Optimum geometry for uniform deposits on a rotating substrate from a point source

The application of an algorithm shows that maximum uniformity of film thickness on a rotating substrate is achieved for a normalized source-to-substrate distance ratio, h/r =1.183.

Atomic Layer Deposition and Photocatalytic Properties of Titanium Dioxide Thin Films

Photocatalytic TiO2 thin films can be highly useful in many environments and applications. They can be used as self-cleaning coatings on top of glass, tiles and steel to reduce the amount of fouling on these surfaces. Photocatalytic TiO2 surfaces have antimicrobial properties making them potentially useful in hospitals, bathrooms and many other places where microbes may cause problems. TiO2 photocatalysts can also be used to clean contaminated water and air. Photocatalytic oxidation and reduction reactions proceed on TiO2 surfaces under irradiation of UV light meaning that sunlight and even normal indoor lighting can be utilized. In order to improve the photocatalytic properties of TiO2 materials even further, various modification methods have been explored. Doping with elements such as nitrogen, sulfur and fluorine, and preparation of different kinds of composites are typical approaches that have been employed. Photocatalytic TiO2 nanotubes and other nanostructures are gaining interest as well. Atomic Layer Deposition (ALD) is a chemical gas phase thin film deposition method with strong roots in Finland. This unique modification of the common Chemical Vapor Deposition (CVD) method is based on alternate supply of precursor vapors to the substrate which forces the film growth reactions to proceed only on the surface in a highly controlled manner. ALD gives easy and accurate film thickness control, excellent large area uniformity and unparalleled conformality on complex shaped substrates. These characteristics have recently led to several breakthroughs in microelectronics, nanotechnology and many other areas. In this work, the utilization of ALD to prepare photocatalytic TiO2 thin films was studied in detail. Undoped as well as nitrogen, sulfur and fluorine doped TiO2 thin films were prepared and thoroughly characterized. ALD prepared undoped TiO2 films were shown to exhibit good photocatalytic activities. Of the studied dopants, sulfur and fluorine were identified as much better choices than nitrogen. Nanostructured TiO2 photocatalysts were prepared through template directed deposition on various complex shaped substrates by exploiting the good qualities of ALD. A clear enhancement in the photocatalytic activity was achieved with these nanostructures. Several new ALD processes were also developed in this work. TiO2 processes based on two new titanium precursors, Ti(OMe)4 and TiF4, were shown to exhibit saturative ALD-type of growth when water was used as the other precursor. In addition, TiS2 thin films were prepared for the first time by ALD using TiCl4 and H2S as precursors. Ti1-xNbxOy and Ti1-xTaxOy transparent conducting oxide films were prepared successfully by ALD and post-deposition annealing. Highly unusual, explosive crystallization behaviour occurred in these mixed oxides which resulted in anatase crystals with lateral dimensions over 1000 times the film thickness.

Copper Diffusion Barrier Deposition on Integrated Circuit Devices by Atomic Layer Deposition Technique

Transfer from aluminum to copper metallization and decreasing feature size of integrated circuit devices generated a need for new diffusion barrier process. Copper metallization comprised entirely new process flow with new materials such as low-k insulators and etch stoppers, which made the diffusion barrier integration demanding. Atomic Layer Deposition technique was seen as one of the most promising techniques to deposit copper diffusion barrier for future devices. Atomic Layer Deposition technique was utilized to deposit titanium nitride, tungsten nitride, and tungsten nitride carbide diffusion barriers. Titanium nitride was deposited with a conventional process, and also with new in situ reduction process where titanium metal was used as a reducing agent. Tungsten nitride was deposited with a well-known process from tungsten hexafluoride and ammonia, but tungsten nitride carbide as a new material required a new process chemistry. In addition to material properties, the process integration for the copper metallization was studied making compatibility experiments on different surface materials. Based on these studies, titanium nitride and tungsten nitride processes were found to be incompatible with copper metal. However, tungsten nitride carbide film was compatible with copper and exhibited the most promising properties to be integrated for the copper metallization scheme. The process scale-up on 300 mm wafer comprised extensive film uniformity studies, which improved understanding of non-uniformity sources of the ALD growth and the process-specific requirements for the ALD reactor design. Based on these studies, it was discovered that the TiN process from titanium tetrachloride and ammonia required the reactor design of perpendicular flow for successful scale-up. The copper metallization scheme also includes process steps of the copper oxide reduction prior to the barrier deposition and the copper seed deposition prior to the copper metal deposition. Easy and simple copper oxide reduction process was developed, where the substrate was exposed gaseous reducing agent under vacuum and at elevated temperature. Because the reduction was observed efficient enough to reduce thick copper oxide film, the process was considered also as an alternative method to make the copper seed film via copper oxide reduction.

An XPS study of the surface oxidation states of metals in some oxide catalysts

Calcined samples of chromia supported on Al2O3, ZnO, or SnO2 show both Cr(VI) and Cr(III) on the surface, Cr(VI) being preponderant in the case of Al2O3-supported catalysts. The proportion of Cr(VI) decreases with increase in Cr content of the calcined catalysts. Reduction of the supported chromia catalysts in H2 at 720 K for 1 hr gives rise to Cr(III) and Cr(V). On carrying out the dehydrogenation of cyclohexane on the chromia catalysts a higher proportion of Cr(V) is found than after treatment with hydrogen. Vanadia supported on Al2O3 or MoO3 shows significant proportion of V(IV) on carrying out the oxidation of toluene on the catalysts. Calcined MoO3 (10%)/Al2O3 shows only Mo(VI) on the surface at 300 K, but on heating to 670 K in vacuum shows the presence of a considerable proportion of Mo(V) which on cooling disproportionates to Mo(IV) and Mo(VI). Mo(V) is noticed on surfaces of this catalyst on reduction with hydrogen as also on carrying out dehydrogenation of cyclohexane. While Bi2MoO6 shows only Mo(VI) on the surface at 300 K, heating it to 670 K in vacuum changes it entirely to Mo(V) which then gives rise to Mo(IV) and Mo(VI) on cooling.

Effect of drying, storage temperature and air exposure on astaxanthin stability from Haematococcus pluvialis

Astaxanthin is a powerful antioxidant with various health benefits such as prevention of age-related macular degeneration and improvement of the immune system, liver and heart function. To improve the post-harvesting stability of astaxanthin used in food, feed and nutraceutical industries, the biomass of the high astaxanthin producing alga Haematococcus pluvialis was dried by spray- or freeze-drying and under vacuum or air at − 20 °C to 37 °C for 20 weeks. Freeze-drying led to 41 higher astaxanthin recovery compared to commonly-used spray-drying. Low storage temperature (− 20 °C, 4 °C) and vacuum-packing also showed higher astaxanthin stability with as little as 12.3 ± 3.1 degradation during 20 weeks of storage. Cost-benefit analysis showed that freeze-drying followed by vacuum-packed storage at − 20 °C can generate AUD600 higher profit compared to spray-drying from 100 kg H. pluvialis powder. Therefore, freeze-drying can be suggested as a mild and more profitable method for ensuring longer shelf life of astaxanthin from H. pluvialis.

Investigations of separated flow over backward facing steps in IISc hypersonic shock tunnel

Two backward facing step (2 mm and 3 mm step height) models are selected for surface heat transfer measurements. The platinum thin film gauges are deposited on the Macor inserts using both hand paint and vacuum sputtering technique. Using the Eckert reference temperature method the heating rates has been theoretically calculated along the flat plate portion of the model and the theoretical estimates are compared with experimentally determined surface heat transfer rate. Theoretical analysis of heat flux distribution down stream of the backward facing step model has been carried out using Gai’s non-dimensional analysis. Based on the measured surface heating rates on the backward facing step, the reattachment distance is estimated for 2 and 3 mm step height at nominal Mach number of 7.6. It has been found from the present study that for 2 and 3 mm step height, it approximately takes about 10 and 8 step heights downstream of the model respectively for the flow to re-attach.

Characterisation of wood–water relationships and transverse anatomy and their relationship to drying degrade

Characterisation of a number of key wood properties utilising ‘state of the art’ tools was achieved for four commercial Australian hardwood species: Corymbia citriodora, Eucalyptus pilularis, Eucalyptus marginata and Eucalyptus obliqua. The wood properties were measured for input into microscopic (cellular level) and macroscopic (board level) vacuum drying models currently under development. Morphological characterisation was completed using a combination of ESEM, optical microscopy and a custom vector-based image analysis software. A clear difference in wood porosity, size, wall thickness and orientation was evident between species. Wood porosity was measured using a combination of fibre and vessel porosity. A highly sensitive microbalance and scanning laser micrometres were used to measure loss of moisture content in conjunction with directional shrinkage on micro-samples of E. obliqua to investigate the validity of measuring collapse-free shrinkage in very thin sections. Collapse-free shrinkage was characterised, and collapse propensity was verified when testing thicker samples. Desorption isotherms were calculated for each species using wood–water relations data generated from shrinkage experiments. Fibre geometry and wood shrinkage anisotropy were used to explain the observed difficulty in drying of the different species in terms of collapse and drying stress-related degrade.

Thermal decomposition of rare-earth trioxalatocobaltates

The thermal decomposition of rare-earth trioxalatocobaltates LnCo(C2O4)3 · x H2O, where Ln = La, Pr, Nd, has been studied in flowing atmospheres of air/oxygen, argon/ nitrogen, carbon dioxide and a vacuum. The compounds decompose through three major steps, viz. dehydration, decomposition of the oxalate to an intermediate carbonate, which further decomposes to yield rare-earth cobaltite as the final product. The formation of the final product is influenced by the surrounding gas atmosphere. Studies on the thermal decomposition of photodecomposed lanthanum trioxalatocobaltate and a mechanical mixture of lanthanum oxalate and cobalt oxalate in 1 : 2 molar ratio reveal that the decomposition behaviour of the two samples is different. The drawbacks of the decomposition scheme proposed earlier have been pointed out, and logical schemes based on results obtained by TG, DTA, DTG, supplemented by various physico-chemical techniques such as gas and chemical analyses, IR and mass spectroscopy, surface area and magnetic susceptibility measurements and X-ray powder diffraction methods, have been proposed for the decomposition in air of rare-earth trioxalatocobaltates as well as for the photoreduced lanthanum salt and a mechanical mixture of lanthanum and cobalt oxalates.

Degenerate surface modes in a magnetized plasma

Electromagnetic surface waves propagating along the plasma-vacuum interface parallel to an applied magnetic field are studied. New modes for which the field components are degenerate, not reported in the earlier investigation of Kotsarenko and Fedorchenko (1969), are found and discussed. These modes, which propagate up to the plasma frequency for all values of the magnetic field, start as forward waves at low frequency but smoothly change into the backward mode as the frequency increases.

Incomplete decomposition of alkali metal azides

The thermal decomposition of sodium azide has been studied in the temperature range 240–360°C in vacuum and under pressure of an inert gas, argon. The results show that the decomposition is partial 360°C. From the observations made in the present work, namely: (i) the decomposition is incomplete both under vacuum and inert gas; (ii) mass spectrometric studies do not reveal any decrease in the intensity of the background species, CO+2, CO+, H2O+, and (iii) sodium metal remains in the ‘free state’ as seen by the formation of a metallic mirror at temperatures above 300°C, it has been argued that the partial nature of decompostion is due to the confinement of the decomposition to intermosaic regions within the lattice.

Thermal decomposition of titanyl oxalates II : Kinetics of decomposition of barium titanyl oxalate

Kinetics of the thermal decomposition of barium titanyl oxalate have been studied. Decomposition of the anhydrous oxalate is complex and deceleratory throughout. Kinetics of decomposition of the intermediate carbonate Ba2Ti2O5CO3 is greatly influenced by the thermal effects during its formation. The sigmoidal (α, t) curves obey a power law equation followed by first order decay. Presence of carbon in the vacuum prepared carbonate has a strong deactivating effect. Decomposition of the carbonate is accompanied by growth in particle size of the product, barium titanate.

Impulse Voltage Breakdown Characteristics of Point-Plane Gaps at Low Pressures

Practical applications of vacuum as an insulator necessitated determining the low-pressure breakdown characteristics of long gap lengths of a point-plane electrode system. The breakdown voltage has been found to vary as the square root of the gap length. Further, with the point electrode as the anode, the values of the breakdown voltages obtained have been found to be larger than those obtained with a plane-parallel electrode system at a corresponding gap length. By applying the theory of the anode heating mechanism as the cause for breakdown, the results have been justified, and by utilizing a field efficiency factor which is the ratio of the average to maximum field, an empirical criterion has been developed. This criterion helps in calculating the breakdown voltage of a nonuniform gap system by the knowledge of the breakdown voltage of a plane-parallel electrode system.

Effect of oxygen partial pressure on the growth of zinc micro and nanostructures

Zinc micro and nanostructures were synthesized in vacuum by condensing evaporated zinc on Si substrate at different gas pressures. The morphology of the grown Zn structures was found to be dependent on the oxygen partial pressure. Depending on oxygen partial pressure it varied from two-dimensional microdisks to one-dimensional nanowire. The morphology and structural properties of the grown micro and nanostructures were studied by scanning electron microscopy (SEM) and X-ray diffraction (XRD). Transmission electron microscopy (TEM) studies on the grown Zn nanowires have shown that they exhibit core/shell-like structures, where a thin ZnO layer forms the shell. A possible growth mechanism behind the formation of different micro and nanostructures has been proposed. In addition, we have synthesized ZnO nanocanal-like structures by annealing Zn nanowires in vacuum at 350 °C for 30 min.

Influence of Solvents on the MWCNT/Adhesive Grade Epoxy Nanocomposites Preparation

In this article, the effect of two solvents, namely dimethyl formamide (DMF) and N-methyl pyrrolidone (NMP), on the dispersion effectiveness and the resulting electrical and mechanical properties of multi-walled carbonanotubes (MNCNT) filled structural adhesive grade epoxy nanocomposites was studied. The solvents were used mainly to reduce the viscosity of the resin system to effectively disperse the nanofiller. The dispersion was carried out under vacuum using high energy sonic waves. SEM was undertaken to study the dispersion effectiveness. Electrical resistivity, tensile properties, and glass transition of the nanocomposites were studied. Between DMF and NMP, the former proved better in terms of dispersion effectiveness and the resulting electrical and mechanical properties of the nanocomposites. Addition of MWCNT into AV138M resulted in an increase in glass transition temperature irrespective of the solvent used and in both cases percolation threshold was found with respect to reduction in electrical resistivity of the nanocomposites. Less agglomeration and hence better interaction between CNT and epoxy was observed in the samples prepared using DMF compared with that using NMP.

The effect of lignin content and lignin modification on Norway spruce wood properties and decay resistance

Three different Norway spruce cutting clones growing in three environments with different soil and climatic conditions were studied. The purpose was to follow variation in the radial growth rate, wood properties and lignin content and to modify wood lignin with a natural monolignol, coniferyl alcohol, by making use of inherent wood peroxidases. In addition, the incorporation of chlorinated anilines into lignin was studied with synthetic model compounds and synthetic lignin preparations to show whether unnatural compounds originating from pesticides could be bound in the lignin polymer. The lignin content of heartwood, sapwood and earlywood was determined by applying Fourier transform infrared (FTIR) spectroscopy and a principal component regression (PCR) technique. Wood blocks were treated with coniferyl alcohol by using a vacuum impregnation method. The effect of impregnation was assessed by FTIR and by a fungal decay test. Trees from a fertile site showed the highest growth rate and sapwood lignin content and the lowest latewood proportion, weight density and modulus of rupture (MOR). Trees from a medium fertile site had the lowest growth rate and the highest latewood proportion, weight density, modulus of elasticity (MOE) and MOR. The most rapidly growing clone showed the lowest latewood proportion, weight density, MOE and MOR. The slowest growing clone had the lowest sapwood lignin content and the highest latewood proportion, weight density, MOE and MOR. Differences between the sites and clones were small, while fairly large variation was found between the individual trees and growing seasons. The cutting clones maintained clone-dependent wood properties in the different growing sites although variation between trees was high and climatic factors affected growth. The coniferyl alcohol impregnation increased the content of different lignin-type phenolic compounds in the wood as well as wood decay resistance against a white-rot fungus, Coriolus versicolor. During the synthetic lignin preparation 3,4-dichloroaniline became bound by a benzylamine bond to β-O-4 structures in the polymer and it could not be released by mild acid hydrolysis. The natural monolignol, coniferyl alcohol, and chlorinated anilines could be incorporated into the lignin polymer in vivo and in vitro, respectively.