Dehydration at the lens surface:surface energy and surfactant persistence

Purpose: Most published surface wettability data are based on hydrated materials and are dominated by the air-water interface. Water soluble species with hydrophobic domains (such as surfactants) interact directly with the hydrophobic domains in the lens polymer. Characterisation of relative polar and non-polar fractions of the dehydrated material provides an additional approach to surface analysis. Method: Probe liquids (water and diiodomethane) were used to characterise polar and dispersive components of surface energies of dehydrated lenses using the method of Owens and Wendt. A range of conventional and silicone hydrogel soft lenses was studied. The polar fraction (i.e. polar/total) of surface energy was used as a basis for the study of the structural effects that influence surfactant persistence on the lens surface. Results: When plotted against water content of the hydrated lens, polar fraction of surface energy (PFSE) values of the dehydrated lenses fell into two rectilinear bands. One of these bands covered PFSE values ranging from 0.4 to 0.8 and contained only conventional hydrogels, with two notable additions: the plasma coated silicone hydrogels lotrafilcon A and B. The second band covered PFSE values ranging from 0.04 to 0.28 and contained only silicone hydrogels. Significantly, the silicone hydrogel lenses with lowest PFSE values (p<0.15) are found to be prone to lipid deposition duringwear. Additionally, more hydrophobic surfactants were found to be more persistent on lenses with lower PFSE values. Conclusions: Measurement of polar fraction of surface energy provides an importantmechanistic insight into surface interactions of silicone hydrogels.

Novel hydrogels for keratoprosthesis

Hydrogels may be described as cross~linked hydrophilic polymers that swell but do not dissolve in water. They have been utilised in many biomedical applications, as there is the potential to manipulate the properties for a given application by changing the chemical structure of the constituent monomers. This project is focused on the development of novel hydrogels for keratoprosthesis (KPro). The most commonly used KPro model consists of a tansparent central stem witb a porous peripheral skirt. Clear poly (methyl methacrylate) (PMMA) core material used in the Strampelli KPros prosthesis has not been the cause of failure found in other core and skirt prostheses. However, epithelialization of this kind of solid, rigid optic material is clearly impossible. The approach to the development of a hydrogeJ for potential KPro use adopted in this work is to develop soft core material to mimic the properties of the natural cornea by incorporating some hydrophilic monomers such as N, N-dimethyacrylamide (NNSMA) N~vinyl pyrrolidone (NVP) and acryloylmorpholine (AMO) with methyl methactylate (MMA). Most of these materials have been used in other ophthalmic applications, such as contact lens. However, an unavoidable limitation of simple .MMA copolymers as conventional hydrogels is poor mechanical strength. The hydrogel for use in this application must be able to withstand the stresses involved during the surgical procedure involved with KPro surgery and the in situ stresses such as the deforming force of the eyelid during the blink cycle. Thus, semi-interpenetrating polymer networks (SIPNs) based on ester polyurethane, AMO, NVP and NNDMA were examined in this work and were found to have much improved mechanical properties at water contents between 40% and 70%. Polyethylene glycol monomethacrylate (PEG MA) was successfully incorporated in order to modulate protein deposition and cell adhesion. Porous peripheral skirts were fabricated using different types of porosigen. The water content mechanical properties, surface properties and cell response of these various materials have been investigated in this thesis. These studies demonstrated that simple hydrogel SIPNs which show isotropic mechanical behaviour, are not ideal KPro materials since they do not mimic the anisotropic behaviour of natural cornea. The final stage of the work has concentrated on the study of hydrogels reinforced with mesh materials. They offer a promising approach to making a hydrogel that is very flexible but strong under tension, thereby having mechanical properties closer to the natural cornea than has been previously possible.

Gas distribution in shallow packed beds

Packed beds have many industrial applications and are increasingly used in the process industries due to their low pressure drop. With the introduction of more efficient packings, novel packing materials (i.e. adsorbents) and new applications (i.e. flue gas desulphurisation); the aspect ratio (height to diameter) of such beds is decreasing. Obtaining uniform gas distribution in such beds is of crucial importance in minimising operating costs and optimising plant performance. Since to some extent a packed bed acts as its own distributor the importance of obtaining uniform gas distribution has increased as aspect ratios (bed height to diameter) decrease. There is no rigorous design method for distributors due to a limited understanding of the fluid flow phenomena and in particular of the effect of the bed base / free fluid interface. This study is based on a combined theoretical and modelling approach. The starting point is the Ergun Equation which is used to determine the pressure drop over a bed where the flow is uni-directional. This equation has been applied in a vectorial form so it can be applied to maldistributed and multi-directional flows and has been realised in the Computational Fluid Dynamics code PHOENICS. The use of this equation and its application has been verified by modelling experimental measurements of maldistributed gas flows, where there is no free fluid / bed base interface. A novel, two-dimensional experiment has been designed to investigate the fluid mechanics of maldistributed gas flows in shallow packed beds. The flow through the outlet of the duct below the bed can be controlled, permitting a rigorous investigation. The results from this apparatus provide useful insights into the fluid mechanics of flow in and around a shallow packed bed and show the critical effect of the bed base. The PHOENICS/vectorial Ergun Equation model has been adapted to model this situation. The model has been improved by the inclusion of spatial voidage variations in the bed and the prescription of a novel bed base boundary condition. This boundary condition is based on the logarithmic law for velocities near walls without restricting the velocity at the bed base to zero and is applied within a turbulence model. The flow in a curved bed section, which is three-dimensional in nature, is examined experimentally. The effect of the walls and the changes in gas direction on the gas flow are shown to be particularly significant. As before, the relative amounts of gas flowing through the bed and duct outlet can be controlled. The model and improved understanding of the underlying physical phenomena form the basis for the development of new distributors and rigorous design methods for them.

Studies in three phase gas-liquid-solid fluidised systems

The work is a logical continuation of research started at Aston some years ago when studies were conducted on fermentations in bubble columns. The present work highlights typical design and operating problems that could arise in such systems as waste water, chemical, biochemical and petroleum operations involving three-phase, gas-liquid-solid fluidisation; such systems are in increasing use. It is believed that this is one of few studies concerned with `true' three-phase, gas-liquid-solid fluidised systems, and that this work will contribute significantly to closing some of the gaps in knowledge in this area. The research work was mainly experimentally based and involved studies of the hydrodynamic parameters, phase holdups (gas and solid), particle mixing and segregation, and phase flow dynamics (flow regime and circulation patterns). The studies have focused particularly on the solid behaviour and the influence of properties of solids present on the above parameters in three-phase, gas-liquid-solid fluidised systems containing single particle components and those containing binary and ternary mixtures of particles. All particles were near spherical in shape and two particle sizes and total concentration levels were used. Experiments were carried out in two- and three-dimensional bubble columns. Quantitative results are presented in graphical form and are supported by qualitative results from visual studies which are also shown as schematic diagrams and in photographic form. Gas and solid holdup results are compared for air-water containing single, binary and ternary component particle mixtures. It should be noted that the criteria for selection of the materials used are very important if true three-phase fluidisation is to be achieved: this is very evident when comparing the results with those in the literature. The fluid flow and circulation patterns observed were assessed for validation of the generally accepted patterns, and the author believes that the present work provides more accurate insight into the modelling of liquid circulation in bubble columns. The characteristic bubbly flow at low gas velocity in a two-phase system is suppressed in the three-phase system. The degree of mixing within the system is found to be dependent on flow regime, liquid circulation and the ratio of solid phase physical properties. Evidence of strong `trade-off' of properties is shown; the overall solid holdup is believed to be a major parameter influencing the gas holdup structure.

The Single drop drying of heat-sensitive materials

The literature relating to the principles and practice of drying of materials, particularly those susceptible to thermal degradation or undesirable loss of volatile components, has been reviewed. Single droplets of heat-sensitive materials were dried whilst suspended in a horizontal wind tunnel from a specially-designed, rotating thermocouple which enabled direct observation of drying behaviour and continuous measurement of droplet temperature as drying progressed. The effects of drying air temperature and initial solids concentration on the potency of various antibiotics, viz. ampicillin, chloramphenicol, oxytetracycline, streptomycin and tetracycline, were assessed using a modified Drug Sensitivity Testing technique. Only ampicillin was heat-sensitive at temperatures above 100°C, e.g. at an air temperature of 115°C its zone diameter was reduced from 100% to 45%. Selected enzymes, viz. dextran sucrase and invertase, were also dried and their residual activities determined by High Performance Liquid Chromatography. The residual activity of dextran sucrase was rapidly reduced at temperatures above 65°C, and the residual activity of invertase reduced rapidly at temperatures above 65°C; but drying with short residence times will retain most of its activity. The performance of various skin-forming encapsulants, viz. rice and wheat starch, dextrin, coffee, skim milk, fructose, gelatine 60 and 150 Bloom, and gum arabic, was evaluated to determine their capabilities for retention of ethanol as a model volatile, under different operating conditions. The effects of initial solids concentration, air velocity and temperature were monitored for each material tested. Ethanol content was analysed by Gas Liquid Chromatography and in some cases dried crusts were removed for examination. Volatiles retention was concluded to depend in all cases upon the rate and nature of the skin formation and selective diffusion phenomena. The results provided further insight into the inter-relationship between temperature, residence time and thermal degradation of heat-sensitive materials. They should also assist in selection of the preferred dryer for such materials, and of the operating parameter to enable maximum retention of the required physico-chemical characteristics in the dried materials.

An assessment of the performance of high density polyethylene copolymers for natural gas distribution pipes

The total thermoplastics pipe market in west Europe is estimated at 900,000 metric tonnes for 1977 and is projected to grow to some 1.3 million tonnes of predominantly PVC and polyolefins pipe by 1985. By that time, polyethylene for gas distribution pipe and fittings will represent some 30% of the total polyethylene pipe market. The performance characteristics of a high density polyethylene are significantly influenced by both molecular weight and type of comonomer; the major influences being in the long-term hoop stress resistance and the environmental stress cracking resistance. Minor amounts of hexene-1 are more effective than comonomers lower in the homologous series, although there is some sacrifice of density related properties. A synergistic improvement is obtained by combining molecular weight increase with copolymerisation. The Long-term design strength of polyethylene copolymers can be determined from hoop stress measurement at elevated temperatures and by means of a separation factor of approximate value 22, extrapolation can be made to room temperature performance for a water environment. A polyethylene of black composition has a sufficiently improved performance over yellow pigmented pipe to cast doubts on the validity of internationally specifying yellow coded pipe for gas distribution service. The chemical environment (condensate formation) that can exist in natural gas distribution networks has a deleterious effect on the pipe performance the reduction amounting to at least two decades in log time. Desorption of such condensate is very slow and the influence of the more aggressive aromatic components is to lead to premature stress cracking. For natural gas distribution purposes, the design stress rating should be 39 Kg/cm2 for polyethylenes in the molecular weight range of 150 - 200,000 and 55 Kg/cm2 for higher molecular weight materials.

Another angle on contact lens surface analysis

Purpose: Dynamic contact angle (DCA) methods have advantages over other contact angle methodologies, not least that they can provide more than single contact angle values. Here we illustrate the use of DCA analysis to provide “fingerprint” characterisation of contact lens surfaces, and the way that different materials change in the early stages of wear. Method: The DCA method involves attaching to a microbalance weighted strips cut from a lens. The strips are then cyclically inserted into and removed from an aqueous solution. Conventionally, readings of force taken from linear portions of the resultant dipping curves are translated into advancing (CAa) and receding contact (CAr) angles. Additionally, analysis of the force versus immersion profile provides a “fingerprint” characterisation of the state of the lens surface. Results: CAa and CAr values from DCA traces provide a useful means of differentiating gross differences in hydrophilicity and molecular mobility of surfaces under particular immersion and emersion conditions, such as dipping rate and dwell times. Typical values for etafilcon A (CAa:63.1; CAr:37) and balafilcon B (CAa:118.4; CAr:36.4) illustrate this. Surface modifications induced in lens manufacture are observed to produce not only changes in these value, which may be small, but also changes in the DCA “fingerprint” (slope, undulations, length of plateau). Interestingly, similar changes are induced in the first few hours of lens wear with some lens-patient combinations. Conclusions: Although single parameter contact angles are useful for material characterisation, information of potential clinical interest can be obtained from more detailed analysis of DCA traces.

Future of contact lens usage

I was recently part of a small committee looking at higher qualifications in contact lens practice and the discussion turned to future technologies. There was mention of different materials and different applications of contact lenses. Drug delivery with contact lenses was discussed as this has been talked about in the literature for a while. The first paper I could find that talked about using contact lenses for drug delivery dates back over 40 years. There was a review paper in CLAE in 2008 that looked specifically at this too [1]. However, where are these products? Why are we not seeing them in the market place? Maybe the technology is not quite there yet, or maybe patents are prohibiting usage or maybe the market is not big enough to develop such products? We do have lenses on the market with slow release of lubricating agents but not therapeutic agents used for ocular or systemic conditions. Contact lenses with pathogen detectors may be part of our contact lens armoury of the future and again we can already see papers in the literature that have trialled this technology for glucose monitoring in diabetics or lactate concentration in the tear film. Future contact lenses may incorporate better optics based on aberration control and we see this starting to emerge with aspheric designs designed to minimise spherical aberration. Irregular corneas can be fitted with topography based designs and again this technology exists and is being used by some manufacturers in their designs already. Moreover, the topography based fitting of irregular corneas is certainly something we see a lot of today and CLAE has seen many articles related to this over the last decade or so. What about further into the future? Well one interesting area must the 3-dimensional contact lenses, or contact lenses with electronic devices built in that simulate a display screen. A little like the virtual display spectacles that are already sold by electronics companies. It does not take much of a stretch of the imagination to see a large electronic company taking this technology on and making it viable. Will we see people on the train watching movies on these electronic virtual reality contact lenses? I think we will, but when is harder to know.

Adverse events and discontinuations during 18 months of silicone hydrogel contact lens wear

PURPOSE. To report differences in the incidence of adverse events and discontinuations found in a group of neophyte contact wearers using two different silicone hydrogel contact lenses on a daily- and continuous-wear basis during an 18-month period. METHODS. Sixty-one subjects were initially examined, and 53 were eligible to participate in the study. Eligible subjects were randomly assigned to wear one of two silicone hydrogel materials: lotrafilcon A or balafilcon A lenses on a daily- or continuous-wear basis. After an initial screening, subjects were monitored weekly for the first month and then after 3, 6, 12, and 18 months. The incidence of adverse events, including corneal infiltrative events, superior epithelial arcuate lesions, and contact lens-induced papillary conjunctivitis, and discontinuations in each of the four contact lens groups were recorded. RESULTS. Twenty-two adverse events were found. A higher incidence of adverse events was found in subjects wearing lotrafilcon A lenses than in those wearing balafilcon A lenses (χ = 4.40, P=0.04). There were fewer adverse events in subjects wearing lenses on a daily-wear basis than in those wearing lenses on a continuous-wear basis (χ = 5.98, P=0.01). Eight subjects discontinued from the study as a result of recurrent corneal infiltrative events (one), vision problems (two), excessive ocular discomfort (one), relocation (one), noncompliance with the study protocol (one), and being lost to follow-up (two). No significant differences were found in the number of discontinuations between the two lens types (χ = 0.66, P=0.42) and wearing regimens (χ = 0.08, P=0.78). CONCLUSIONS. Lotrafilcon A lenses were associated with a higher incidence of adverse events than balafilcon A lenses were, and this difference is attributed to the difference in the incidence of corneal infiltrative events. Subjects wearing lenses on a daily-wear basis had fewer adverse events than did subjects wearing lenses on a continuous-wear basis. Both lens types and wearing regimens showed a similar incidence of discontinuations. © 2007 Lippincott Williams & Wilkins, Inc.

Optical immersion of mid-infrared LEDs and photodiodes for gas-sensing applications

The high gains in performance predicted for optical immersion are difficult to achieve in practice due to total internal reflection at the lens/detector interface. By reducing the air gap at this interface optical tunneling becomes possible and the predicted gains can be realized in practical devices. Using this technique we have demonstrated large performance gains by optically immersing mid-infrared heterostructure InA1Sb LEDs and photodiodes using hypershperical germanium lenses. The development of an effective method of optical immersion that gives excellent optical coupling has produced a photodiode with a peak room temperature detectivity (D*) of 5.3 x 109 cmHz½W-1 at λpeak=5.4μm and a 40° field of view. A hyperspherically immersed LED showed a f-fold improvement in the external efficiency, and a 3-fold improvement in the directionality compared with a conventional planar LED for f/2 optical systems. The incorporation of these uncooled devices in a White cell produced a NO2 gas sensing system with 2 part-per-million sensitivity, with an LED drive current of <5mA. These results represent a significant advance in the use of solid state devices for portable gas sensing systems.

The design of contact lens based ocular drug delivery systems for single-day use:part (I) structural factors, surrogate ophthalmic dyes and passive diffusion studies

The poor retention and efficacy of instilled drops as a means of delivering drugs to the ophthalmic environment is well-recognised. The potential value of contact lenses as a means of ophthalmic drug delivery, and consequent improvement of pre-corneal retention is one obvious route to the development of a more effective ocular delivery system. Furthermore, the increasing availability and clinical use of daily disposable contact lenses provides the platform for the development of viable single-day use drug delivery devices based on existing materials and lenses. In order to provide a basis for the effective design of such devices, a systematic understanding of the factors affecting the interaction of individual drugs with the lens matrix is required. Because a large number of potential structural variables are involved, it is necessary to achieve some rationalisation of the parameters and physicochemical properties (such as molecular weight, charge, partition coefficients) that influence drug interactions. Ophthalmic dyes and structurally related compounds based on the same core structure were used to investigate these various factors and the way in which they can be used in concert to design effective release systems for structurally different drugs. Initial studies of passive diffusional release form a necessary precursor to the investigation of the features of the ocular environment that over-ride this simple behaviour. Commercially available contact lenses of differing structural classifications were used to study factors affecting the uptake of the surrogate actives and their release under 'passive' conditions. The interaction between active and lens material shows considerable and complex structure dependence, which is not simply related to equilibrium water content. The structure of the polymer matrix itself was found to have the dominant controlling influence on active uptake; hydrophobic interaction with the ophthalmic dye playing a major role. © The Author(s) 2014 Reprints and permissions: sagepub.co.uk/journalsPermissions.nav.

Modeling of Cylindrical Couette Flow of Rarefied Gas Between Rotating Cylinders

Петър Господинов, Добри Данков, Владимир Русинов, Стефан Стефанов - Изследвано е цилиндрично течение на Кует за разреден газ между два въртящи се цилиндъра. Получени са профилите на налягането, скоростта и температурата по метода на прякото статистическо моделиране (DSMC) и чрез числено решаване на уравненията на Навие-Стокс за свиваем флуид. Резултатите сочат много добро съвпадение за малки числа на Кнудсен Kn = 0.02. Показано е, че при различни кинематични гранични условия, газът изостава или избързва спрямо скоростта на стената, или има поведение на твърдо еластично тяло. Получените резултати са важни при решаването на неравнинни, задачи от микрофлуидиката с отчитане на ефектите на кривината.

Exploration of a simple, low cost, micro gas turbine recuperator solution for a domestic combined heat and power unit

For micro gas turbines (MGT) of around 1 kW or less, a commercially suitable recuperator must be used to produce a thermal efficiency suitable for use in UK Domestic Combined Heat and Power (DCHP). This paper uses computational fluid dynamics (CFD) to investigate a recuperator design based on a helically coiled pipe-in-pipe heat exchanger which utilises industry standard stock materials and manufacturing techniques. A suitable mesh strategy was established by geometrically modelling separate boundary layer volumes to satisfy y + near wall conditions. A higher mesh density was then used to resolve the core flow. A coiled pipe-in-pipe recuperator solution for a 1 kW MGT DCHP unit was established within the volume envelope suitable for a domestic wall-hung boiler. Using a low MGT pressure ratio (necessitated by using a turbocharger oil cooled journal bearing platform) meant unit size was larger than anticipated. Raising MGT pressure ratio from 2.15 to 2.5 could significantly reduce recuperator volume. Dimensional reasoning confirmed the existence of optimum pipe diameter combinations for minimum pressure drop. Maximum heat exchanger effectiveness was achieved using an optimum or minimum pressure drop pipe combination with large pipe length as opposed to a large pressure drop pipe combination with shorter pipe length. © 2011 Elsevier Ltd. All rights reserved.

Self-assembled SnO2 micro- and nanosphere-based gas sensor thick films from an alkoxide-derived high purity aqueous colloid precursor

Tin oxide is considered to be one of the most promising semiconductor oxide materials for use as a gas sensor. However, a simple route for the controllable build-up of nanostructured, sufficiently pure and hierarchical SnO2 structures for gas sensor applications is still a challenge. In the current work, an aqueous SnO2 nanoparticulate precursor sol, which is free of organic contaminants and sorbed ions and is fully stable over time, was prepared in a highly reproducible manner from an alkoxide Sn(OR)4 just by mixing it with a large excess of pure neutral water. The precursor is formed as a separate liquid phase. The structure and purity of the precursor is revealed using XRD, SAXS, EXAFS, HRTEM imaging, FTIR, and XRF analysis. An unconventional approach for the estimation of the particle size based on the quantification of the Sn-Sn contacts in the structure was developed using EXAFS spectroscopy and verified using HRTEM. To construct sensors with a hierarchical 3D structure, we employed an unusual emulsification technique not involving any additives or surfactants, using simply the extraction of the liquid phase, water, with the help of dry butanol under ambient conditions. The originally generated crystalline but yet highly reactive nanoparticles form relatively uniform spheres through self-assembly and solidify instantly. The spheres floating in butanol were left to deposit on the surface of quartz plates bearing sputtered gold electrodes, producing ready-for-use gas sensors in the form of ca. 50 μm thick sphere-based-films. The films were dried for 24 h and calcined at 300°C in air before use. The gas sensitivity of the structures was tested in the temperature range of 150-400°C. The materials showed a very quickly emerging and reversible (20-30 times) increase in electrical conductivity as a response to exposure to air containing 100 ppm of H2 or CO and short (10 s) recovery times when the gas flow was stopped.

Superior gas-sensing performance of amorphous CdO nanoflake arrays prepared at room temperature

Highly sensitive and selective detection of volatile organic compounds (VOCs) with fast response time is imperative based on safety requirements, yet often remains a challenge. Herein, we propose an effective solution, preparing a novel gas sensor comprised of amorphous nanoflake arrays (a-NFAs) with specific surface groups. The sensor was produced via an extremely simple process in which a-NFAs of CdO were deposited directly onto an interdigital electrode immersed in a chemical bath under ambient conditions. Upon exposure to a widely used VOC, diethyl ether (DEE), the sensor exhibits excellent performance, more specifically, the quickest response, lowest detection limit and highest selectivity ever reported for DEE as a target gas. The superior gas-sensing properties of the prepared a-NFAs are found to arise from their open trumpet-shaped morphology, defect-rich amorphous nature, and surface CO groups.