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.

Design of films for oral dosage formulations

A novel method for tablet coating was studied where a thin polymer film was cast (pre-formed film), dried and applied as a coating hence eliminating the need for using any solvent during the actual coating process. A pre-formed film is initially heating to a temperature where it becomes flexible, a vacuum is applied and the film is then pulled around the tablet. The proposed films (gelatine or cellulose-based) were characterised in terms of their dissolution, swelling, mechanical and thermal properties prior to using them in the novel coating process; selected films were then coated onto tablets containing paracetamol or ibuprofen and the effect of the film on the subsequent dissolution was evaluated. It was found that the pre-formed films could be designed to be fast dissolving and mechanically strong to withstand the stress from the coating process. Also metoclopramide was incorporated in a gelatine film-coating formulation which was then successfully coated on paracetamol-containing core. Gelatin-based films were found to be successful in the novel coating process therefore to be suitable as finished coatings for immediate release dosage forms. Orally disintegrating dosage forms have been identified as a favourable dosage form due to the following reasons: fast onset of drug release, easy to use, not painful and possible increase of amount absorbed to systemic circulation. Selected films formulated for coating studies were also successfully formulated to contain active ingredient suitable for orally disintegrating dosage form; cellulose-based naratriptan-films were studied as orally disintegrating dosage forms of where the effect of formulation on the film properties was studied. It was found that strength of the film can affect the dissolution of the film but it may be the inclusion of specific excipients in the formulation which affect the penetration of the drug through mucosa.

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.

Environmental degradation of polyethylene-based plastics

The criteria involved in the degradation of polyethylene-based degradable polymer samples have been investigated, with a view to obtaining a clearer mechanism of photo-biodegradation. The compatibility of degradable polymer samples during materials recycling was also studied. Commercial and laboratory prepared degradable polymer samples were oxidised in different environments and the oxidation products formed were studied using various analytical chromatographic and spectroscopic techniques such as HPLC, FT-IR and NMR. It was found that commercial degradable polymer samples which are based on the ECO systems, degrade predominantly via the Norrish II process, whereas the other degradable systems studied (starch-filled polyethylene systems, transition metal systems, including metal carboxylate based polyethylene systems and the photoantioxidant-activator systems) photodegrade essentially via the Norrish I process. In all cases, the major photoxidation products extracted from the degradable polymer samples were found to be carboxylic acids, although, in the polymer itself a mixture of carbonyl containing products such as esters, lactones, ketones and aldehydes was observed. The study also found that the formation of these hydrophilic carbonyl products causes surface swelling of the polymer, thus making bioerosion possible. It was thus concluded that environmental degradation of LDPE is a two step process, the initiation stage being oxidation of the polymer which gives rise to bioassimilable products, which are consequently bioeroded in the second stage, (the biodegradation step). Recycling of the degradable polymer samples as 10% homogeneous and heterogeneous blends was carried out using a single screw extruder (180°C and 210°C) and an internal mixer (190°C). The study showed that commercial degradable polymer samples may be recycled with a minimal loss in their properties.

The study and characterisation of water-based latices used for can coating interiors

Water-based latices, used in the production of internal liners for beer/beverage cans, were investigated using a number of analytical techniques. The epoxy-graft-acrylic polymers, used to prepare the latices, and films, produced from those latices, were also examined. It was confirmed that acrylic polymer preferentially grafts onto higher molecular weight portions of the epoxy polymer. The amount of epoxy remaining ungrafted was determined to be 80%. This figure is higher than was previously thought. Molecular weight distribution studies were carried out on the epoxy and epoxy-g-acrylic resins. A quantitative method for determining copolymer composition using GPC was evaluated. The GPC method was also used to determine polymer composition as a function of molecular weight. IR spectroscopy was used to determine the total level of acrylic modification of the polymers and NMR was used to determine the level of grafting. Particle size determinations were carried out using transmission electron microscopy and dynamic light scattering. Levels of stabilising amine greatly affected the viscosity of the latex, particle size and amount of soluble polymer but the core particle size, as determined using TEM, was unaffected. NMR spectra of the latices produced spectra only from solvents and amine modifiers. Using solid-state CP/MAS/freezing techniques spectra from the epoxy component could be observed. FT-IR spectra of the latices were obtained after special subtraction of water. The only difference between the spectra of the latices and those of the dry film were due to the presence of the solvents in the former. A distinctive morphology in the films produced from the latices was observed. This suggested that the micelle structure of the latex survives the film forming process. If insufficient acrylic is present, large epoxy domains are produced which gives rise to poor film characteristics. Casting the polymers from organic solutions failed to produce similar morphology.

Tissue engineering of co-cultured skin substitutes using biocomposite membranes based on collagen and polycaprolactone

The preparation and characterisation of collagen: PCL, gelatin: PCL and gelatin/collagen:PCL biocomposites for manufacture of tissue engineered skin substitutes are reported. Films of collagen: PLC, gelatin: PCL (1:4, 1:8 and 1:20 w/w) and gelatin/collagen:PCL (1:8 and 1:20 w/w) biocomposites were prepared by impregnation of lyophilised collagen and/or gelatin mats by PCL solutions followed by solvent evaporation. In vitro assays of total protein release of collagen:PCL and gelatin: PCL biocomposite films revealed an expected inverse relationship between the collagen release rate and the content of synthetic polymer in the biocomposite samples that may be exploited for controlled presentation and release of biopharmaceuticals such as growth factors. Good compatibility of all biocomposite groups was proven by interaction with 3T3 fibroblasts, normal human epidermal keratinocytes (NHEK), and primary human epidermal keratinocytes (PHEK) and dermal fibroblasts (PHDF) in vitro respectively. The 1:20 collagen: PCL materials exhibiting good cell growth curves and mechanical characteristics were selected for engineering of skin substitutes in this work. The tissue-engineered skin model based on single-donor PHEK and PHDF with differentiated confluent epidermal layer and fibrous porous dermal layer was then developed successfully in vitro proven by SEM and immunohistochemistry assay. The following in vivo animal study on athymic mice revealed early complete wound healing in 10 days and good integration of co-cultured skin substitutes with adjacent mice skin structures. Thus the co-cultured skin substitutes based on 1:20 collagen: PCL biocomposite membranes was proven in principle. The approach to skin modelling reported here may find application in wound treatment, gene therapy and screening of new pharmaceuticals.

The study of ultra-low energy deposition of hydrogenated amorphous carbon thin films

This thesis is dedicated to the production and analysis of thin hydrogenated amorphous carbon films. A cascaded arc plasma source was used to produce a high density plasma of hydrocarbon radicals that deposited on a substrate at ultra low energies. The work was intended to create a better understanding of the mechanisms responsible for the film formation, by an extensive analysis on the properties of the films in correlation with the conditions used in the plasma cell. Two different precursors were used: methane and acetylene. They revealed a very different picture for the mechanism of film formation and properties. Methane was less successful, and the films formed were soft, with poor adhesion to the substrate and decomposing with time. Acetylene was the better option, and the films formed in this case were harder, with better adhesion to the substrate and stable over time. The plasma parameters could be varied to change the character of films, from polymer-like to diamond-like carbon. Films deposited from methane were grown at low deposition rates, which increased with the increase in process pressure and source power and decreased with the increase in substrate temperature and in hydrogen fraction in the carrier gas. The films had similar hydrogen content, sp3 fractions, average roughness (Ra) and low hardness. Above a deposition temperature of 350°C graphitization occurred - an increase in the sp2 fraction. A deposition mechanism was proposed, based upon the reaction product of the dissociative recombination of CH4+. There were small differences between the chemistries in the plasma at low and high precursor flow rates and low and high substrate temperatures; all experimental conditions led to formation of films that were either polymer-like, soft amorphous hydrogenated carbon or graphitic-like in structure. Films deposited from acetylene were grown at much higher deposition rates on different substrates (silicon, glass and plastics). The film quality increased noticeably with the increase of relative acetylene to argon flow rate, up to a certain value, where saturation occurred. With the increase in substrate temperature and the lowering of the acetylene injection ring position further improvements in film quality were achieved. The deposition process was scaled up to large area (5 x 5 cm) substrates in the later stages of the project. A deposition mechanism was proposed, based upon the reaction products of the dissociative recombination of C2H2 +. There were large differences between the chemistry in the plasma at low and medium/high precursor flow rates. This corresponded to large differences in film properties from low to medium flow rates, when films changed their character from polymer-like to diamond-like, whereas the differences between films deposited at medium and high precursor flow rates were small. Modelling of the film growth on silicon substrates was initiated and it explained the formation of sp2 and sp3 bonds at these very low energies. However, further improvements to the model are needed.

TiN-based coatings on fuel cladding tubes for advanced nuclear reactors

Titanium nitride (TiN) thin films are coated on HT-9 and MA957 fuel cladding tubes and bars to explore their mechanical strength, thermal stability, diffusion barrier properties, and thermal conductivity properties. The ultimate goal is to implement TiN as an effective diffusion barrier to prevent the inter-diffusion between the nuclear fuel and the cladding material, and thus lead to a longer lifetime of the cladding tubes. Mechanical tests including hardness and scratch tests for the samples before and after thermal cycle tests show that the films have a high hardness of 28GPa and excellent adhesion properties despite the thermal treatment. Thermal conductivity measurements demonstrate that the thin TiN films have very minimal impact on the overall thermal conductivity of the MA957 and HT-9 substrates, i.e., the thermal conductivity of the uncoated HT-9 and MA957 substrates was 26.25 and 28.44 W m-1 K-1, and that of the coated ones was 26.21 and 28.38W m-1 K-1, respectively. A preliminary Ce diffusion test on the couple of Ce/TiN/HT-9 suggests that TiN has excellent material compatibility and good diffusion barrier properties.

Novel three-component blends based on poly(L-lactide)

A significant number of poly a-ester homologues of poly(L-lactide) (PLLA) have been synthesized and used in miscibility studies together with conventional isomeric diacid-diol polyester variants, poly ß-esters (based on ß-hydroxybutyrate (HB) and ß-hydroxyvalerate (HV)), poly e-caprolactone (PCL), poly e-caprolactone copolymers (e.g. poly(L-lactide-co-caprolactone), and a series of cellulose-based polymers (e.g. cellulose acetate butyrate (CAB), cellulose acetate propionate (CAP)). A combinatorial approach to rapid miscibility screening using 96-well plates and a uv-visible multi-wavelength plate reader has been developed enabling the clarity of PLLA-based multi-component blend films to be observed. Using these techniques and materials, the ternary phase compatibility diagrams of a range of three-component blend films was prepared, illustrating ranges of behavior varying from miscible blends giving rise to clear films to immiscible blends which are opaque. In this way, novel three-component blends of PLLA/CAB/PCL were developed which are miscible when the CAB content is more than 30%, PLLA less than 80% and PCL less than 60%.

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.

Composite cell support membranes based on collagen and polycaprolactone for tissue engineering of skin

The preparation and characterisation of collagen:PCL composites for manufacture of tissue engineered skin substitutes and models are reported. Films having collagen:PCL (w/w) ratios of 1:4, 1:8 and 1:20 were prepared by impregnation of lyophilised collagen mats by PCL solutions followed by solvent evaporation. In vitro assays of collagen release and residual collagen content revealed an expected inverse relationship between the collagen release rate and the content of synthetic polymer in the composite that may be exploited for controlled presentation and release of biopharmaceuticals such as growth factors. DSC analysis revealed the characteristic melting point of PCL at around 60°C and a tendency for the collagen component, at high loading, to impede crystallinity development within the PCL phase. The preparation of fibroblast/composite constructs was investigated using cell culture as a first stage in mimicking the dermal/epidermal structure of skin. Fibroblasts were found to attach and proliferate on all the composites investigated reaching a maximum of 2×105/cm2 on 1:20 collagen:PCL materials at day 8 with cell numbers declining thereafter. Keratinocyte growth rates were similar on all types of collagen:PCL materials investigated reaching a maximum of 6.6×104/cm2 at day 6. The results revealed that composite films of collagen and PCL are favourable substrates for growth of fibroblasts and keratinocytes and may find utility for skin repair. © 2003 Elsevier Ltd. All rights reserved.

A co-cultured skin model based on cell support membranes

Tissue engineering of skin based on collagen:PCL biocomposites using a designed co-culture system is reported. The collagen:PCL biocomposites having collagen:PCL (w/w) ratios of 1:4, 1:8, and 1:20 have been proven to be biocompatible materials to support both adult normal human epidermal Keratinocyte (NHEK) and mouse 3T3 fibroblast growth in cell culture, respectively, by Dai, Coombes, et al. in 2004. Films of collagen:PCL biocomposites were prepared using non-crosslinking method by impregnation of lyophilized collagen mats with PCL/dichloromethane solutions followed by solvent evaporation. To mimic the dermal/epidermal structure of skin, the 1:20 collagen:PCL biocomposites were selected for a feasibility study of a designed co-culture technique that would subsequently be used for preparing fibroblast/biocomposite/keratinocyte skin models. A 55.3% increase in cell number was measured in the designed co-culture system when fibroblasts were seeded on both sides of a biocomposite film compared with cell culture on one surface of the biocomposite in the feasibility study. The co-culture of human keratinocytes and 3T3 fibroblasts on each side of the membrane was therefore studied using the same co-culture system by growing keratinocytes on the top surface of membrane for 3 days and 3T3 fibroblasts underneath the membrane for 6 days. Scanning electron microscopy (SEM) and immunohistochemistry assay revealed good cell attachment and proliferation of both human keratinocytes and 3T3 fibroblasts with these two types of cells isolated well on each side of the membrane. Using a modified co-culture technique, a co-cultured skin model presenting a confluent epidermal sheet on one side of the biocomposite film and fibroblasts populated on the other side of the film was developed successfully in co-culture system for 28 days under investigations by SEM and immunohistochemistry assay. Thus, the design of a co-culture system based on 1:20 (w/w) collagen:PCL biocomposite membranes for preparation of a bi-layered skin model with differentiated epidermal sheet was proven in principle. The approach to skin modeling reported here may find application in tissue engineering and screening of new pharmaceuticals. © 2005 Elsevier Inc. All rights reserved.

Study on fatigue and energy-dissipation properties of nanolayered Cu/Nb thin films

Energy dissipation and fatigue properties of nano-layered thin films are less well studied than bulk properties. Existing experimental methods for studying energy dissipation properties, typically using magnetic interaction as a driving force at different frequencies and a laser-based deformation measurement system, are difficult to apply to two-dimensional materials. We propose a novel experimental method to perform dynamic testing on thin-film materials by driving a cantilever specimen at its fixed end with a bimorph piezoelectric actuator and monitoring the displacements of the specimen and the actuator with a fibre-optic system. Upon vibration, the specimen is greatly affected by its inertia, and behaves as a cantilever beam under base excitation in translation. At resonance, this method resembles the vibrating reed method conventionally used in the viscoelasticity community. The loss tangent is obtained from both the width of a resonance peak and a free-decay process. As for fatigue measurement, we implement a control algorithm into LabView to maintain maximum displacement of the specimen during the course of the experiment. The fatigue S-N curves are obtained.

Effect of methane concentration in hydrogen plasma on hydrogen impurity incorporation in thick large-grained polycrystalline diamond films

We investigate the impact of methane concentration in hydrogen plasma on the growth of large-grained polycrystalline diamond (PCD) films and its hydrogen impurity incorporation. The diamond samples were produced using high CH4 concentration in H2 plasma and high power up to 4350 W and high pressure (either 105 or 110 Torr) in a microwave plasma chemical vapor deposition (MPCVD) system. The thickness of the free-standing diamond films varies from 165 µm to 430 µm. Scanning electron microscopy (SEM), micro-Raman spectroscopy and Fourier-transform infrared (FTIR) spectroscopy were used to characterize the morphology, crystalline and optical quality of the diamond samples, and bonded hydrogen impurity in the diamond films, respectively. Under the conditions employed here, when methane concentration in the gas phase increases from 3.75% to 7.5%, the growth rate of the PCD films rises from around 3.0 µm/h up to 8.5 µm/h, and the optical active bonded hydrogen impurity content also increases more than one times, especially the two CVD diamond specific H related infrared absorption peaks at 2818 and 2828 cm−1 rise strongly; while the crystalline and optical quality of the MCD films decreases significantly, namely structural defects and non-diamond carbon phase content also increases a lot with increasing of methane concentration. Based on the results, the relationship between methane concentration and diamond growth rate and hydrogen impurity incorporation including the form of bonded infrared active hydrogen impurity in CVD diamonds was analyzed and discussed. The effect of substrate temperature on diamond growth was also briefly discussed. The experimental findings indicate that bonded hydrogen impurity in CVD diamond films mainly comes from methane rather than hydrogen in the gas source, and thus can provide experimental evidence for the theoretical study of the standard methyl species dominated growth mechanism of CVD diamonds grown with methane/hydrogen mixtures.

Impact of high microwave power on hydrogen impurity trapping in nanocrystalline diamond films grown with simultaneous nitrogen and oxygen addition into methane/hydrogen plasma

In this work, we study for the first time the influence of microwave power higher than 2.0 kW on bonded hydrogen impurity incorporation (form and content) in nanocrystalline diamond (NCD) films grown in a 5 kW MPCVD reactor. The NCD samples of different thickness ranging from 25 to 205 μm were obtained through a small amount of simultaneous nitrogen and oxygen addition into conventional about 4% methane in hydrogen reactants by keeping the other operating parameters in the same range as that typically used for the growth of large-grained polycrystalline diamond films. Specific hydrogen point defect in the NCD films is analyzed by using Fourier-transform infrared (FTIR) spectroscopy. When the other operating parameters are kept constant (mainly the input gases), with increasing of microwave power from 2.0 to 3.2 kW (the pressure was increased slightly in order to stabilize the plasma ball of the same size), which simultaneously resulting in the rise of substrate temperature more than 100 °C, the growth rate of the NCD films increases one order of magnitude from 0.3 to 3.0 μm/h, while the content of hydrogen impurity trapped in the NCD films during the growth process decreases with power. It has also been found that a new H related infrared absorption peak appears at 2834 cm-1 in the NCD films grown with a small amount of nitrogen and oxygen addition at power higher than 2.0 kW and increases with power higher than 3.0 kW. According to these new experimental results, the role of high microwave power on diamond growth and hydrogen impurity incorporation is discussed based on the standard growth mechanism of CVD diamonds using CH4/H2 gas mixtures. Our current experimental findings shed light into the incorporation mechanism of hydrogen impurity in NCD films grown with a small amount of nitrogen and oxygen addition into methane/hydrogen plasma.