Sensing properties of e-beam evaporated nanostructured pure and iron-doped tungsten oxide thin films

Gas sensing properties of nanostructured pure and iron-doped WO3 thin films are discussed. Electron beam evaporation technique has been used to obtain nanostructured thin films of WO3 and WO3:Fe with small grain size and porosity. Atomic force microscopy has been employed to study the microstructure. High sensitivity of both films towards NO2 is observed. Doping of the tungsten oxide film with Fe decreased the material resistance by a factor of about 30 when exposed to 5 ppm NO2. The high sensitivity is attributed to an improved microstructure of the films obtained through e-beam evaporation technique, and subsequent annealing at 300oC for 1 hour.

A microanalytical study of the surfaces of normal, delipidized, and artificially “resurfaced” articular cartilage

The surface amorphous layer of articular cartilage is of primary importance to its load-bearing and lubrication function. This lipid-filled layer is degraded/disrupted or eliminated when cartilage degenerates due to diseases. This article examines further the characteristic of this surface overlay using a combination of microscopy and imaging methods to evaluate the hypothesis that the surface of articular cartilage can be repaired by exposing degraded cartilage to aqueous synthetic lipid mixtures. The preliminary results demonstrate that it is possible to create a new surface layer of phospholipids on the surface of cartilage following artificial lipid removal, but such a layer does not possess enough mechanical strength for physiological function when created with either unsaturated palmitoyloleoyl- phosphatidylcholine or saturated dipalmitoyl-phosphatidylcholine component of joint lipid composition alone. We conclude that this may be due to low structural cohesivity, inadequate time of exposure, and the mix/content of lipid in the incubation environment.

Thermally evaporated tungsten oxide (WO3) thin films for gas sensing applications

In this thesis, the author proposed and developed gas sensors made of nanostructured WO3 thin film by a thermal evaporation technique. This technique gives control over film thickness, grain size and purity. The device fabrication, nanostructured material synthesis, characterization and gas sensing performance have been undertaken. Three different types of nanostructured thin films, namely, pure WO3 thin films, iron-doped WO3 thin films by co-evaporation and Fe-implanted WO3 thin films have been synthesized. All the thin films have a film thickness of 300 nm. The physical, chemical and electronic properties of these films have been optimized by annealing heat treatment at 300ºC and 400ºC for 2 hours in air. Various analytical techniques were employed to characterize these films. Atomic Force Microscopy and Transmission Electron Microscopy revealed a very small grain size of the order 5-10 nm in as-deposited WO3 films, and annealing at 300ºC or 400ºC did not result in any significant change in grain size. X-ray diffraction (XRD) analysis revealed a highly amorphous structure of as-deposited films. Annealing at 300ºC for 2 hours in air did not improve crystallinity in these films. However, annealing at 400ºC for 2 hours in air significantly improved the crystallinity in pure and iron-doped WO3 thin films, whereas it only slightly improved the crystallinity of iron-implanted WO3 thin film as a result of implantation. Rutherford backscattered spectroscopy revealed an iron content of 0.5 at.% and 5.5 at.% in iron-doped and iron-implanted WO3 thin films, respectively. The RBS results have been confirmed using energy dispersive x-ray spectroscopy (EDX) during analysis of the films using transmission electron microscopy (TEM). X-ray photoelectron spectroscopy (XPS) revealed significant lowering of W 4f7/2 binding energy in all films annealed at 400ºC as compared with the as-deposited and 300ºC annealed films. Lowering of W 4f7/2 is due to increase in number of oxygen vacancies in the films and is considered highly beneficial for gas sensing. Raman analysis revealed that 400ºC annealed films except the iron-implanted film are highly crystalline with significant number of O-W-O bonds, which was consistent with the XRD results. Additionally, XRD, XPS and Raman analyses showed no evidence of secondary peaks corresponding to compounds of iron due to iron doping or implantation. This provided an understanding that iron was incorporated in the host WO3 matrix rather than as a separate dispersed compound or as catalyst on the surface. WO3 thin film based gas sensors are known to operate efficiently in the temperature range 200ºC-500 ºC. In the present study, by optimizing the physical, chemical and electronic properties through heat treatment and doping, an optimum response to H2, ethanol and CO has been achieved at a low operating temperature of 150ºC. Pure WO3 thin film annealed at 400ºC showed the highest sensitivity towards H2 at 150ºC due to its very small grain size and porosity, coupled with high number of oxygen vacancies, whereas Fe-doped WO3 film annealed at 400ºC showed the highest sensitivity to ethanol at an operating temperature of 150ºC due to its crystallinity, increased number of oxygen vacancies and higher degree of crystal distortions attributed to Fe addition. Pure WO3 films are known to be insensitive to CO, but iron-doped WO3 thin film annealed at 300ºC and 400ºC showed an optimum response to CO at an operating temperature of 150ºC. This result is attributed to lattice distortions produced in WO3 host matrix as a result of iron incorporation as substitutional impurity. However, iron-implanted WO3 thin films did not show any promising response towards the tested gases as the film structure has been damaged due to implantation, and annealing at 300ºC or 400ºC was not sufficient to induce crystallinity in these films. This study has demonstrated enhanced sensing properties of WO3 thin film sensors towards CO at lower operating temperature, which was achieved by optimizing the physical, chemical and electronic properties of the WO3 film through Fe doping and annealing. This study can be further extended to systematically investigate the effects of different Fe concentrations (0.5 at.% to 10 at.%) on the sensing performance of WO3 thin film gas sensors towards CO.

Porohyperelastic analysis to explore mechanical properties of chondrocytes using numerical modeling and experiments : a finite element study

There are many continuum mechanical models have been developed such as liquid drop models, solid models, and so on for single living cell biomechanics studies. However, these models do not give a fully approach to exhibit a clear understanding of the behaviour of single living cells such as swelling behaviour, drag effect, etc. Hence, the porohyperelastic (PHE) model which can capture those aspects would be a good candidature to study cells behaviour (e.g. chondrocytes in this study). In this research, an FEM model of single chondrocyte cell will be developed by using this PHE model to simulate Atomic Force Microscopy (AFM) experimental results with the variation of strain rate. This material model will be compared with viscoelastic model to demonstrate the advantages of PHE model. The results have shown that the maximum value of force applied of PHE model is lower at lower strain rates. This is because the mobile fluid does not have enough time to exude in case of very high strain rate and also due to the lower permeability of the membrane than that of the protoplasm of chondrocyte. This behavior is barely observed in viscoelastic model. Thus, PHE model is the better model for cell biomechanics studies.

Pt/Graphene Nano-sheet Based Hydrogen Gas Sensor

In this paper, we present gas sensing properties of Pt/graphene-like nano-sheets towards hydrogen gas. The graphene-like nano-sheets were produced via the reduction of spray-coated graphite oxide deposited on SiC substrates by hydrazine vapor. Structural and morphological characterizations of the graphene sheets were analyzed by scanning electron and atomic force microscopy. Current-voltage and dynamic responses of the sensors were investigated towards different concentrations of hydrogen gas in a synthetic air mixture at 100°C. A voltage shift of 100 mV was recorded at 1 mA reverse bias current.

Graphene-like nano-sheets/36° LiTaO3 surface acoustic wave hydrogen gas sensor

Presented is the material and gas sensing properties of graphene-like nano-sheets deposited on 36° YX lithium tantalate (LiTaO3) surface acoustic wave (SAW) transducers. The graphene-like nano-sheets were characterized via scanning electron microscopy (SEM), atomic force microscopy(AFM)and X-ray photoelectron spectroscopy (XPS). The graphenelike nano-sheet/SAW sensors were exposed to different concentrations of hydrogen (H2) gas in a synthetic air at room temperature. The developed sensors exhibit good sensitivity towards low concentrations of H2 in ambient conditions, as well as excellent dynamic performance towards H2 at room temperature.

Ethanol sensitivity of thermally evaporated nanostructured WO3 thin films doped and implanted with Fe

Ethanol sensing performance of gas sensors made of Fe doped and Fe implanted nanostructured WO3 thin films prepared by a thermal evaporation technique was investigated. Three different types of nanostructured thin films, namely, pure WO3 thin films, iron-doped WO3 thin films by co-evaporation and Fe-implanted WO3 thin films have been synthesized. All the thin films have a film thickness of 300 nm. The physical, chemical and electronic properties of these films have been optimized by annealing heat treatment at 300ºC and 400ºC for 2 hours in air. Various analytical techniques were employed to characterize these films. Atomic Force Microscopy and Transmission Electron Microscopy revealed a very small grain size of the order 5-10 nm in as-deposited WO3 films, and annealing at 300ºC or 400ºC did not result in any significant change in grain size. This study has demonstrated enhanced sensing properties of WO3 thin film sensors towards ethanol at lower operating temperature, which was achieved by optimizing the physical, chemical and electronic properties of the WO3 film through Fe doping and annealing.

Effectiveness of cysteine proteases on protein/pigment film removal

Objective: Theaflavin (TF) from the black tea can react to human salivary proline-rich proteins (PRPs) to form stains on exposed dental surfaces. Here, we employed a model of protein/pigment film using TF and dephosphorylated bovine b-casein (Db-CN), which has an extended conformation, similar to that of salivary PRPs, on a sensor surface to assess the efficacy of cysteine proteases (CPs) including papain, stem bromelain, and ficin, on removing TF bound to Db-CN and the control TF readsorption on the residual substrate surfaces was also measured. Methods: The protein/pigment complex film was built by using a quartz crystal microbalance with dissipation (QCM-D). The efficacies of CPs were assessed by Boltzman equation model. The surface details were detected by grazing angle infrared spectroscopy spectra, atomic force microscopy images, and contact angles. Results: The efficacy order of CPs on hydrolyzing protein/pigment complex film is ficin > papain > bromelain. The results from grazing angle infrared spectroscopy spectra, atomic force microscopy images, and contact angles demonstrated that TF bound on the Db- CN was effectively removed by the CPs, and the amount of TF readsorption on both the residual film of the Db-CN/TF and the Db-CN was markedly decreased after hydrolysis. Conclusion: This study indicates the potential application of the CPs for tooth stain removal and suggests that these enzymes are worthy of further investigation for use in oral healthcare.

The mechanics of microdamage and microfracture in trabecular bone

This thesis presents a study using mechanical testing techniques combined with advanced computational methods to examine the mechanics of bone. It contributes novel observations and analysis of how bones fail at the microscopic level, which will be valuable in furthering our understanding and the treatment of bone damage in health and disease, including osteoporosis.

Size characterization of airborne SiO2 nanoparticles with on-line and off-line measurement techniques : an interlaboratory comparison study

Results of an interlaboratory comparison on size characterization of SiO2 airborne nanoparticles using on-line and off-line measurement techniques are discussed. This study was performed in the framework of Technical Working Area (TWA) 34—“Properties of Nanoparticle Populations” of the Versailles Project on Advanced Materials and Standards (VAMAS) in the project no. 3 “Techniques for characterizing size distribution of airborne nanoparticles”. Two types of nano-aerosols, consisting of (1) one population of nanoparticles with a mean diameter between 30.3 and 39.0 nm and (2) two populations of non-agglomerated nanoparticles with mean diameters between, respectively, 36.2–46.6 nm and 80.2–89.8 nm, were generated for characterization measurements. Scanning mobility particle size spectrometers (SMPS) were used for on-line measurements of size distributions of the produced nano-aerosols. Transmission electron microscopy, scanning electron microscopy, and atomic force microscopy were used as off-line measurement techniques for nanoparticles characterization. Samples were deposited on appropriate supports such as grids, filters, and mica plates by electrostatic precipitation and a filtration technique using SMPS controlled generation upstream. The results of the main size distribution parameters (mean and mode diameters), obtained from several laboratories, were compared based on metrological approaches including metrological traceability, calibration, and evaluation of the measurement uncertainty. Internationally harmonized measurement procedures for airborne SiO2 nanoparticles characterization are proposed.

An exploratory study of the potential of resurfacing articular cartilage with synthetic phospholipids

This thesis is aimed at further understanding the uppermost lipid-filled membranous layer (i.e. surface amorphous layer (SAL)) of articular cartilage and to develop a scientific framework for re-introducing lipids onto the surface of lipid-depleted articular cartilage (i.e. "resurfacing"). The outcome will potentially contribute to knowledge that will facilitate the repair of the articular surface of cartilage where degradation is limited to the loss of the lipids of the SAL only. The surface amorphous layer is of utmost importance to the effective load-spreading, lubrication, and semipermeability (which controls its fluid management, nutrient transport and waste removal) of articular cartilage in the mammalian joints. However, because this uppermost layer of cartilage is often in contact during physiological function, it is prone to wear and tear, and thus, is the site for damage initiation that can lead to the early stages of joint condition like osteoarthritis, and related conditions that cause pain and discomfort leading to low quality of life in patients. It is therefore imperative to conduct a study which offers insight into remedying this problem. It is hypothesized that restoration (resurfacing) of the surface amorphous layer can be achieved by re-introducing synthetic surface-active phospholipids (SAPL) into the joint space. This hypothesis was tested in this thesis by exposing cartilage samples whose surface lipids had been depleted to individual and mixtures of synthetic saturated and unsaturated phospholipids. The surfaces of normal, delipidized, and relipidized samples of cartilage were characterized for their structural integrity and functionality using atomic force microscope (AFM), confocal microscope (COFM), Raman spectroscopy, magnetic resonance imaging (MRI) with image processing in the MATLAB® environment and mechanical loading experiments. The results from AFM imaging, confocal microscopy, and Raman spectroscopy revealed a successful deposition of new surface layer on delipidized cartilage when incubated in synthetic phospholipids. The relipidization resulted in a significant improvement in the surface nanostructure of the artificially degraded cartilage, with the complete SAPL mixture providing better outcomes in comparison to those created with the single SAPL components (palmitoyl-oleoyl-phosphatidylcholine, POPC and dipalmitoyl-phosphatidylcholine, DPPC). MRI analysis revealed that the surface created with the complete mixture of synthetic lipids was capable of providing semipermeability to the surface layer of the treated cartilage samples relative to the normal intact surface. Furthermore, deformation energy analysis revealed that the treated samples were capable of delivering the elastic properties required for load bearing and recovery of the tissue relative to the normal intact samples, with this capability closer between the normal and the samples incubated in the complete lipid mixture. In conclusion, this thesis has established that it is possible to deposit/create a potentially viable layer on the surface of cartilage following degradation/lipid loss through incubation in synthetic lipid solutions. However, further studies will be required to advance the ideas developed in this thesis, for the development of synthetic lipid-based injections/drugs for treatment of osteoarthritis and other related joint conditions.

In vitro biocompatibility of different polyester membranes

Nowadays, synthetic biodegradable polymers, such as aliphatic polyesters, are largely used in tissue engineering. They provide several advantages compared to natural materials which use is limited by immunocompatibility, graft availability, etc. In this work, poly(L-lactic) acid (PLLA), poly(DL-lactic) acid (PDLA), poly-epsilon-caprolactone (PCL), poly(L-lactic)-co-caprolactone (molar ratio 70/30) (PLCL) were selected because of their common use in tissue engineering. The membranes were elaborated by solvent casting. Membrane morphology was investigated by atomic force microscopy. The membranes were seeded with human fibroblasts from cell line CRL 2703 in order to evaluate the biocompatibility by the Alamar blue test. The roughness of the membranes ranged from 4 nm for PDLA to 120 nm and they presented very smooth surface except for PCL which beside a macroscopic structure due to its hydrophobicity. Human fibroblasts proliferated over 28 days on the membranes proving the non-in vitro toxicity of the materials and of the processing method. A further step will be the fabrication of three-dimensional scaffold for tissue engineering and the treatment of the scaffolds to augment cell adhesion.

Early stages of growth of YBa2Cu3O7-δ high Tc superconducting films on (001) Y-ZrO2 substrates

The early stages of growth of high quality YBa2Cu 3O7-δ (YBCO) films grown on (001) Y-ZrO2 (YSZ) substrates by pulsed laser deposition have been studied using a combination of atomic force microscopy and transmission electron microscopy. A one unit cell thick YBCO layer and relatively large CuO particles formed in the initial stages. Additional YBCO grew on top of the first layer in the form of one or a few unit cell high c-axis oriented islands about 30 nm in diameter. The rounded islands subsequently coalesced into faceted domains. Elongated Y 2BaCuO5 particles nucleated after the first layer of YBCO. A highly textured BaZrO3 layer formed between the YSZ and the YBCO with a cube-on-cube dominant orientation relationship with respect to the YBCO film.

Microstructure and properties of artificial grain boundaries in epitaxial YBA2Cu3O7-δ thin films grown on [001] tilt YZrO2 bicrystals

The microstructure of artificial grain boundaries in YBa2Cu3O7-δ (YBCO) thin films grown on [001] tilt YZrO2 (YSZ) bicrystal substrates has been characterized using transmission electron microscopy and atomic force microscopy. Despite a relatively straight morphology of the substrate boundaries, the film boundaries were wavy. The waviness was a result of the combined effects of grooving at the substrate boundaries prior to the film deposition and an island-growth mechanism for YBCO on YSZ substrates. The dihedral angle of the groove walls varied with the misorientation angle and depended on the symmetry of the substrate boundary. The amplitudes of the film boundary waviness compared well with the widths of the grooves. In addition, the grooves induced local bending of the YBCO lattice planes and additional tilt components perpendicular to the c-axis close to the film boundaries. © 1995.

Formation of polyaniline/Pt nanoparticle composite films and their electrocatalytic properties

Polyaniline (PANI) thin films modified with platinum nanoparticles have been prepared by several methods, characterised and assessed in terms of electrocatalytic properties. These composite materials have been prepared by the in situ reduction of a platinum salt (K2PtCl4) by PANI, in a variety of solvents, resulting in the formation of platinum nanoparticles and clusters of different sizes. The further deposition of platinum clusters at spin cast thin films of PANI/Pt composites from a neutral aqueous solution of K2PtCl4 has also been demonstrated. Thin-film electrodes prepared from these materials have been investigated for their electrocatalytic activity by studying hydrazine oxidation and dichromate reduction. The properties of the composite materials have been determined using UV–visible spectroscopy, atomic force microscopy and transmission electron microscopy. The nature of the material formed is strongly dependent on the solvent used to dissolve PANI, the method of preparation of the PANI/Pt solution and the composition of the spin cast thin film before subsequent deposition of platinum from the aqueous solution of K2PtCl4.