Optimal catalyst thickness in titanium dioxide fixed film reactors: Mathematical modelling and experimental validation

The use of immobilised TiO2 for the purification of polluted water streams introduces the necessity to evaluate the effect of mechanisms such as the transport of pollutants from the bulk of the liquid to the catalyst surface and the transport phenomena inside the porous film. Experimental results of the effects of film thickness on the observed reaction rate for both liquid-side and support-side illumination are here compared with the predictions of a one-dimensional mathematical model of the porous photocatalytic slab. Good agreement was observed between the experimentally obtained photodegradation of phenol and its by-products, and the corresponding model predictions. The results have confirmed that an optimal catalyst thickness exists and, for the films employed here, is 5 μm. Furthermore, the modelling results have highlighted the fact that porosity, together with the intrinsic reaction kinetics are the parameters controlling the photocatalytic activity of the film. The former by influencing transport phenomena and light absorption characteristics, the latter by naturally dictating the rate of reaction.

The anodized crystalline WO3 nanoporous network with enhanced electrochromic properties

We demonstrate that a three dimensional (3D) crystalline tungsten trioxide (WO3) nanoporous network, directly grown on a transparent conductive oxide (TCO) substrate, is a suitable working electrode material for high performance electrochromic devices. This nanostructure, with achievable thicknesses of up to 2 μm, is prepared at room temperature by the electrochemical anodization of a RF-sputtered tungsten film deposited on a fluoride doped tin oxide (FTO) conductive glass, under low applied anodic voltages and mild chemical dissolution conditions. For the crystalline nanoporous network with thicknesses ranging from 0.6 to 1 μm, impressive coloration efficiencies of up to 141.5 cm2 C−1 are achieved by applying a low coloration voltage of −0.25 V. It is also observed that there is no significant degradation of the electrochromic properties of the porous film after 2000 continuous coloration–bleaching cycles. The remarkable electrochromic characteristics of this crystalline and nanoporous WO3 are mainly ascribed to the combination of a large surface area, facilitating increased intercalation of protons, as well as excellent continuous and directional paths for charge transfer and proton migration in the highly crystalline material.

Synthesis and applications of carbon nanomaterials for energy generation and storage

The world is facing an energy crisis due to exponential population growth and limited availability of fossil fuels. Over the last 20 years, carbon, one of the most abundant materials found on earth, and its allotrope forms such as fullerenes, carbon nanotubes and graphene have been proposed as sources of energy generation and storage because of their extraordinary properties and ease of production. Various approaches for the synthesis and incorporation of carbon nanomaterials in organic photovoltaics and supercapacitors have been reviewed and discussed in this work, highlighting their benefits as compared to other materials commonly used in these devices. The use of fullerenes, carbon nanotubes and graphene in organic photovoltaics and supercapacitors is described in detail, explaining how their remarkable properties can enhance the efficiency of solar cells and energy storage in supercapacitors. Fullerenes, carbon nanotubes and graphene have all been included in solar cells with interesting results, although a number of problems are still to be overcome in order to achieve high efficiency and stability. However, the flexibility and the low cost of these materials provide the opportunity for many applications such as wearable and disposable electronics or mobile charging. The application of carbon nanotubes and graphene to supercapacitors is also discussed and reviewed in this work. Carbon nanotubes, in combination with graphene, can create a more porous film with extraordinary capacitive performance, paving the way to many practical applications from mobile phones to electric cars. In conclusion, we show that carbon nanomaterials, developed by inexpensive synthesis and process methods such as printing and roll-to-roll techniques, are ideal for the development of flexible devices for energy generation and storage – the key to the portable electronics of the future.

Preparation and characterisation of tri-calcium phosphate scaffolds with tunnel-like macro-pores for bone tissue engineering

Calcium Phosphate ceramics have been widely used in tissue engineering due to their excellent biocompatibility and biodegradability. In the physiological environment, they are able to gradually degrade, absorbed and promote bone growth. Ultimately, they are capable of replacing damaged bone with new tissue. However, their low mechanical properties limit calcium phosphate ceramics in load-bearing applications. To obtain sufficient mechanical properties as well as high biocompatibility is one of the main focuses in biomaterials research. Therefore, the current project focuses on the preparation and characterization of porous tri-calcium phosphate (TCP) ceramic scaffolds. Hydroxapatite (HA) was used as the raw material, and normal calcium phosphate bioglass was added to adjust the ratio between calcium and phosphate. It was found that when 20% bioglass was added to HA and sintered at 1400oC for 3 hours, the TCP scaffold was obtained and this was confirmed by X-ray diffraction (XRD) analysis. Test results have shown that by applying this method, TCP scaffolds have significantly higher compressive strength (9.98MPa) than those made via TCP powder (<3MPa). Moreover, in order to further increase the compressive strength of TCP scaffolds, the samples were then coated with bioglass. For normal bioglass coated TCP scaffold, compressive strength was 16.69±0.5MPa; the compressive strength for single layer mesoporous bioglass coated scaffolds was 15.03±0.63MPa. In addition, this project has also concentrated on sizes and shapes effects; it was found that the cylinder scaffolds have more mechanical property than the club ones. In addition, this project performed cell culture within scaffold to assess biocompatibility. The cells were well distributed in the scaffold, and the cytotoxicity test was performed by 3-(4,5)-dimethylthiahiazo(-z-y1)-3,5-di- phenytetrazoliumromide (MTT) assay. The Alkaline Phosphatase (Alp) activity of human bone marrow mesenchymal stem cell system (hBMSCs) seeded on scaffold expressed higher in vitro than that in the positive control groups in osteogenic medium, which indicated that the scaffolds were both osteoconductive and osteoinductive, showing potential value in bone tissue engineering.

In situ SANS study of the surface and pore filling adsorption of subcritical and supercritical CO2 in porous silica as a function of pore size

We applied small-angle neutron scattering (SANS) and ultra small-angle neutron scattering (USANS) to monitor evolution of the CO2 adsorption in porous silica as a function of CO2 pressure and temperature in pores of different sizes. The range of pressures (0 < P < 345 bar) and temperatures (T=18 OC, 35 OC and 60 OC) corresponded to subcritical, near critical and supercritical conditions of bulk fluid. We observed that the adsorption behavior of CO2 is fundamentally different in large and small pores with the sizes D > 100 Å and D < 30 Å, respectively. Scattering data from large pores indicate formation of a dense adsorbed film of CO2 on pore walls with the liquid-like density (ρCO2)ads≈0.8 g/cm3. The adsorbed film coexists with unadsorbed fluid in the inner pore volume. The density of unadsorbed fluid in large pores is temperature and pressure dependent: it is initially lower than (ρCO2)ads and gradually approaches it with pressure. In small pores compressed CO2 gas completely fills the pore volume. At the lowest pressures of the order of 10 bar and T=18 OC, the fluid density in smallest pores available in the matrix with D ~ 10 Å exceeds bulk fluid density by a factor of ~ 8. As pressure increases, progressively larger pores become filled with the condensed CO2. Fluid densification is only observed in pores with sizes less than ~ 25 – 30 Å. As the density of the invading fluid reaches (ρCO2)bulk~ 0.8 g/cm3, pores of all sizes become uniformly filled with CO2 and the confinement effects disappear. At higher densities the fluid in small pores appears to follow the equation of state of bulk CO2 although there is an indication that the fluid density in the inner volume of large pores may exceed the density of the adsorbed layer. The equivalent internal pressure (Pint) in the smallest pores exceeds the external pressure (Pext) by a factor of ~ 5 for both sub- and supercritical CO2. Pint gradually approaches Pext as D → 25 – 30 Å and is independent of temperature in the studied range of 18 OC ≤ T ≤ 60 OC. The obtained results demonstrate certain similarity as well as differences between adsorption of subcritical and supercritical CO2 in disordered porous silica. High pressure small angle scattering experiments open new opportunities for in situ studies of the fluid adsorption in porous media of interest to CO2 sequestration, energy storage, and heterogeneous catalysis.

Matrix metalloproteinase biosensor based on a porous silicon reflector

Matrix metalloproteinases (MMPs) are proteolytic enzymes important to wound healing. In non-healing wounds, it has been suggested that MMP levels become dysfunctional, hence it is of great interest to develop sensors to detect MMP biomarkers. This study presents the development of a label-free optical MMP biosensor based on a functionalised porous silicon (pSi) thin film. The biosensor is fabricated by immobilising a peptidomimetic MMP inhibitor in the porous layer using hydrosilylation followed by amide coupling. The binding of MMP to the immobilised inhibitor translates into a change of effective optical thickness (EOT) over the time. We investigate the effect of surface functionalisation on the stability of pSi surface and evaluate the sensing performance. We successfully demonstrate MMP detection in buffer solution and human wound fluid at physiologically relevant concentrations. This biosensor may find application as a point-of-care device that is prognostic of the healing trajectory of chronic wounds.

Toughness and toughening mechanisms of porous thin films

Toughness is the ability of a material to deform plastically and to absorb energy before fracture. The first of its kind, this book covers the most recent developments in the toughening of hard coatings and the methodologies for measuring the toughness of thin films and coatings. The book looks at the present status of toughness for coatings and discusses high-temperature nanocomposite coatings, porous thin films, laser treated surface layers, cracking resistance, indentation techniques, sliding contact fracture, IPN hybrid composites for protection, and adhesion strength.

Effects of metal ion concentration on electrodeposited CuZnSn film and its application in kesterite Cu2ZnSnS4solar cells

In this study, effects of concentrations of Cu(II), Zn(II) and Sn(II) ions in the electrolytic bath solution on the properties of electrochemically deposited CuZnSn (CZT) films were investigated. Study of the composition of a CZT film has shown that the metallic content (relative atomic ratio) in the film increased linearly with increase in the metal ion concentration. It is the first time that the relationship of the compositions of the alloy phases in the co-electrodeposited CZT film with the concentration of metal ions has been revealed. The results have confirmed that the formation and content of Cu6Sn5 and Cu5Zn8 alloy phases in the film were directly controlled by the concentration of Cu(II). SEM measurements have shown that Sn(II) has significant impact on film morphology, which became more porous as a result of the larger nucleation size of tin. The changes in the surface properties of the films was also confirmed by chronoamperometry characteristic (i–t) deposition curves. By optimization of metal ion concentrations in the electrolyte solution, a copper-poor and zinc-rich kesterite Cu2ZnSnS4 (CZTS) film was synthesized by the sulfurization of the deposited CZT film. The solar cell with the CZTS film showed an energy conversion efficiency of 2.15% under the illumination intensity of 100 mW cm 2.

Micropolar flow in a porous channel with high mass transfer

Two dimensional flow of a micropolar fluid in a porous channel is investigated. The flow is driven by suction or injection at the channel walls, and the micropolar model due to Eringen is used to describe the working fluid. An extension of Berman's similarity transform is used to reduce the governing equations to a set of non-linear coupled ordinary differential equations. The latter are solved for large mass transfer via a perturbation analysis where the inverse of the cross-flow Reynolds number is used as the perturbing parameter. Complementary numerical solutions for strong injection are also obtained using a quasilinearisation scheme, and good agreement is observed between the solutions obtained from the perturbation analysis and the computations.

Investigation of RuO2/Ta2O5 thin film evolution by thermogravimetry combined with mass spectrometry

The thermal evolution process of RuO2–Ta2O5/Ti coatings with varying noble metal content has been investigated under in situ conditions by thermogravimetry combined with mass spectrometry. The gel-like films prepared from alcoholic solutions of the precursor salts (RuCl3·3H2O, TaCl5) onto titanium metal support were heated in an atmosphere containing 20% O2 and 80% Ar up to 600 °C. The evolution of the mixed oxide coatings was followed by the mass spectrometric ion intensity curves. The cracking of retained solvent and the combustion of organic surface species formed were also followed by the mass spectrometric curves. The formation of carbonyl- and carboxylate-type surface species connected to the noble metal was identified by Fourier transform infrared emission spectroscopy. These secondary processes–catalyzed by the noble metal–may play an important role in the development of surface morphology and electrochemical properties. The evolution of the two oxide phases does not take place independently, and the effect of the noble metal as a combustion catalyst was proved.