Effect of contact surfaces on the thermal and photoxidation of dehydrated castor oil

The effect of stainless steel, glass, zirconium and titanium enamel surfaces on the thermal and photooxidative toughening mechanism of dehydrated castor oil films deposited on these surfaces was investigated using different analytical and spectroscopic methods. The conjugated and non-conjugated double bonds were identified and quantified using both Raman spectroscopy and 1D and 2D NMR spectroscopy. The disappearance of the double bonds in thermally oxidised oil-on-surface films was shown to be concomitant with the formation of hydroperoxides (determined by iodometric titration). The type of the surface had a major effect on the rate of thermal oxidation of the oil, but all of the surfaces examined had resulted in a significantly higher rate of oxidation compared to that of the neat oil. The highest effect was exhibited by the stainless steel surface followed by zirconium enamel, titanium enamel and glass. The rate of thermal oxidation of the oil-on-steel surface (at 100 °C, based on peroxide values) was more than five times faster than that of oil-on-glass and more than 21 times faster than the neat oil when compared under similar thermal oxidative conditions. The rate of photooxidation at 60 °C of oil-on-steel films was found to be about one and half times faster than their rate of thermal oxidation at the same temperature. Results from absorbance reflectance infrared microscopy with line scans taken across the depth of thermally oxidised oil-on-steel films suggest that the thermal oxidative toughening mechanism of the oil occurs by two different reaction pathways with the film outermost layers, i.e. furthest away from the steel surface, oxidising through a traditional free radical oxidation process involving the formation of various oxygenated products formed from the decomposition of allylic hydroperoxides, whereas, in the deeper layers closer to the steel surface, crosslinking reactions predominate.

Refractive error, cognitive demand and nearwork-induced transient myopia

Purpose. Whereas many previous studies have identified the association between sustained near work and myopia, few have assessed the influence of concomitant levels of cognitive effort. This study investigates the effect of cognitive effort on near-work induced transient myopia (NITM). Methods. Subjects comprised of six early onset myopes (EOM; mean age 23.7 yrs; mean onset 10.8 yrs), six late-onset myopes (LOM; mean age 23.2 yrs; mean onset 20.0 yrs) and six emmetropes (EMM; mean age 23.8 yrs). Dynamic, monocular, ocular accommodation was measured with the Shin-Nippon SRW-5000 autorefractor. Subjects engaged passively or actively in a 5 minute arithmetic sum checking task presented monocularly on an LCD monitor via a Badal optical system. In all conditions the task was initially located at near (4.50 D) and immediately following the task instantaneously changed to far (0.00 D) for a further 5 minutes. The combinations of active (A) and passive (P) cognition were randomly allocated as P:P; A:P; A:A; P:A. Results. For the initial near task, LOMs were shown to have a significantly less accurate accommodative response than either EOMs or EMMs (p < 0.001). For the far task, post hoc analyses for refraction identified EOMs as demonstrating significant NITM compared to LOMs (p < 0.05), who in turn showed greater NITM than EMMs (p < 0.001). The data show that for EOMs the level of cognitive activity operating during the near and far tasks determines the persistence of NITM; persistence being maximal when active cognition at near is followed by passive cognition at far. Conclusions. Compared with EMMs, EOMs and LOMs are particularly susceptible to NITM such that sustained near vision reduces subsequent accommodative accuracy for far vision. It is speculated that the marked NITM found in EOM may be a consequence of the crystalline lens thinning shown to be a developmental feature of EOM. Whereas the role of small amounts of retinal defocus in myopigenesis remains equivocal, the results show that account needs to be taken of cognitive demand in assessing phenomena such as NITM.

Ion bombardment induced compositional changes in compound semiconductor surfaces studied by XPS combined with LEISS

Surface compositional change of GaP, GaAs, GaSb, InP, InAs, InSb, GeSi and CdSe single crystals due to low keV noble gas ion beam bombardment has been investigated by combining X-ray Photoelectron Spectroscopy (XPS) and Low Energy Ion Scattering Spectroscopy (LEISS). The purpose of using this complementary analytical method is to obtain more complete experimental evidence of ion beam modification in surfaces of compound semiconductors and GeSi alloy to improve the understanding of the mechanisms responsible for these effects. Before ion bombardment the sample surfaces were analysed nondestructively by Angular Resolved XPS (ARXPS) and LEISS to get the initial distribution of surface composition. Ion bombardment experiments were carried out using 3keV argon ions with beam current of 1μA for a period of 50 minutes, compositional changes in the surfaces of compound semiconductors and GeSi alloy were monitored with normal XPS. After ion bombardment the surfaces were re-examined with ARXPS and LEISS. Both XPS and LEISS results showed clearly that ion bombardment will change the compositional distribution in the compound semiconductor and GeSi surfaces. In order to explain the observed experimental results, two major theories in this field, Sigmund linear collision cascade theory and the thermodynamic models based on bombardment induced Gibbsian surface segregation and diffusion, were investigated. Computer simulation using TRIM code was also carried out for assistance to the theoretical analysis. Combined the results obtained from XPS and LEISS analyses, ion bombardment induced compositional changes in compound semiconductor and GeSi surfaces are explained in terms of the bombardment induced Gibbsian surface segregation and diffusion.

Spectroscopic studies of field-induced electron emission from isolated microstructures

A detailed investigation has been undertaken into the field induced electron emission (FIEE) mechanism that occurs at microscopically localised `sites' on uncoated and dielectric coated metallic electrodes. These processes have been investigated using two dedicated experimental systems that were developed for this study. The first is a novel combined photo/field emission microscope, which employs a UV source to stimulate photo-electrons from the sample surface in order to generate a topographical image. This system utilises an electrostatic lens column to provide identical optical properties under the different operating conditions required for purely topographical and combined photo/field imaging. The system has been demonstrated to have a resolution approaching 1m. Emission images have been obtained from carbon emission sites using this system to reveal that emission may occur from the edge triple junction or from the bulk of the carbon particle. An existing UHV electron spectrometer has been extensively rebuilt to incorporate a computer control and data acquisition system, improved sample handling and manipulation and a specimen heating stage. Details are given of a comprehensive study into the effects of sample heating on the emission process under conditions of both bulk and transient heating. Similar studies were also performed under conditions of both zero and high applied field. These show that the properties of emission sites are strongly temperature and field dependent thus indicating that the emission process is `non-metallic' in nature. The results have been shown to be consistent with an existing hot electron emission model.

NMR spectroscopy in the presence of ultrasound and other perturbations

The work described in this thesis has been concerned with exploring the potential uses of ultrasound in Nuclear Magnetic Resonance (NMR) spectroscopy, The NMR spectra of liquids provide detailed structural information that may be deduced from the chemical shifts and spin-spin coupling, that are evident in the narrow resonances, arising from some of the nuclear broadening interactions being reduced to zero. In the solid state, all of the nuclear broadening interactions are present and broad lines in the NMR spectrum are observed. Current techniques employed to reduce the line widths in solids are based on coherent averaging techniques such as MAS NMR1,2 which can remove first order interactions. Recently DOR3 and DAS4 have become available to remove higher order interactions. SINNMR (Sonically Induced Narrowing of the NMR spectra of solids) has been reported by Homer et al5 and developed by Homer and Howard6 to reduce the line widths of solids. The basis of their work is the proposal that a colloidal suspension of solid particles can be made to move like large molecules by using ultrasonic agitation. The advantage of the technique is that the particles move incoherently removing all of the nuclear interactions responsible for broad lines. This thesis describes work on the extension of SINNMR by showing that the line width of 27AI and 11B for the glass Na20/B203/AI203 can be reduced by placing solid particles in a colloidal suspension. Further line width reduction is possible by applying ultrasound, at 2 MHz, of sufficient intensity. It is proposed that a cavitation field is responsible for imparting sufficient rotational motion to the solid particles to partially average the nuclear interactions responsible for broad lines. Rapid stirring of the colloidal suspension generates turbulent flow, however, the motion is insufficient to narrow the line widths for 27AI in the glass. Investigations of sonochemical reactions for in situ rate measurements by NMR have been made. 8y using the Weissler reaction7, it has been shown that ultrasonic cavitation is possible up to 10MHz. Preliminary studies have been carried out into the rate of ultrasonic polymerisation of methylmethacrylate by NMR. Long range order in liquid crystals can imposed when they are aligned in the presence a magnetic field. The degree of alignment can be monitored by NMR using, for example a deuterated solute added to the liquid crystal8. Ultrasonic streaming can then be employed to deflect the directors of the liquid crystal from their equilibrium position, resulting in a change In the NMR spectrum. The angle of deflection has been found for the thermotropic liquid crystal (I35) to be ca, 35° and for the lyotropic (ZLI-1167) to be ca, 20°, Mechanical stirring can used to re- orientate the liquid crystal but was found to give a smaller deflection, In a separate study, that did not use ultrasound, it has been found that the signal to noise ratio of 13C NMR signals can be enhanced by rapidly stirring a Iiquid. Accelerating the diffusion of nuclei out of the coil region enables M0 to be re-established more rapidly than the normal relaxation process. This allows the pulse repetition rate to be reduced without saturating the spin system. The influence of varying the relaxation delay, acquisition time and inter-pulse delay have been studied and parameters optimised. By studying cholesterol the technique was found to be most effective for nuclei with long relaxation times, such as quaternary carbon sites. Key Worde: NMR, Ulf.rasciund, 1,.lqi.fi!:l cryllltalt!h SCll1C1otlemlstryl I!r1hano~d algnflllf

A method of fundamental solutions for transient heat conduction in layered materials

In this paper we investigate an application of the method of fundamental solutions (MFS) to transient heat conduction in layered materials, where the thermal diffusivity is piecewise constant. Recently, in Johansson and Lesnic [A method of fundamental solutions for transient heat conduction. Eng Anal Boundary Elem 2008;32:697–703], a MFS was proposed with the sources placed outside the space domain of interest, and we extend that technique to numerically approximate the heat flow in layered materials. Theoretical properties of the method, as well as numerical investigations are included.

Nearwork-induced transient myopia (NITM) in anisometropia

Objective: To assess the magnitude of nearwork-induced transient myopia (NITM) under binocular viewing conditions separately in each eye of individuals with mild to moderate anisometropia to determine the relationship between NITM and their interocular refractive error. Methods: Forty-three children and young adults with anisometropia [cycloplegic spherical equivalent (SE) difference >1.00 D] were tested (ages 9-28 years). NITM was measured with binocular viewing separately in each eye after binocularly performing a sustained near task (5 D) for 5 min incorporating a cognitive demand using an open-field, infrared autorefractor (Grand-Seiko, WAM-5500). Data were averaged over 10 s bins for 3 min in each eye. Initial NITM, its decay time (DT), and its decay area (DA) were determined. A-scan ultrasound ocular biometry was also performed to determine the axial length of each eye. Results: The more myopic eye exhibited increased initial NITM, DT, and DA as compared to the less myopic eye (0.21 ± 0.16 D vs 0.15 ± 0.13 D, p = 0.026; 108.4 ± 64.3 secs vs 87.0 ± 65.2 secs, p = 0.04; and 17.6 ± 18.7 D*secs vs 12.3 ± 15.7 D*secs, p = 0.064), respectively. The difference in DA and the difference in SE between the more versus less myopic eye were significantly correlated (r = 0.31, p = 0.044). Furthermore, 63% (27/43), 56% (24/43), and 70% (30/43) of the more myopic eyes exhibited increased initial NITM, longer DT, and larger DA, respectively, than found in the less myopic eye. Conclusions: In approximately two-thirds of the anisometropic individuals, the initial NITM and its decay area were significantly increased in the more myopic eye as compared to the less myopic eye. NITM may play an important role in the development of interocular differences in myopia, although a causal relationship is yet to be established. Furthermore, the findings have potentially important implications regarding accommodative control and interocular accommodative responsitivity in anisometropia, in particular for anisomyopia. © 2013 The College of Optometrists.

Nearwork-induced transient myopia in preadolescent Hong Kong Chinese

PURPOSE. To compare the magnitude and time course of nearwork-induced transient myopia (NITM) in preadolescent Hong Kong Chinese myopes and emmetropes. METHOD. Forty-five Hong Kong Chinese children, 35 myopes and 10 emmetropes aged 6 to 12 years (median, 7.5), monocularly viewed a letter target through a Badal lens for 5 minutes at either 5.00- or 2.50-D accommodative demand, followed by 3 minutes of viewing the equivalent target at optical infinity. Accommodative responses were measured continuously with a modified, infrared, objective open-field autorefractor. Accommodative responses were also measured for a countercondition: viewing of a letter target for 5 minutes at optical infinity, followed by 3 minutes of viewing the target at a 5.00-D accommodative demand. The results were compared with tonic accommodation and both subject and family history of refractive error. RESULTS. Retinal-blur-driven NITM was significantly greater in Hong Kong Chinese children with myopic vision than in the emmetropes after both near tasks, but showed no significant dose effect. The NITM was still evident 3 minutes after viewing the 5.00-D near task for 5 minutes. The magnitude of NITM correlated with the accommodative drift after viewing a distant target for more than 4 minutes, but was unrelated to the subjects' or family history of refractive error. CONCLUSIONS. In a preadolescent ethnic population with known predisposition to myopia, there is a significant posttask blur-driven accommodative NITM, which is sustained for longer than has previously been found in white adults.

Laser-induced breakdown spectroscopy quantitative analysis method via adaptive analytical line selection and relevance vector machine regression model

Abstract A new LIBS quantitative analysis method based on analytical line adaptive selection and Relevance Vector Machine (RVM) regression model is proposed. First, a scheme of adaptively selecting analytical line is put forward in order to overcome the drawback of high dependency on a priori knowledge. The candidate analytical lines are automatically selected based on the built-in characteristics of spectral lines, such as spectral intensity, wavelength and width at half height. The analytical lines which will be used as input variables of regression model are determined adaptively according to the samples for both training and testing. Second, an LIBS quantitative analysis method based on RVM is presented. The intensities of analytical lines and the elemental concentrations of certified standard samples are used to train the RVM regression model. The predicted elemental concentration analysis results will be given with a form of confidence interval of probabilistic distribution, which is helpful for evaluating the uncertainness contained in the measured spectra. Chromium concentration analysis experiments of 23 certified standard high-alloy steel samples have been carried out. The multiple correlation coefficient of the prediction was up to 98.85%, and the average relative error of the prediction was 4.01%. The experiment results showed that the proposed LIBS quantitative analysis method achieved better prediction accuracy and better modeling robustness compared with the methods based on partial least squares regression, artificial neural network and standard support vector machine.

A laser induced breakdown spectroscopy quantitative analysis method based on the robust least squares support vector machine regression model

Data fluctuation in multiple measurements of Laser Induced Breakdown Spectroscopy (LIBS) greatly affects the accuracy of quantitative analysis. A new LIBS quantitative analysis method based on the Robust Least Squares Support Vector Machine (RLS-SVM) regression model is proposed. The usual way to enhance the analysis accuracy is to improve the quality and consistency of the emission signal, such as by averaging the spectral signals or spectrum standardization over a number of laser shots. The proposed method focuses more on how to enhance the robustness of the quantitative analysis regression model. The proposed RLS-SVM regression model originates from the Weighted Least Squares Support Vector Machine (WLS-SVM) but has an improved segmented weighting function and residual error calculation according to the statistical distribution of measured spectral data. Through the improved segmented weighting function, the information on the spectral data in the normal distribution will be retained in the regression model while the information on the outliers will be restrained or removed. Copper elemental concentration analysis experiments of 16 certified standard brass samples were carried out. The average value of relative standard deviation obtained from the RLS-SVM model was 3.06% and the root mean square error was 1.537%. The experimental results showed that the proposed method achieved better prediction accuracy and better modeling robustness compared with the quantitative analysis methods based on Partial Least Squares (PLS) regression, standard Support Vector Machine (SVM) and WLS-SVM. It was also demonstrated that the improved weighting function had better comprehensive performance in model robustness and convergence speed, compared with the four known weighting functions.