An XPS study of pulsed plasma polymerised allyl alcohol film growth on polyurethane

The growth of highly functionalised poly allyl alcohol films by pulsed plasma polymerisation of CH2 double bond; length as m-dashCHCH2OH on biomedical grade polyurethane has been followed by X-ray photoelectron spectroscopy (XPS) and contact angle measurements. Film thickness is observed to increase approximately linearly with plasma modification time, suggesting a layer-by-layer growth mode of poly allyl alcohol. Water contact angle measurements reveal the change in the surface free energy of wetting decreases linearly with plasma modification up to the monolayer point after which a constant limiting value of −24 mJ m−2 was attained. Films prepared at 20 W plasma power with a duty cycle of 10 μs:500 μs exhibit a high degree of hydroxyl (single bondOH) retention with minimal fragmentation of the monomer observed. Increasing the plasma power up to 125 W is found to improve single bondOH retention at the expense of ether formation generating films close to the monomer stoichiometry. Duty cycle plays an important role in controlling both film composition and thickness, with longer off times increasing single bondOH retention, while longer on times enhance allyl alcohol film growth.

Nanoscratch and nanowear testing of TiN coatings on M42 steel

Constant load, progressive load and multipass nanoscratch (nanowear) tests were carried out on 500 and 1500 nm TiN coatings on M42 steel chosen as model systems. The influences of film thickness, coating roughness, scratch direction relative to the grinding grooves on the critical load in the progressive load test and number of cycles to failure in the wear test have been determined. Progress towards the development of a suitable methodology for determining the scratch hardness from nanoscratch tests is discussed. © 2011 W. S. Maney & Son Ltd.

An investigation of thin amorphous carbon-based sputtered coatings for MEMS and micro-engineering applications

The work presented in this thesis describes an investigation into the production and properties of thin amorphous C films, with and without Cr doping, as a low wear / friction coating applicable to MEMS and other micro- and nano-engineering applications. Firstly, an assessment was made of the available testing techniques. Secondly, the optimised test methods were applied to a series of sputtered films of thickness 10 - 2000 nm in order to: (i) investigate the effect of thickness on the properties of coatingslcoating process (ii) investigate fundamental tribology at the nano-scale and (iii) provide a starting point for nanotribological coating optimisation at ultra low thickness. The use of XPS was investigated for the determination of Sp3/Sp2 carbon bonding. Under C 1s peak analysis, significant errors were identified and this was attributed to the absence of sufficient instrument resolution to guide the component peak structure (even with a high resolution instrument). A simple peak width analysis and correlation work with C KLL D value confirmed the errors. The use of XPS for Sp3/Sp2 was therefore limited to initial tentative estimations. Nanoindentation was shown to provide consistent hardness and reduced modulus results with depth (to < 7nm) when replicate data was suitably statistically processed. No significant pile-up or cracking of the films was identified under nanoindentation. Nanowear experimentation by multiple nanoscratching provided some useful information, however the conditions of test were very different to those expect for MEMS and micro- / nano-engineering systems. A novel 'sample oscillated nanoindentation' system was developed for testing nanowear under more relevant conditions. The films were produced in an industrial production coating line. In order to maximise the available information and to take account of uncontrolled process variation a statistical design of experiment procedure was used to investigate the effect of four key process control parameters. Cr doping was the most significant control parameter at all thicknesses tested and produced a softening effect and thus increased nanowear. Substrate bias voltage was also a significant parameter and produced hardening and a wear reducing effect at all thicknesses tested. The use of a Cr adhesion layer produced beneficial results at 150 nm thickness, but was ineffective at 50 nm. Argon flow to the coating chamber produced a complex effect. All effects reduced significantly with reducing film thickness. Classic fretting wear was produced at low amplitude under nanowear testing. Reciprocating sliding was produced at higher amplitude which generated three body abrasive wear and this was generally consistent with the Archard model. Specific wear rates were very low (typically 10-16 - 10-18 m3N-1m-1). Wear rates reduced exponentially with reduced film thickness and below (approx.) 20 nm, thickness was identified as the most important control of wear.

Influence of pretreatment on corrosion behaviour of duplex zinc/polymer coatings on steel substrates

An investigation has been undertaken to determine the major factors influencing the corrosion resistance of duplex-zinc coatings on steel substrates.Premature failure of these systems has been attributed to the presence of defects such as craters and pinholes in the polymer film and debonding of the polymer film from the zinc substrate.Defects found on commercially produced samples have been carefully characterised using metallographic and scanning electron microscopy techniques. The influence of zinc substrate surface roughness, polymer film thickness and degassing of conversion coatings films on the incidence of defects has been determined.Pretreatments of the chromate, chromate-phosphate, non chromate, and alkali-oxide types were applied and the conversion coatings produced characterised with respect to their nature and composition. The effect of degassing on the properties of the films was also investigated. Electrochemical investigations were carried out to determine the effect of the presence of the eta or zeta phase as the outermost layer of the galvanized coating.Flow characteristics of polyester on zinc electroplated hot-dip continuous and batch galvanized and zinc sprayed samples were investigated using hot-stage microscopy. The effects of different pretreatments and degassing after conversion coating formation on flow characteristics were determined.Duplex coatings were subjected to the acetic acid salt spray test. The effect on adhesion was determined using an indentation debonding test and the results compared with those obtained using cross-cut/peel and pull-off tests. The locus of failure was determined using scanning electron microscopy and X-ray photoelectron spectroscopy techniques.

Size-dependent radiation tolerance in ion irradiated TiN/AlN nanolayer films

Interface effects on ion-irradiation tolerance properties are investigated in nanolayered TiN/AlN films with individual layer thickness varied from 5 nm to 50 nm, prepared by pulsed laser deposition. Evolution of the microstructure and hardness of the multilayer films are examined on the specimens before and after He ion-implantation to a fluence of 4 × 10 m at 50 keV. The suppression of amorphization in AlN layers and the reduction of radiation-induced softening are observed in all nanolayer films. A clear size-dependent radiation tolerance characteristic is observed in the nanolayer films, i.e., the samples with the optimum layer thickness from 10 nm to 20 nm show the best ion irradiation tolerance properties, and a critical layer thickness of more than 5 nm is necessary to prevent severe intermixing. This study suggests that both the interface characteristics and the critical length scale (layer thickness) contribute to the reduction of the radiation-induced damages in nitride-based ceramic materials. © 2013 Elsevier B.V. All rights reserved.

Direct measurement of coherency limits for strain relaxation in heteroepitaxial core/shell nanowires

The growth of heteroepitaxially strained semiconductors at the nanoscale enables tailoring of material properties for enhanced device performance. For core/shell nanowires (NWs), theoretical predictions of the coherency limits and the implications they carry remain uncertain without proper identification of the mechanisms by which strains relax. We present here for the Ge/Si core/shell NW system the first experimental measurement of critical shell thickness for strain relaxation in a semiconductor NW heterostructure and the identification of the relaxation mechanisms. Axial and tangential strain relief is initiated by the formation of periodic a/2 〈110〉 perfect dislocations via nucleation and glide on {111} slip-planes. Glide of dislocation segments is directly confirmed by real-time in situ transmission electron microscope observations and by dislocation dynamics simulations. Further shell growth leads to roughening and grain formation which provides additional strain relief. As a consequence of core/shell strain sharing in NWs, a 16 nm radius Ge NW with a 3 nm Si shell is shown to accommodate 3% coherent strain at equilibrium, a factor of 3 increase over the 1 nm equilibrium critical thickness for planar Si/Ge heteroepitaxial growth. © 2012 American Chemical Society.

Anterior ophthalmic imaging

Improvements in imaging chips and computer processing power have brought major advances in imaging of the anterior eye. Digitally captured images can be visualised immediately and can be stored and retrieved easily. Anterior ocular imaging techniques using slitlamp biomicroscopy, corneal topography, confocal microscopy, optical coherence tomography (OCT), ultrasonic biomicroscopy, computerised tomography (CT) and magnetic resonance imaging (MRI) are reviewed. Conventional photographic imaging can be used to quantify corneal topography, corneal thickness and transparency, anterior chamber depth and lateral angle and crystalline lens position, curvature, thickness and transparency. Additionally, the effects of tumours, foreign bodies and trauma can be localised, the corneal layers can be examined and the tear film thickness assessed. © 2006 The Authors.

Electrografting of poly (carbazole-co-acrylamide) onto highly oriented pyroltic graphite. A cyclovoltammetric, atomic force microscopic and ellipsometric study

The electrocopolymerization of carbazole and acrylamide on highly oriented pyrolytic graphite (HOPG) from ACN solutions via cyclovoltammetry (CV) was studied in order to evaluate the possibility to deposit uniform and thin but pinhole-free and still reactive coatings onto graphite-like substrates. The morphology of the coatings was investigated using atomic force microscopy and the coating thicknesses and optical parameters were measured using ellipsometry. It was found that under the chosen conditions thin (coating thickness hf>180 nm) and relatively smooth (root mean square surface roughness RMS<150 nm) P(Cz-co-AAm)-coatings exhibiting a uniform globuoidal morphology can be deposited onto graphite. From a certain coating thickness (hf>50 nm) no pinholes could be detected. It was found that the thickness of the deposited coatings increases almost linearly with increasing number of CV-cycles while keeping all other experimental parameters (scan rate and comonomer concentration ratio) constant. No influence of the comonomer concentration ratio on the film thickness and coating appearance could be observed, however, at quite low initial concentrations. However, the CV-scanning rate has quite a significant influence on the thickness of the deposited coatings. Higher scan rates (100 mV/s) result in thin (hf≈22 nm) coatings whereas at lower scan rates (<50 mV/s) coatings with thicknesses of approximately 50 nm were obtained. The optical coating parameters (the refractive index n and extinction coefficient k) seem to be independent of the deposition parameters and therefore averaged values of n̄=1.54±0.03 and k̄=0.08±0.03 were obtained.

Hydrothermally stable, conformal, sulfated zirconia monolayer catalysts for glucose conversion to 5-HMF

The grafting and sulfation of zirconia conformal monolayers on SBA-15 to create mesoporous catalysts of tunable solid acid/base character is reported. Conformal zirconia and sulfated zirconia (SZ) materials exhibit both Brönsted and Lewis acidity, with the Brönsted/Lewis acid ratio increasing with film thickness and sulfate content. Grafted zirconia films also exhibit amphoteric character, whose Brönsted/Lewis acid site ratio increases with sulfate loading at the expense of base sites. Bilayer ZrO2/SBA-15 affords an ordered mesoporous material with a high acid site loading upon sulfation and excellent hydrothermal stability. Catalytic performance of SZ/SBA-15 was explored in the aqueous phase conversion of glucose to 5-HMF, delivering a 3-fold enhancement in 5-HMF productivity over nonporous SZ counterparts. The coexistence of accessible solid basic/Lewis acid and Brönsted acid sites in grafted SZ/SBA-15 promotes the respective isomerization of glucose to fructose and dehydration of reactively formed fructose to the desired 5-HMF platform chemical.

Cling film as a barrier against CJD in corneal contact A-scan ultrasonography

Purpose: To determine the validity of covering a corneal contact transducer probe with cling film as protection against the transmission of Creutzfeldt-Jakob disease (CJD). Methods: The anterior chamber depth, lens thickness and vitreous chamber depth of the right eyes of 10 subjects was recorded, under cycloplegia, with and without cling film covering over the transducer probe of a Storz Omega Compu-scan Biometric Ruler. Measurements were repeated on two occasions. Results: Cling film covering did not influence bias or repeatability. Although the 95% limits of agreement between measurements made with and without cling film covering tended to exceed the intrasessional repeatability, they did not exceed the intersessional repeatability of measurements taken without cling film. Conclusions: The results support the use of cling film as a disposable covering for corneal contact A-scan ultrasonography to avoid the risk of spreading CJD from one subject to another. © 2003 The College of Optometrists.

An investigation of thin film magnetic recording media

Mechanical, physical and chemical changes in the surface of commercial thin film metal evaporated magnetic recording media have been correlated to recording error and signal degradation measurements. Modified and adapted commercial Hi-8 video recorders have been used for sample generation whilst analytical techniques such as SXPS,IMS and SEM have been employed in the surface characterisation. The durability of the media was assessed through stop motion (still frame) and cycling tests, where error growth and signal degradation were measured as a function of running time. The tests were performed under ambient (22°C, 40% RH) and high humidity (22°C, 80% RH) conditions. Characterisation of the lubricant layer on each tape was performed through models based on XPS and angle resolved XPS. The lubricant thickness can significantly affect the durability and signal output level of a thin film tape and thus it is important that reliable quantification can be achieved. Various models were considered for determining the lubricant thickness although ultimately, the most suitable technique was deemed to be a model that assumed a uniform layer structure. In addition to thin film metal evaporated media, equivalent durability tests and surface analysis experiments were performed using a commercial metal particle tape in order that comparisons could be made between the two types of recording media. The signal performance of the thin film metal evaporated media was found to be quite different from that for the metal particle tape since dropout errors and signal degradation increased at a much earlier stage. Extensive surface analyses enabled the mechanisms responsible for media failure and error growth to be identified in the ME and MP tapes and these were found to result from cyclic stressing and fatigue on the immediate substrate of the media.

Effect of a liposomal spray on the pre-ocular tear film

Purpose: With the potential to address evaporative dry eye, a novel spray has been developed in which phospholipid liposomes are delivered to the tear film via the surface of the closed eyelid. This study evaluated the short-term effects of liposomal spray application on the lipid and stability characteristics of the pre-ocular tear film in normal eyes. Methods: Twenty-two subjects (12M, 10F) aged 35.1 ± 7.1 years participated in this prospective, randomised, double-masked investigation in which the liposomal spray was applied to one eye, and an equal volume of saline spray (control) applied to the contralateral eye. Lipid layer grade (LLG), non-invasive tear film stability (NIBUT) and tear meniscus height (TMH) were evaluated at baseline, and at 30, 60, 90 and 135 minutes post-application. Subjective reports of comfort were also compared. Results: Treated and control eyes were not significantly different at baseline (p>0.05). Post-application, LLG increased significantly, at 30 and 60 minutes, only in the treated eyes (p=0.005). NIBUT also increased significantly in the treated eyes only (p<0.001), at 30, 60 and 90 minutes. TMH did not alter significantly (p>0.05). Comfort improved relative to baseline in 46% of treated and 18% of control eyes, respectively, at 30 minutes post-application. Of those expressing a preference in comfort between the eyes, 68% preferred the liposomal spray. Conclusions: Consistent with subjective reports of improved comfort, statistically and clinically significant improvements in lipid layer thickness and tear film stability are observed in normal eyes for at least an hour after a single application of a phospholipid liposomal spray.

Making political films politically?:the film-making practice of Jean-Luc Godard

This thesis attempts to re-examine the work of Jean-Luc Godard and in particular the claims which have been made for it as the starting-point for a revolutionary cinema.This re-examination involves, firstly, a critical summary of the development of Structuralist thinking, from its origins in linguistics, with Saussure, through to its influence on Marxism, with Althusser. It is this `Structural Marxism' which prepared the ground for a view of Godard as a revolutionary film-maker so its influences on film theory in the decade after 1968 is traced in journals such as Cahiers du Cinéma and Screen and in the work of their editors and contributors. Godard's relationship with such theories was a complex one and some of the cross-breeding is revealed in a brief account of his own ideas about his film-making. More important, however is his practice as a committed `political' film-maker between 1968 and 1972 which is analysed in terms of the responses it makes to the cultural opportunities offered in the period after the revolutionary situation of May 1968. The severe problems revealed by that analysis may be partially resolved in Godard's greatest `political' achievement Tout va bien, but a comparative analysis proves that in earlier `a-political' films such as Vivre sa vie, he was creating more meaningful and perhaps even more revolutionary art, whose formal experimentation is more organically linked to its subject and whose ability to communicate ideas far oustrips the later work. In conclusion some indications are suggested of a more fruitful basis for Marxist theories of art than Structural variants, seeking a non-formalist approach in the work of Marx, of Trotsky, of Brecht and Lukacs.

Polymer film formulations for the preparation of enteric pharmaceutical capsules

Objectives. Standard pharmaceutical capsules are designed to dissolve in the acidic environment of the stomach releasing the encapsulated contents for absorption. When release is required further along the gastrointestinal tract capsules can be coated with acid insoluble polymers to enable passage through the stomach and dissolution in the intestine. This paper describes formulations that have the potential to be used to produce two-piece hard capsules for post-gastric delivery without the requirement of an exterior coat. Methods. The formulation uses three polysaccharides: sodium alginate, hypromellose and gellan gum to provide acid insolubility and the ability to form capsules using standard industrial equipment. Key findings. The rheological profile, on cooling, of the base material, water content and thickness of the films were shown to be comparable with those of commercial capsules. The capsules remained intact for 2 h in 100 mm HCl at pH 1.2, and within 5 min of being removed from the acid and submerged in phosphate-buffered saline at pH 6.8 were ruptured. Conclusions. Selected formulations from this study have potential for use as delayed release capsules.

Thin film bearings with phase change of lubricant

The possible evaporation of lubricant in fluid film bearings has been investigated theoretically and by experiment using a radial flow hydrostatic bearing supplied with liquid refrigerant R114. Good correlation between measured and theoretical values was obtained using a bespoke computational fluid dynamic model in which the flow was assumed to be laminar and adiabatic. The effects of viscous dissipation and vapour generation within the fluid film are fully accounted for by applying a fourth order Runge-Kutta routine to satisfy the radial and filmwise transverse constraints of momentum, energy and mass conservation. The results indicate that the radial velocity profile remains parabolic while the flow remains in the liquid phase and that the radial rate of enthalpy generation is then constant across the film at a given radius. The results also show that evaporation will commence at a radial location determined by geometry and flow conditions and in fluid layers adjacent to the solid boundaries. Evaporation is shown to progress in the radial direction and the load carrying capacity of such a bearing is reduced significantly. Expressions for the viscosity of the liquid/vapour mixture found in the literature survey have not been tested against experimental data. A new formulation is proposed in which the suitable choice of a characteristic constant yields close representation to any of these expressions. Operating constraints imposed by the design of the experimental apparatus limited the extent of the surface over which evaporation could be obtained, and prevented clear identification of the most suitable relationship for the viscosity of the liquid/vapour mixture. The theoretical model was extended to examine the development of two phase flow in a rotating shaft face seal of uniform thickness. Previous theoretical analyses have been based on the assumption that the radial velocity profile of the flow is always parabolic, and that the tangential component of velocity varies linearly from the value at the rotating surface, to zero at the stationary surface. The computational fluid dynamic analysis shows that viscous shear and dissipation in the fluid adjacent to the rotating surface leads to developing evaporation with a consequent reduction in tangential shear forces. The tangential velocity profile is predicted to decay rapidly through the film, exhibiting a profile entirely different to that assumed by previous investigators. Progressive evaporation takes place close to the moving wall and does not occur completely at a single radial location, as has been claimed in earlier work.