Novel mechanism for high speed growth of transparent and conducting tin oxide thin films by spray pyrolysis

A novel mechanism is proposed for efficient manipulation of transport forces acting on the droplets during spray pyrolytic deposition of thin films. A ‘‘burst mode’’ technique of spraying is used to adjust the deposition conditions so as to transport the droplets under the new mechanism. Transparent, conducting thin films of undoped tin oxide prepared by this method showed significant improvement in growth rate. The films are found to be of fairly good quality with optical transmission of 82% and sheet resistance of 35 Ω/☒. The films are chemically homogeneous and grow preferentially along 〈200〉 direction.

Methanol oxidation on carbon-supported platinum-tin electrodes in sulfuric acid

A study is made of the electrooxidation of methanol in sulfuric acid on carbon-supported electrodes containing platinum-tin bimetal catalysts that are prepared by an in situ potentiometric-characterization route. The catalysts are investigated by employing chemical analyses, X-ray diffraction (XRD), X-ray absorption-near-edge spectroscopy (XANES) and X-ray photoelectron spectroscopy (XPS) data in conjunction with electrochemical measurements. From the electrochemical data, it is inferred that while an electrode with (3:1) Pt-Sn/C catalyst involves a two-electron rate-limiting step akin to platinum-on-carbon electrodes, it is shifted to a one-electron mechanism on electrodes with (3:2)Pt-Sn/C, (3:3)Pt-Sn/C, and (3:4)Pt-Sn/C catalysts. The study suggests that the tin content in the platinum-tin bimetal catalyst produces: (i) a charge transfer from tin to platinum; (ii) an increase in the coverage of adsorbed methanolic residues with increase in the tin content, as indicated by the shift in rest potential of the electrodes towards the reversible value for oxidation of methanol (0.043 V versus SHE), and (iii) a decrease in the overall content of higher valent platinum sites in the catalyst.

Methanol oxidation on carbon-supported platinum-tin electrodes in sulfuric acid

A study is made of the electrooxidation of methanol in sulfuric acid on carbon-supported electrodes containing platinum-tin bimetal catalysts that are prepared by an in situ potentiometric-characterization route. The catalysts are investigated by employing chemical analyses, X-ray diffraction (XRD), X-ray absorption-near-edge spectroscopy (XANES) and X-ray photoelectron spectroscopy (XPS) data in conjunction with electrochemical measurements. From the electrochemical data, it is inferred that while an electrode with (3:1) Pt-Sn/C catalyst involves a two-electron rate-limiting step akin to platinum-on-carbon electrodes, it is shifted to a one-electron mechanism on electrodes with (3:2)Pt-Sn/C, (3:3)Pt-Sn/C, and (3:4)Pt-Sn/C catalysts. The study suggests that the tin content in the platinum-tin bimetal catalyst produces: (i) a charge transfer from tin to platinum; (ii) an increase in the coverage of adsorbed methanolic residues with increase in the tin content, as indicated by the shift in rest potential of the electrodes towards the reversible value for oxidation of methanol (0.043 V versus SHE), and (iii) a decrease in the overall content of higher valent platinum sites in the catalyst.

Substrate-dependent structure, microstructure, composition and properties of nanostructured TiN films

Titanium nitride films of a thickness of similar to 1.5 mu m were deposited on amorphous and crystalline substrates by DC reactive magnetron sputtering at ambient temperature with 100% nitrogen in the sputter gas. The growth of nanostructured, i.e. crystalline nano-grain sized, films at ambient temperature is demonstrated. The microstructure of the films grown on crystalline substrates reveals a larger grain size/crystallite size than that of the films deposited on amorphous substrates. Specular reflectance measurements on films deposited on different substrates indicate that the position of the Ti-N 2s band at 2.33 eV is substrate-dependent, indicating substrate-mediated stoichiometry. This clearly demonstrates that not only structure and microstructure, but also chemical composition of the films is substrate-influenced. The films deposited on amorphous substrates display lower hardness and modulus values than the films deposited on crystalline substrates, with the highest value of hardness being 19 GPa on a lanthanum aluminate substrate. (C) 2011 Elsevier Ltd. All rights reserved.

Mechanism of ?-cleavage in the excited states of keto sulfides

The beta-cleavage process in photoexcited ketones of structure RCOCH2X (X = CH2CH3, OCH3, SCH3; R = CH3, Ph) has been studied using the configuration interaction procedure within the framework of MINDO/3. The results explain qualitatively why the beta-cleavage process is faster than the alpha-cleavage process in keto sulfides while in keto ethers the reverse is true.

Role of spacer chain length in dimeric micellar organization. Small angle neutron scattering and fluorescence studies

Micelles of different dimeric amphiphiles Br-, n-C(16)H(33)NMe(2)(+) -(CH)(m)-N(+)Me(2)-n-C16H33, Br- (where m = 3, 4, 5, 6, 8, 10, and 12) adapt different morphologies and internal packing arrangements in aqueous media depending on their spacer chain length (m). Detailed measurements of small angle neutron scattering (SANS) cross sections from different bis-cationic, dimeric surfactant micelles in aqueous media (D2O) are reported. The data have been analyzed using the Hayter and Penfold model for macro ion solution to compute the interparticle structure factor S(Q) taking into account the screened Coulomb interactions between the dimeric micelles. The SANS analysis clearly indicated that the extent of aggregate growth and the variations of shapes of the dimeric micelles depend primarily on the spacer chain length. With spacer chain length, m less than or equal to 4, the propensity of micellar growth was particularly pronounced. The effects of the variation of the concentration of dimeric surfactants with m = 5 and 10 on the SANS spectra and the effects of the temperature variation for the micellar system with m = 10 were also examined. The critical micelle concentrations (cmc) and their microenvironmental feature, namely, the microviscosities that the dimeric micellar aggregates offer to a solubilized, extrinsic fluorescence probe, 1,6-diphenyl-1,3,5-hexatriene, were also determined. The changes of cmcs and microviscosities as a function of spacer chain length have been explained in terms of conformational variations and progressive looping of the spacer in micellar core upon increasing m values.

Investigations on sodium tin phosphate and tin pyrophosphate glasses

Glasses of the alkali tin phosphate system have been investigated. The infrared absorption and fluorescence spectra of the glasses have been examined. It is found that tin is present in both + 2 and + 4 oxidation states. Also tin ions occupy four- or six-coordinated sites in the glass.

Vesicle formation from dimeric surfactants through ion-pairing. Adjustment of polar headgroup separation leads to control over vesicular thermotropic properties

Eight new vesicle-forming dimeric surfactants are synthesized: the polar headgroup separation in such dimeric amphiphiles strongly influences their vesicular thermotropic phase-transition behaviour.

Small-angle neutron scattering studies of different mixed micelles composed of dimeric and monomeric cationic surfactants

Measurements of small-angle neutron scattering (SANS) cross sections from different mixed micelles composed of CTAB and Br-, n-C16H33N+Me2-(CH2)(m)N+Me2-n-C16H33, Br- (16-m-16, 2Br(-), where m = 3, 5, and 10), in aqueous media (D2O) are reported. The data have been analyzed using the Hayter and Penfold model for macroion solution to compute the interparticle structure factor S(Q) taking into account the screened Coulomb interactions between the micelles. The aggregate composition matches with that predicted from an ideal mixing model. The SANS analysis further indicates that the extent of aggregate growth and the Variations of shapes of the mixed micelles could be modulated by the amount of dimeric surfactant present in these mixtures. With the spacer chain length m less than or equal to 4 in the dimeric surfactant, the propensity of micellar growth is particularly pronounced. The effect of the variation of the temperature for the mixed micellar system (23.1 mol % of 16-3-16, 2Br(-)) was also examined. The systemic microviscosities that the mixed micellar aggregates offer to a solubilized, extrinsic fluorescence probe, 1,6-diphenyl-1,3,5-hexatriene, were determined. The variation of the microviscosities of the mixed micelles as a function of percentages of the dimeric surfactants could be explained in terms of conformational variations and progressive looping of the spacer chain of dimeric surfactants in mixed micellar aggregates with increasing m values.

Synthesis and vesicle formation from novel pseudoglyceryl dimeric lipids. Evidence of formation of widely different membrane organizations with exceptional thermotropic properties

Eight new bis-cationic dimeric lipids 2a-h have been synthesized; TEM of their aqueous dispersions confirmed the vesicle formation and from the thermal, spectroscopic, DLS and XRD studies it has been revealed that they form three different kinds of membranous aggregate depending on the m-value.

Micellar structures of dimeric surfactants with phosphate head groups and wettable spacers: A small-angle neutron scattering study

Dimeric or gemini surfactants consist of two hydrophobic chains and two hydrophilic head groups covalently connected by a hydrophobic or hydrophilic spacer. This paper reports the small-angle neutron scattering (SANS) measurements from aqueous micellar solutions of two different recently developed types of dimeric surfactants: (i) bis-anionic C16H33PO4--(CH2)(m)-PO4-C16H33,2Na(+) dimeric surfactants composed of phosphate head groups and a hydrophobic polymethylene spacer, referred to as 16-m-16,2Na(+), for spacer lengths m = 2, 4, 6, and 10, (ii) bis-cationic C16H33N+(CH3)(2)-CH2-(CH2-O-CH2)(p)-CH2-N+ (CH3)(2)C16H33,2Br(-) dimeric surfactants composed of dimethylammonium head groups and a wettable polyethylene oxide spacer, referred to as 16-CH2-p-CH2-16,2Br(-), for spacer lengths p = 1 - 3. The micellar structures of these surfactants are compared with the earlier studied bis-cationic C16H33N+ (CH3)(2)-(CH2)(m)-N+ (CH3)(2)C16H33,2Br(-) dimeric surfactants composed of dimethylammonium head groups and a hydrophobic polymethylene spacer, referred to as 16-m-16,2Br(-). It is found that 16-m-16,2Na(+), similar to 16-m-16,2Br(-), form various micellar structures depending on the spacer length. Micelles an disklike for rn = 2, rodlike for m = 4, and prolate ellipsoidal fur m = 6 and 10. The micelles of 16-CH2-p-CH2-16,2Br(-) are prolate ellipsoidal for all the values of p = 1 - 3. It is also found that micelles of 16-m-16,2Na(+) and 16-CH2-p-CH2-16,2Br(-) are large in comparison to those of 16-in-16,2Br(-) for similar spacer lengths. This is connected with the fact that both in 16-m-16,2Na(+) and 16-CH2-p-CH2-16,2Br(-), the head group or the spacer is more hydrated as compared to that in the 16-m-16,2Br(-). An increase in the hydration of the spacer or the head group increases the screening of the Coulomb repulsion between the charged head groups. This effect has been found to be more pronounced in the dimeric surfactants having wettable spacers. [S1063-651X(99)00303-7].

Synthesis and vesicle formation from dimeric pseudoglyceryl lipids with (CH2)(m) spacers: pronounced m-value dependence of thermal properties, vesicle fusion, and cholesterol complexation

Eight new dimeric lipids, in which the two Me2N+ ion headgroups are separated by a variable number of polymethylene units [-(CH2)(m)-], have been synthesized. The electron micrograph (TEM) and dynamic light scattering (DLS) of their aqueous dispersions confirmed the formation of vesicular-type aggregates. The vesicle sizes and morphologies were found to depend strongly on the m value, the method, and thermal history of the vesicle preparation. Information on the thermotropic properties of the resulting vesicles was obtained from microcalorimetry and temperature-dependent fluorescence anisotropy measurements. Interestingly, the T-m values for these vesicles revealed a nonlinear dependence on spacer chain length (m value). These vesicles were able to entrap riboflavin. The rates of permeation of the OH- ion under an imposed transmembrane pH gradient were also found to depend significantly on the m value. X-Ray diffraction of the cast films of the lipid dispersions elucidated the nature and the thickness of these membrane organizations, and it was revealed that these lipids organize in three different ways depending on the m value. The EPR spin-probe method with the doxylstearic acids 5NS, 12NS, and 16NS, spin-labeled at various positions of stearic acid, was used to establish, the chain-flexibility gradient and homogeneity of these bilayer assemblies. The apparent fusogenic propensities of these bipolar tetraether lipids were investigated in the presence of Na2SO4 with fluorescence-resonance energy-transfer fusion assay. Small unilamellar vesicles formed from 1 and three representative biscationic lipids were also studied with fluorescence anisotropy and H-1 NMR spectroscopic techniques in the absence and the presence of varying amounts of cholesterol.

Vesicle formation from dimeric ion-paired amphiphiles. Control over vesicular thermotropic and ion-transport properties as a function of intra-amphiphilic headgroup separation

A novel series of vesicle-forming ion-paired amphiphiles, bis(hexadecyldimethylammonium)alkane dipalmitate (1a-1h), containing four chains were synthesized with two isolated headgroups. In each of these amphiphiles, the two headgroup charges are separated by a flexible polymethylene spacer chain -[(CH2)(m)]- of varying lengths (m) such that the length and the conformation of the spacer chain determine the intra-"monomer" headgroup separation. Transmission electron microscopy indicated that each of these forms bilayer membranes upon dispersion in aqueous media. The vesicular properties of these aggregates have been examined by differential scanning calorimetry and temperature-dependent fluorescence anisotropy measurements. Interestingly, their T-m values decreased with the increase in the m value. Thus while the apparent T-m of the lipid with m = 2 (1a) is 74.1 degrees C, the corresponding value observed for the lipid with m = 12 (1h) is 38.9 degrees C. The fluorescence anisotropy values (r) for 1b-1g were quite high (r similar to 0.3) compared to that of 1h (r similar to 0.23) at 20-30 degrees C in their gel states. On the other hand, the r value for vesicular 1b beyond melting was higher (0.1) compared to any of those for 1c-1h (similar to 0.04-0.06). X-ray diffraction of the cast films was performed to understand the nature and the thickness of these membrane organizations. The membrane widths ranged from 30 to 51 A as the m values varied. The entrapment of a small water-soluble solute, riboflavin, by the individual vesicular aggregates, and their sustenance: under an imposed transmembrane pH gradient have also been examined. These results show that all lipid vesicles entrap riboflavin and that generally the resistance to OH- permeation decreases with the increase in m value. Finally,all the above observations were comparatively analyzed, and on the basis of the calculated structures of these lipids, it was possible to conclude that membrane propel-ties can be modulated by spacer chain length variation of the ion-paired amphiphiles.

Nitride synthesis using ammonia and hydrazine - a thermodynamic panorama

Because of the wide variety of projected applications of ultrapure nitrides in advanced technologies, there is interest in developing new cost-effective methods of synthesis. Explored in this study is the use of ammonia and hydrazine for the synthesis of nitrides from oxides, sulfides and chlorides. Even when the standard Gibbs energy change for the nitridation reactions involved are moderately positive, the reaction can be made to proceed by lowering the partial pressure of the product gas below its equilibrium value. Use of a metastable form of precursor in the nanometric size range is an alternative method to facilitate nitridation. Ellingham-Richardson-Jeffes diagrams are used for a panoramic presentation of the driving force for each set of reactions as a function of temperature. Oxides are the least promising precursors for nitride synthesis; sulfides offer a larger synthetic window for many useful nitrides such as BN, AlN, InN, VN, TiN, ThN and Si3N4. The standard Gibbs free energy changes for reactions involving chlorides with either ammonia or hydrazine are much more negative. Hydrazine is a more powerful nitriding agent than ammonia. The metastability of hydrazine requires that it be introduced into a reactor through a water-cooled lance. The use of volatile halides with ammonia or hydrazine offers the potential for synthesis of pure and doped nanocrystalline nitrides. Nitride thin films can also be prepared by suitable adaptations of the chloride route. (C) 2002 Kluwer Academic Publishers.

Study of embedded lead-tin nanoparticles in aluminum matrix

Nanoembedded lead-tin alloys in aluminum matrix were synthesized by rapid solidification processing. These melt-spun aluminum alloys were then investigated using XRD, EDX and TEM. The XRD study reveals that the melt-spun samples contain elemental aluminum, lead and tin. The TEM analysis shows that embedded particles in aluminium matrix have a distinct two-phase contrast of lead and tin. The lead and tin in these nanoalloys exhibit an orientation relationship with the matrix aluminum and with each other. DSC studies were conducted to reveal the melting and solidification characteristics of these embedded nanoalloys. DSC thermograms exhibit features of multiple solidification exotherms on thermal cycling, which can be attributed to sequential melting and solidification of lead and tin in the respective alloys.