Transmission electron microscopy of nanocomposite CrB-N thin films

This paper reports on the preparation and characterization of CrBN nanocomposite coatings for low friction, low wear and high thermostability applications. Sputtered CrBN thin films were prepared in order to obtain a composite structure consisting of hard CrB₂ and CrN crystallites as well as hexagonal BN lubricant phase by unbalanced magnetron sputtering (UBM) of a CrB₂ target in an Ar/N₂ gas discharge. Coatings, with a total thickness of 4.5-5.5 μm, were deposited at 450 °C on silicon single-crystal substrates. A nanocomposite structure was obtained by increasing the nitrogen content of the sputtering gas. The coating microstructure was investigated on selected samples by high-resolution transmission electron microscopy. The films were generally found to consist of crystallites of a 1-4 nm size embedded in amorphous matrix. This crystalline phase was identified by electron diffraction as hexagonal CrB₂ for low nitrogen content and cubic CrN for high nitrogen content. In the medium composition range, the structure was amorphous, still keeping the two-phase morphology. The use of high-resolution imaging mode helped to reveal the composition of the amorphous phase which seems predominantly to consist of boron nitride.     

Forbidden energy band gap in diluted a-Ge1 − xSix:N films

By means of electron gun evaporation Ge_1 − xSi_x:N thin films, in the entire range 0 ≤ x ≤ 1, were prepared on Si (100) and glass substrates. The initial vacuum reached was 6.6 × 10^− 4 Pa, then a pressure of 2.7 × 10^− 2 Pa of high purity N₂ was introduced into the chamber. The deposition time was 4 min. Crucible-substrate distance was 18 cm. X-ray diffraction patterns indicate that all the films were amorphous (a-Ge_1 − xSi_x:N). The nitrogen concentration was of the order of 1 at% for all the films. From optical absorption spectra data and by using the Tauc method the energy band gap (E_g) was calculated. The Raman spectra only reveal the presence of SiSi, GeGe, and SiGe bonds. Nevertheless, infrared spectra demonstrate the existence of SiN and GeN bonds. The forbidden energy band gap (E_g) as a function of x in the entire range 0 ≤ x ≤ 1 shows two well defined regions: 0 ≤ x ≤ 0.67 and 0.67 ≤ x ≤ 1, due to two different behaviors of the band gap, where for x > 0.67 exists an abruptly change of E_g(x). In this case E_g(x) versus x is different to the variation of E_g in a-Ge_1 − xSi_x and a-Ge_1 − xSi_x:H. This fact can be related to the formation of Ge₃N₄ and GeSi₂N₄ when x ≤ 0.67, and to the formation of Si₃N₄ and GeSi₂N₄ for 0.67 ≤ x.     

Degradation of cyanobacteria toxin by advanced oxidation processes

Advanced oxidation processes (AOPs) using O(3), H(2)O(2), O(3)/H(2)O(2), O(3)/Fe(II), and Fenton treatment were investigated for the degradation of aqueous solutions of cyanobacteria. The effects of concentration of reactants, temperature, and pH on toxins degradation were monitored and the reaction kinetics was assessed. O(3) alone or combined with either H(2)O(2) or Fe(II) were efficient treatment for toxins elimination. A higher toxin oxidation tendency was observed with Fenton reaction; total toxins degradation (MC-LR and MC-RR) was achieved in only 60s. The ozonation treatment was successfully described by second-order kinetics model, with a first-order with respect to the concentration of either ozone or toxin. At 20 degrees C, with initial concentration of MC-LR of 1mg/L, the overall second-order reaction rate constant ranged from 6.79 x 10(4) to 3.49 x 10(3)M(-1)s(-1) as the solution pH increased from 2 to 11. The reaction kinetics of the other AOPs (O(3)/H(2)O(2), O(3)/Fe(II), and Fenton), were fitted to pseudo first-order kinetics. A rapid reaction was observed to took place at higher initial concentrations of O(3), H(2)O(2) and Fe(II), and higher temperatures. At pH 3, initial concentration of toxin of 1mg/L, the pseudo first-order rate constant, achieved by Fenton process, was in order of 8.76+/-0.7s(-1).     

Effect of evaporated copper and aluminum on post-annealed SiOC(-H) films deposited using plasma-enhanced chemical vapor deposition

Low dielectric constant SiOC(-H) films were deposited on p-type Si(100) substrates by plasma-enhanced chemical vapor deposition (PECVD) using dimethyldimethoxysilane (DMDMOS, C₄H₁₂O₂Si) and oxygen gas as precursors. We studied the detailed electrical characterization of SiOC(-H)/p-Si(100) interfaces using different experimental parameters for using the multilevel interconnections in ultra large-scale integrated circuits (ULSI). To improve the SiOC(-H)/p-Si(100) interface, the wafer was cleaned using the RCA process and rinsed with deionized water. The deposited SiOC(-H) films were annealed at different temperatures ranging from 250 to 450 °C in a vacuum. The interface properties of the SiOC(-H)/p-Si(100) with Cu/SiOC(-H)/p-Si(100)/Al metal-insulator-semiconductor (MIS) structures were investigated by capacitance-voltage (C-V) measurement with a flat band shift by electric field stress. Trapped charge, fixed oxide charge, and the interface trap density of SiOC(-H) films were related to the dielectric breakdown and leakage current density at the SiOC(-H)/p-Si(100) interface. From these analyses, detailed electrical properties defining the interface states of the MIS structures were reported.     

Joining of CBN abrasive grains to medium carbon steel with AgCu/Ti powder mixture as active brazing alloy

In order to develop new generation brazed CBN grinding wheels, the joining experiments of CBN abrasive grains and medium carbon steel using the powder mixture of AgCu alloy and pure Ti as active brazing alloy are carried out at elevated temperature under high vacuum condition. The relevant characteristics of the special powder mixture, the microstructure of the interfacial region, which are both the key factors for determining the joining behavior among the CBN grains, the filler layer and the steel substrate, are investigated extensively by means of differential thermal analysis (DTA), scanning electron microscope (SEM) and energy dispersion spectrometer (EDS), as well X-ray diffraction (XRD) analysis. The results show that, similar to AgCuTi filler alloy, AgCu/Ti powder mixture exhibits good soakage capability to CBN grains during brazing. Moreover, Ti in the powder mixture concentrates preferentially on the surface of the grains to form a layer of needlelike TiN and TiB compounds by chemical metallurgic interaction between Ti, N and B at high temperature. Additionally, based on the experimental results, the brazing and joining mechanism is deeply discussed in a view of thermodynamic criterion and phase diagram of TiBN ternary system.     

An assessment of the role of intracellular reductive capacity in the biological clearance of triarylmethane dyes

The second-order rate constants (at pH 7, 25 degrees C) for the reduction of three cationic triarylmethane dyes [pararosaniline (PR+), malachite green (MG+), methyl green (MeG+)] by NADH were 1.4 x 10(-2) to 6.7 x 10(-2)mM(-1)min(-1). Based on these values the intracellular nonenzymatic reduction of TAM+ to TAM-H by endogenous NADH was estimated to proceed with an average half-life of 30 min. Rapid and significant adduct formation was observed with the thiol, 3-mercaptopropionic acid (MPA), suggesting that the primary intracellular form of the dyes must be a thiol adduct and that the conversion to adduct form takes place within ms-s. These time frames, when compared to the min-h time frame for microbial clearance of triarylmethanes from culture media, suggest that transport must be the rate-limiting step in non-adsorptive (chemical) clearance of the dyes and that the presence of enzymes to complement the nonenzymatic reductive and adduct-forming activities cited serves a kinetically limited purpose. It appears that a superior catalytic scavenger will be one with a superior transport capacity.     

New 3-((2′:2″,5″:2-terthiophene)-3″-yl) acrylic acid as active layer for organic field-effect transistor

Most functionalized thiophenes are difficult to electropolymerize due to nucleophilicity that will attack the radical cation inhibiting polymerization. However, we have successfully electrodeposited a newly synthesized functionalized terthiophene monomer 3-((2′:2″,5″:2-terthiophene)-3″-yl) acrylic acid (TAA) as an active layer of a organic field-effect transistor (OFET). The polymer was then oxidized in order to increase its conductivity. Various oxidizing potentials were experimented and their effect on the OFET's charge mobility was examined. A mobility of 0.25 cm² (V s)⁻¹ is achieved with an oxidizing potential of 0.9 V after vacuum drying.     

Role of microstructures on the growth of long fatigue cracks

An analysis is presented to understand the role of microstructures on the two crack growth driving force parameters, and , without invoking the extrinsic crack closure concepts. Microstructural variables considered are: grain size, precipitates and stacking fault energy. It is shown that is strongly affected by the scale of the microstructure, such as grain size or precipitate spacing. For each case, the mode of slip deformation and environment affects the fatigue resistance as represented by . However, the microstructures seem to have a smaller effect on . Also, the enhanced planarity of slip from the reduction in stacking fault energy has a pronounced effect on when compared with the materials deforming under homogeneous slip.     

Biodegradable polymers and their layered silicate nanocomposites: In greening the 21st century materials world

This review aims at highlighting on recent developments in preparation, characterization, properties, crystallization behaviors, melt rheology, processing, and future applications possibilities of biodegradable polymers and their layered silicate nanocomposites. These materials are attracting considerable interest in materials science research. Montmorillonite and hectorite are among the most commonly used smectite-type layered silicates for the preparation of nanocomposites. In their pristine form they are hydrophilic in nature, and this property makes them very difficult to disperse into biodegradable polymer matrices. The most common strategy to overcome this difficulty is to replace the interlayer clay cations with quarternized ammonium or phosphonium cations, preferably with long alkyl chains.

A wide range of biodegradable polymer matrices is described in this review with a special emphasis on polylactide because of more eco-friendliness from its origin as contrast to the fully petroleum-based biodegradable polymers and control of carbon dioxide balance after their composting.

Preparative techniques include (i) intercalation of polymers or prepolymers from solution, (ii) in situ intercalative polymerization method, and (iii) melt intercalation method.

This new family of composite materials frequently exhibits remarkable improvements of mechanical and material properties when compared with virgin polymers or conventional micro- and macro-composites. Improvements can include a high storage modulus both in solid and molten states, increased tensile and flexural properties, a decrease in gas permeability and flammability, increased heat distortion temperature and thermal stability, increase in the biodegradation rate, and so forth.