formation of Si–O–P linkages playing only a minor role. In terms of crystallization, at low concentrations (≤5 mol.%), P₂O₅ promotes the crystallization of nepheline (NaAlSiO₄), while at higher concentrations (≥10 mol.%), it tends to suppress (completely or incompletely depending on the glass chemistry) the crystallization in glasses. When correlating the structure of glasses with their crystallization behavior, the MAS NMR results highlight the importance of the substitution/replacement of Si–O–Al linkages by Al–O–P, Si–O–B, and B–O–P linkages in the suppression of nepheline crystallization in glasses. The results have been discussed in the context of (1) the problem of nepheline crystallization in Hanford high-level waste glasses and (2) designing vitreous waste forms for the immobilization of phosphate-rich dehalogenated Echem salt waste.